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December 2009

Journal of

Petrotech Society Special Coverage on Nanotechnology

Petrotech Wishes its Patrons A Happy New Year 2010

Journal of the Petrotech Society

Volume V Issue. 5

December 2009

Editorial Dear Reader, New Year greetings from PETROTECH SOCIETY! Another issue of our house magazine is in your hands. We sincerely hope that the prime objective of Knowledge dissemination is getting served by such Publication. The magazine carries important articles from lead industry experts both in upstream and downstream sectors. The contents are also exhibited on our website www. and have been emailed to our patrons for their appreciation. The hard copy is meant for our academic associates and also student population.

Year 2009 has been an eventful year for Petrotech Society. Some of the main Highlight of our activities are detailed below.


Industry Educational Tour: Under an MoU with University of Alberta, Canada, a group of 18 Industry executives visited the university of Alberta, at Edmonton, Canada and other neighbouring industries to know about the latest advancements made by Canadian Hydrocarbon Industry specially in the field of Research facilities and related sophisticated equipment. This was a good learning experience for all participants. Efforts will continue to bring Petrotech Society in the international arena by building up relationships with many such international bodies in the coming year.

Student Chapters: As part of our two pronged strategy, many industry experts have visited various institutes/universities to deliver hands-on type talks to final year students. This has been well received by the institutes and student community. Experts from Industry visited these chapters to deliver lectures on practical aspects of industry. This has helped in promoting the exchange of information/study material as required by chapter members from time to time.

Two more chapters have been added this year, taking this total to six chapters. These are: •

Indian School of Mines, Dhanbad

Osmania University

Maharashtra Institute of Technology, Pune

University of Petroleum & Energy Studies, Dehradun

Rajiv Gandhi Institute of Technology, Rae Bareilly

Institute of Petroleum Technology, Gandhi Nagar

New Membership: Schlumberger Asia Services Ltd has joined the Society as New Corporate Member raising the total strength to 31. Efforts are on to enroll more members.

Annual Schools/Regional Seminars: Regular Annual Schools both in upstream and downstream areas as formalized and incorporated in the Society Calendar were held during the year in collaboration with ONGC and IOCL. Besides, annual R&D conclaves have been started to share knowledge and give impetus to R&D advancement. Like last year, a seminar on “Hydrocarbon Industry Growth- prospects & Challenges in North East” was organized at Numaligarh Refinery for participants from North East. Similar seminar for academia & Industry was Organised in Collaboration with CPCL at Chennai wherein 66 Participants from Industry & Academia participated. Parallely, a round table on Academia & industry was also organised which was attended by senior Professors, heads of departments from Technical Institutes from south India and Director, IIT Chennai.

New Associations: Petrotech Society Associated with India Energy Forum and ORF for organizing 8th Petro India during November 2009. The society also associated with Security Watch India, for exposing Industry executives to latest security challenges in Petroleum installations and transportation of Petroleum products.

Veterans Forum: In line with the decision of the Governing Council of Petrotech Society, the first meeting of the PETROTECH Veterans’ Forum was held on 20th November 2009 at Hotel Le-Meridien, New Delhi. A presentation was made by representatives of well known knowledge partner M/s PFC Energy on the theme “Energy Security: Where do we go from here?” The meeting was attended by 15 members of the forum. All members appreciated the launch of this forum.

PETROTECH 2010: Preparations are in full swing for the next international conference and exhibition PETROTECH 2010. The first Core Committee was held on 9th July 2009 where the theme of the conference “Global Energy Equilibrium” was finalized. Secretary MOPNG presided over the meeting Deliberations on various issues as also on the theme of the conference were held. It was also decided to prepone the event to 31st October to 3rd November 2010 as January month was felt to be prone to weather problems. As you are aware PETROTECH 2009, The 8th International Oil & Gas Conference and Exhibition was a grand success for which Team IOCL deserves all appreciation. The Society has thus embarked on a long journey of continued excellence which needs your patronage at all times. Year 2010 is expected to be equally busy year with continued focus on knowledge dissemination through Seminars and schools for the benefit of industry patrons, Efforts would continue to improve our international stature enabling the Society to get a bigger canvass to perform its dutiful role as enshrined in its articles of association.

Wishing you a very happy and Prosperous year 2010!

J L Raina Secretary General & CEO Petrotech





Upstream Oil and Gas: New Realities, New Challenges


R.S. Sharma

Case Histories: Improved Horizontal Well Cleanup and Sweep Efficiency with Nozzle-Based Inflow Control Devices in Sandstone and Carbonate Reservoirs


A.H. Sunbul, J.E. Lauritzen, D.E. Hembling, A. Majdpour, Saudi Aramco; A.G. Raffn, M. Zeybek, T. Moen, Schlumberger

Downstream Paving Grade Bitumen In India: New Opportunities


Sonal Maheshwari, Biswanath Saha, P. Senthivel and N. V. Choudary

Nanotechnology Nanotechnology: Application Potentials in Petroleum Industry


Dr. S K Hait, Dr. D K Tuli and Mr. Anand Kumar

Nanotechnology: Energy and Environment


Madhur Sharma, Sangeeta Nagar, Avni Jain, Sachit Goyal, Bhushan Shinde, Maneesha Pande and Ashok N. Bhaskarwar

Human Resources Editorial Board

Excellence: Creating organizational collectively


Ashis Sen J L Raina Editor

Secretary General & CEO, PETROTECH Society

Gas Isotopic Composition Of coalbed methane desorbed from barakar coals of damodar valley gondwana coalfields and its implication


Malay Rudra and P N Hajra G Sarpal Secretary

Geologic & Engineering Controls: The Energy Resource Potential of Gas Hydrates


T. S. Collett Suman Gupta Manager

The views expressed by the authors are their own, and do not neccessarily represent that of the Petrotech Society.

Printed and published by Petrotech Society at Core 8, Scope Complex, 3rd Floor, New Delhi - 110 003 India

Corporate News International Oil Scenario - Extracts MoU between Indian Oil and Deakin University on “Collaborative Research� Seminars and Annual Schools Regional Meets Industry Academia Industry Awareness International Footings Events PETROTECH 2010

33 47 60 61 61 62 63 63 63 64

Dear Colleagues, At the outset, let me wish you a very happy and professionally fulfilling New Year. We have just bid adieu to 2009. It was a significant year for PETROTECH Society. We successfully held the 8th edition of our biennial International Oil & Gas Conference ‘PETROTECH-2009’. We celebrated a decade of excellence of the Society and felicitated its founding members. A new platform, ‘PETROTECH Veterans Forum’, has been launched to harmess the collective knowledge and experience of pertoleum sector veterans. An e-Newsletter, ‘Petrascope’, has been launched to bring speed in information sharing and to save trees. In addition, various important seminars and workshops have been held under the banner of Industry-Academia Interface and Industry Awareness programmes to garner and disseminate the knowledge of this prolific hydrocarbon industry. To overcome the disadvantages of weather contraints of January month, we have preponed the schedule of the next edition of biennial International Oil & Gas Conference. This conference is now slated to be held during 31st October – 3rd November, 2010. The theme for Petrotech – 2010 is ‘Global Energy Equilibrium’. this deceptively simple theme encapsulates myriad dimensions and perspectives. It will be a most enlightening experience to witness learned hydrocarbon experts and global pundits of the associated geo-political spectrum respond to this theme. For the first time, PETROTECH has been tying up with the WPC Youth Forum. As a part of this branding, young participants from select institutes will be eligible for special discounts and privileges. ONGC has been entrusted to organize ‘PETROTECH-2010’. I am happy to share that considerable progress has been made in all the fronts. We are alreaddy privileged to have the confirmation of the Hon’ble Prime Minister to inaugurate the event. We are very much excited to make this event a grand success. PETROTECH Journal has already carved its special place among the intelligantsia of Indian Petroleum Industry. Through this issue of the Journal, I would like to solicit their active participation in Petrotech-2010; by taking part in various intellectual discourses, displaying latest technical acumen and presenting brilliant scientific and technical acumen and presenting brilliant scientific and technical papers alongside the best international exhibitors and intellectuals of the industry. I am sure all bright geoscientists and engineers from Indian Petroleum Industry would like to avail the opportunity at Petrotech-2010 to showcase their cutting-edge research, technology advancements and experiential learning in adapting new technology. Petrotech Journal will document some of these brilliant ideations in the coming days. Happy reading...

R S Sharma Chairman, Petrotech Society

Foreword Dear Colleagues, It’s a matter of immense pleasure to bring December ‘09 issue of PETROTECH Journal. The first meeting of Veterans Forum was held on 20th November ‘09 and the Petrotech Chairman needs to be complimented for his commendable efforts in conceptualizing the Forum and finally making it a reality. We are sure that the vast experience which this Forum shares will benefit the Indian Oil and Gas Industry and its future. Also Petrotech society in its endeavor to continuously improve its knowledge sharing process started “Petroscope”, the monthly E news letter. “In a time of turbulence and change, it is more true than ever that knowledge is power.” The above mentioned line once said by John F Kennedy, very well captures the dynamism of the Oil & Gas industry. In such turbulent times, Companies who are better informed are better equipped and have readiness to weather adverse situations. Petrotech Journal with its wide range of diverse articles brings you the latest in technological developments and experiences. We are thankful to our industry colleagues for their contribution and for being part of our knowledge sharing effort to enhance Industry standards and practices. We look forward to your continued support. Business Community witnessed an unprecedented volatility last year in a very short spam of time. Learning from last year’s experience we are set to grow further in this New Year. Let me take this opportunity to wish everyone a Very Happy and Prosperous New Year. May this year bring in new aspirations, new hopes and many more opportunities of working with each other for the prosperity & development. Hope readers will find the current issue informative and worth keeping… Happy reading!!!

Naresh Kumar Managing Director, Jindal Drilling & Industries Limited


Oil and Gas New Realities, New Challenges R.S. Sharma Chairman & Managing Director, Oil and Natural Gas Corporation Ltd.

R S Sharma

Mr R S Sharma is the Chairman and Managing Director of India’s flagship Navratna Public Sector Undertaking, Oil and Natural Gas Corporation. He is a Fellow Member of the Institute of Cost and Works Accountants of India and an Associate Member of the Indian Institute of Bankers. Mr Sharma is also the Chairman of Mangalore Refieries and Petrochemicals Limited, ONGC Videsh Limited, and other group companies of ONGC.

Introduction Since the dawn of civilization energy has been the prime mover of growth and prosperity. After the usage of wood and animal dung cakes for centuries, we discovered coal during the Bronze Age. Large scale coal mining developed during the Industrial Revolution made coal the prime source of energy. Invention of steam engine, locomotives, etc., brought the desired speed in the wheel of civilization. But they were neither enough to satiate our thirst for growth, nor efficient enough to propel the growth of modern civilization at a rate we desired to. It was the month of August, 1859, just 150 years ago, the driller ‘Uncle Billy’ Smith struck oil in Titusville, USA. And with that discovery, the whole concept of energy use for civilization and modernization changed dramatically for ever. In the twentieth century, the most convenient fuel, ‘oil’, along with natural gas replaced coal as the most preferred fuel. Today, in the first decade of twenty-first century, oil and gas touch every facet of our life. Dependence on oil and gas is so intense that even thought of any supply disruption sends shock wave the world over. We are worriedly dependent on oil and gas. Daniel Yergin in the prologue of his epic ‘The Prize’ writes, “The role of oil- and anxiety about its supply- is a primary consideration of the Internet and the era of globalization that characterizes the first decade of the twenty-first century. In particular, three great themes underlie the story of oil.” The three themes that Daniel lists are: i) the rise and development of capitalism and modern business with oil. (“Oil is the world’s biggest and most pervasive business, the greatest of the great industries that arose in the last decades of nineteenth century,” he writes); ii) oil as a commodity intimately intertwined with national strategies and global politics and power and iii) how ours has become a “Hydrocarbon Society” and we, in the language of anthropologists, “Hydrocarbon Man”. Taking cue from these themes and considering the unprecedented rate of


Petrotech Journal December Issue 2009

growth of human aspiration for prosperity, it could easily be said that, in terms of energy scenario of the world in twenty-first century, the greatest reality is that the demand for oil and gas is going to exist and the greatest challenge is to ensure sustainable supply of oil and gas in years to come.

Changing energy landscape Since the dawn of the oil-age about 150 million years ago, the world is estimated to have consumed more than 1,300 billion barrels of oil, out of which 293 billion barrels i.e. about 21% of the total consumption so far, has been consumed in the last decade alone (from 1999 to 2008). It would not be inappropriate to index the development and prosperity with the energy consumption. The biggest energy consuming centers of today are the most prosperous regions in the world. Similarly, the development profile and carbon footprint in the developing nations could be mapped based on energy consumption trends. For example, the Asia Pacific region accounted for just 15% of the total primary energy consumption in the world in 1970. Whereas in 2003, the same region is found to be the largest energy consuming centre accounting for about 34% of the total consumption in the world. In less than four decades, the global energy landscape has dramatically

changed. And this single change has caused wide ramifications on the entire business environment. India, with 16% of the world population and just having 0.5% of known crude oil and 0.6% of natural gas reserves, is quite unfavorably placed as far as hydrocarbon resources are concerned. Meeting growing energy demand of fast developing India remains a challenge and will remain so in the near future also. Self sufficiency in crude oil has always been a dream and desire of every nation as it proved itself as the foundations of prosperity. As far as achieving self sufficiency in energy supply for India is concerned, it has two dimensions. First, finding and producing new reserves of hydrocarbons (oil and gas), as well as maintaining production levels from the existing fields; second, developing non conventional and alternate sources of energy in sustainable and cost effective manner for reducing demand pressure on oil. During the last decade (1998-2008), India’s primary energy consumption has increased from 291 MTOE (Million Tonne Oil Equivalent) to 433.3 MTOE (48.9% rise), whereas the consumption of oil and gas has increased from 114.5 MTOE to 172.2 MTOE (up by 50.4%). The share of oil and gas in the total energy basket is inching upwards despite less domestic supply. This has substantially increased our dependence on oil & gas import.

During the same period (1998-2008), while the import of total primary commercial energy has increased by 69%, the import of oil & gas combine has gone up by 88%. However, the country has also realised record growth rate during this period. Its GDP (PPP) has increased from estimated $ 1.3 trillion in 1998 to $ 3.3 trillion in 2008 (up by 53.6%).

Oil & Gas supply: Realities & Challenges The apprehension about sustainable supply of oil in long-term has prevailed in the market since the day oil became a commodity. The speculators have always played conveniently with this apprehension. Projected supply constraints and speculators grip on commodity exchanges witnessed unprecedented rally in oil prices; peaking to $147 per barrel in mid-2008. Then there was a debacle. We witnessed one of the worst recessions in global economy. Rightly, speculation and high oil prices is cited one of the reasons for meltdown. Oil witnessed demand destruction. However, it is strongly felt that that this demand destruction is just temporary and demand for oil and gas is bound to bounce back the moment global economy gains confidence. The moment green shoots in global economy became visible, oil

prices started showing upward curve; from $35 per barrel to now in the range of $75-80 per barrel which seems to be in the Goldilocks’-range. However, fundamentally oil prices may see similar volatility which we witnessed until the first half of 2008. Temporary shock in oil prices had devastating impact on many prior committed investments for sustaining future supplies. This has caused a long term blow for the supply side of the market. Investment crunch coupled with technical facts that the size and number of new discoveries are constantly shrinking, the major producing fields have aged and the technology required for exploring and exploiting new sources and frontiers are inadequate are compounding the apprehension of sustained supply in future. No doubt oil industry is in the era of constantly changing realities. Against this dynamics taking a firm step towards future solutions is the biggest challenge. Fact remains, it is rather impossible to tame volatility of the oil industry which has become the epitome of the global economy. Its benchmarks and curves have direct consequential implications for the mankind in any part of the globe. In tight energy demand scenario there is no other option than to look for all options which are feasible and sustainable. Bio-fuel as an option and economic substitute for oil may not be the single reason for imbalanced agriculture pattern globally. There are other reasons but the fact remains that large scale production of maize, at the cost of other crops, or large scale use of sugar cane for producing bio-fuels is leading to crippling shortage of critical food crops with direct impact on its prices. The new buzz words ‘agflation’, ‘foodflation’, etc., and their indices are interpreted as end of the world of cheap food; like end of the easy oil. “The Economist” quoted Josette Sheeran of the World Food Program, a United Nations agency, calling it as a “silent tsunami” which is really disturbing; and at the epicenter of this disturbance is oil – just unimaginable. The same oil which shaped this urban-centric civili-

zation, invading every facets of human life; redefining convenience and ushering prosperity. The drawn correlation of oil prices with food prices and resultant imbalances is a serious concern and this demands oil industry to look for corrective measures beyond such distortions. The apprehension of supply constraints coupled with price volatility are not the obvious statement of pessimism. It is all about acknowledging the harsh realities of the present day’s oil business. “Global Witness”, in its October 2009 report “Heads in the sand” questioning IEA’s overconfidence, outlines – “the world is facing a twin emergency brought out by the confluence of climate and energy crises”. It lists – oil field depletion, declining discovery rates, insufficient new projects and increasing demand as the fundamental underlying problems for securing sufficient oil supply. However, on the other hand, on a positive note, CERA in its Nov’2009 report states that – hydrocarbon liquids are a finite resource; but based on recent trends in exploration and appraisal activity there should be more than an adequate inventory of physical resources available to increase supply to meet anticipated levels of demand in the time frame up to 2030. Such contradictory schools of thoughts are not new for this industry. Its technical complexities and resultant uncertainties, political stake and chain-effect on all other industries in any economy have always caused such argumentative opinions. Deloitte Centre for Energy Solutions in its report ‘Oil & Gas reality Check: Petrotech Journal December Issue 2009


objective – green energy solutions at affordable price for sustenance of future human civilization.


Ten of the top issues facing companies in the coming year’ has comprehensively summarized the challenges of present oil & gas industry. The report has flagged ten issues as follows: i) The cash crunch; economic uncertainty may supply shortage, ii) Counting the costs; elevated expenses squeeze margins, iii)Regulatory complexity; global operations demand robust processes, iv) Missing in action; talent shortages loom, v) Boosting reserves at bargain prices; the pace of mergers and acquisitions accelerates, vi) Nowhere to go; market access limited by resource nationalism, vii) The end of easy oil; reserves are getting harder to reach and extract, viii) Playing it safe; Health and safety remain critical concerns, ix) An inconvenient truth; Carbon reduction targets rise in prominence and x) It’s not easy being green; an alternative strategy is mandatory. All these issues are not new; Journal of Petroleum Technology (JPT) had also flagged similar ten issues in its July 2008 issue. The issue is that the industry has never come together to accept the fact that the epicenter of these challenges is just one – growing demand for energy and looming shortages, if corrective measures are not put in place. The industry has also to propose the way forward for the demand side management including improvement in efficiency in all its usages. It is also imperative for the industry to provide green solutions for favourable environmental footprints. This is not conflicting but complementing engagement as far as sustainable development is concerned.


Petrotech Journal December Issue 2009

The way forward Inclusive growth of civilization will challenge the oil industry to ensure this sustainable supply. Beyond this, on supply side, there is a need for establishing linear correlation between demand and capacity buildup. This correlation has third and a very important dimension i.e., investment which more or less boils down to the localized business interest of the countries or corporates. The boundary conditions of these localized interests need to be redefined. This may require extraordinary level of cooperation among the producers and consumers. There is also an urgent need to rationalize cost of oil field services which emerged as a biggest challenge for the oil industry in the boom days.

The oil and gas industry has always offered unique challenges, both for the suppliers as well as consumers. Because of high stake, its business environment has often been murky with greed and avarice. At the same time, the passion for innovation and entrepreneurship has always discovered new heights of achievement. Whatever it may be, there is no doubt that the human civilization has immensely been benefitted by this industry. At the advent of a new decade in twentyfirst century, the realities and challenges of oil industries have definitely changed. Demand pressure or supply constraints or related volatility are showing complex side-effects which has wide ramifications to the global economy. The industry will have to redefine its boundary conditions to address new realities and the new challenges. Green energy solutions at affordable cost will challenge the industry to extend its capabilities through innovative technology solutions and collective response. We will have to recognize ‘Energy’ as a collective issue.

The industry, in one hand, needs to dilute complexities in the market, limit volatility. Going beyond the geo-political factors, adopting greater transparency of market information and data would be a pragmatic step to establish linear correlations. On the other hand, technologically the industry needs to be more accurate, cost effective and precise. Failure rates have to be minimized. Developing new technologies for tomorrow becomes imperative.

It is hoped that all the realities and the challenges of this industry will be addressed by the new generation with new ideas, new technologies and new sociopolitical perspectives for even greater prosperity and a brighter tomorrow.

Neutralizing these shortages would require support from resource holders and host countries through enabling tax regimes. In this regard, NOCs, who directly control over 80 percent of world’s reserves, will have to play a vital role in future capacity build up.

To this effect, companies in energy business or related to it will have to establish meaningful synergy with one


• • •

• • •

The Prize; Daniel Yergin BP Statistical Review 2009 Heads in the sand; Global Witness, October 2009 The future of global oil supply; IHS CERA, November 2009 Oil & Gas reality check; Deloitte, 2009 Wikipedia Index mundi


Case Histories Improved Horizontal Well Cleanup and Sweep Efficiency with Nozzle-Based Inflow Control Devices in Sandstone and Carbonate Reservoirs A.H. Sunbul, J.E. Lauritzen, D.E. Hembling, A. Majdpour, Saudi Aramco; A.G. Raffn, M. Zeybek, T. Moen, Schlumberger

Abstract This paper discusses the PLT-correlated results of two test wells completed during 2006; one in sandstone and one in a carbonate reservoir, with the new completion technology of nozzlebased passive inflow control devices (ICD) which improves performance of wells with reservoir challenges as described: 1. In highly productive sandstone reservoirs, horizontal wells suffer from uneven flow profile and subsequent premature cresting/coning effects. In general, there is a tendency to produce more at the heel than at the toe of horizontal wells, which contributes to poor well cleanup at the toe. Additionally, excessively increasing the rate and/or horizontal well length can increase the risk of limiting sweep efficiency, resulting in bypassed reserves1. 2. In carbonate reservoirs, permeability variations and fractures can cause uneven inflow profile and accelerate water and gas breakthroughs. Wells

with early gas or water breakthrough have to be shut-in until remedial plans are decided and implemented, resulting in deferred production. The main reservoir objectives for applying passive ICD technology in the two test wells are: a. Sandstone: Decrease the influence of heel-toe effects and high permeability zones; hereby deferring water/ gas breakthrough, improving well cleanup and sweep efficiency.

b. Carbonate: Control flow rates from high permeability intervals and to limit production from each compartment based on lateral offset from the gas-oil contact to prevent premature gas breakthrough. The test well PLT-logs were correlated to static reservoir simulations. Analyses of the well performances show that the objectives of both completions were achieved. By having proper matches of the completions with ICD,

Fig. 1: a) ICD unit integrated in a sand control screen. Screen ensures a solids-managed flow (allow particles < 45 μm to be produced), length 12m=one joint. b) An ICD completion example with packers for every ICD joint in a naturally fractured reservoir.

the value over standard completions can be evaluated. Post-evaluation of the completion designs based on the PLT-log results has increased our understanding of the nozzle-based ICD performance. As a result several approaches for completing well in both sandstone and carbonate reservoirs with ICD have been recommended in order to achieve optimized inflow performance.

Introduction Two trial wells with nozzle-based passive ICD systems were designed and completed in 2006; one for sandstone and one for carbonate reservoirs. To evaluate and approve the new ICD completion, these wells were production logged and the results were carefully analyzed. The most important feature of the ICD completion is the self-adjusting effect of flow variations anywhere along the well trajectory and whenever they occur during entire well life. The key benefits are:

with these nozzles is that at least one or more of the nozzles will be exposed to inflow of fluid, making the system reliable for cleaning up the well even if the well has been left with solids-laden fluids down hole for a longer period before the well is put on production. Figure 1b shows a schematic of a well with packers to divide the lateral into compartments of permeability variations. The benefits of having packers supporting the ICD completion are: a) Permeability variations are captured and segmented. b) High productivity (high permeability) intervals are controlled by lower number of ICD units run in those segments, preventing cresting/coning in those segments. c) Inflow of gas or water through fractured zones can be isolated or highly restricted. d) Annular flow between compartments is prevented.

e) Potential wet zones can be isolated while the rest of the well can produce dry oil. When a barefoot or a conventional horizontal well is put on production, the filter cake is preferentially lifted at the heel of the well as a function of the heel to toe pressure gradient (Figure 2a and b). This leads to poor inflow performance due to higher completion skins at the toe. Usually as the horizontal well length increases, the inflow profile and corresponding recovery degrades because of insufficient well cleanup and lesser contribution from the toe. For a horizontal well with ICD completion, flow rate per compartment is restricted (Figure 2c). At higher rates, a higher differential pressure is created and transmitted along the completion to other compartments and eventually to the toe. This differential pressure created lifts the filter cake off the formation face and additionally cleans the near wellbore damage, resulting in:

Fig. 2: Principle of improved wellbore cleanup

1) Increased well life and reserves due to improved sweep efficiency. 2) Delayed gas and water breakthrough. 3) Decreased water/gas rates after breakthrough when water/gas mobility is higher than oil. 4) Improved well cleanup. The pressure drop through the ICD unit is generated by the flowing fluid through the nozzles (Figure 1a), described by a part of the Bernoulli equation: (Eq. 1) Where: ∆pN= pressure across ICD nozzles, Cu= units conversion constant, ρ= density of fluid, v= velocity, Cv= dimensionless flow coefficient for the nozzle, q= rate and A= total cross section area of the nozzles. The ICD unit is equipped with at least 2 or more nozzles and the pressure drop across the unit is designed based on the reservoir characteristics and flow rates in order to achieve the objectives of the well. An advantage


Petrotech Journal December Issue 2009

Fig. 3: Principle of a standard screen completion compared to an ICD. a) Flux into wellbore, screen completion (Blue line) and ICD completion (Pink line). b) Comparison of the pressures along the well bore.

a) Skin reduction b) Higher well PI c) Enhanced sweep efficiency Once ICD units are introduced into the completion, an additional pressure drop is created in the system. It is therefore very important to design the ICD unit pressure drop in accordance with the reservoir properties to achieve a design with the lowest possible ICD pressure drop and still achieve the objectives.

The high permeability zone of 2 Darcy is having less draw-down (∆pF2) while the low permeability zone of 1 Darcy is having a higher draw-down (∆pF1), and the relationship is as follows:

To compare the PLT results with the PI potential for the well, it is assumed that an ideal horizontal well is performing according to2:


(Eq. 3)

Where: ∆pFi is the pressure from the reservoir into the annulus and ∆pNi is the pressure from the annulus to the tubing = pressure across the ICD unit.

t should be noted that an estimate of the Pwf from this equation is not including friction loss along the horizontal well length. The Pwf may therefore be slightly more optimistic than the actual PLT measurement. The evaluation of the well PI for both PLT and theoretical has been completed for the two trial wells in order to measure and understand their performance.

Figure 3 shows the principle of a standard screen completion compared to an ICD completion in a reservoir with 1 Darcy and 2 Darcy zones simulated in a static reservoir model. The two zones are supposed to be completed with a packer separating the annular flow between the zones. For a conventional completion the draw-down into the completion is shown as the ∆PF.

Simulating the two different completion types at the same rates, the flow rates for the zones are re¬distributed (Figure 3a) and as a consequence the ICD completion will be able to defer gas or water breakthrough in high permeability layers. In addition, over time this will assure a much better sweep efficiency of the reservoir, because it is less likely that oil will be left behind in low permeability intervals.

With an ICD completion the total draw-down into the completion is described as the ∆PICD, and we observe that the draw-down pressure ∆PF of the original horizontal well is now being re-distributed between the two zones when completed with an ICD completion.

Using the principle of Figure 3, the well PI for an ICD completion at the sandface (annulus) can be estimated, because when the flow rate per segment is known from the PLT-logging, we can calculate the pressure drop across the nozzle-based ICD units per segment from Eq. 1.

Fig. 4: Sandstone ICD completion with packers for every second joint

Fig. 5: Raw PLT-log data of rate vs. length of the well. Green: lower rate and Brown: higher rate. Dashed lines indicate initial PLT runs, and the solid lines indicate repeated PLT runs.

Sandstone Reservoir Trial Well The sandstone ICD well was completed in November 2006 (Figure 4). The objectives of the ICD completion were to reduce the heel-toe effect, deferring gas and water breakthrough. It was decided to test having a large number of packers to achieve better inflow control. The well has a total of 30 packers, i.e., approximately one packer for every second joint. This can be achieved very reliably and cost-effectively with small swellable elastomer packers. The well was put on production for approximately four months at about 6-7 MSTB/D before the PLT-logging. During logging shown in Figure 5, it became obvious that the well most likely had not been properly cleaned up, and the logging tool had problems reaching TD. At the low rate, the well stopped short of TD by 650 ft due to solids-laden mud in the toe of the well (Figure 5, Green dashed line). This was not expected because the well had produced over a relatively long time period to ensure proper cleanup prior to the PLT. After increasing the rate to about 9-10 MSTB/D for just four hours, repeating the logging at this higher rate, the well could be logged to an additional 350 feet of measured depth. Now the well showed improved flux to a nearly perfect inflow profile across the entire production interval (Figure 5, Brown dashed line). This quantitatively demonstrates that the higher rate resulted in a significant Petrotech Journal December Issue 2009


Table 1: PLT results compared to theoretical calculated Well Pl and static reservoir model Pl with skin 0 Rate during PLT From PLT Pwf Pl PLT Pl Sandface From Theory Pwf Pl Sandface

Low Choke 6450 6800

High Choke 10150 10500


2853 717 1032

2853 756 1144

2846 634 1104

2846 656 1205

Psi STB/D/psi STB/D/psi

2854.3 1307

2853.7 1307

2847.4 1307

2846.7 1307

psi STB/D/psi

Fig. 6: Inflow per segment and cumulative rate: a) Comparison of the PLT results with static model skin 0. b) Match of PLT results with static model adjusted skin and permeability.

rate the static model is under predicting with about 100-200 STB/D/psi, which we will look further into in details below. Calculating the inflow per segment (Figure 6a) reveals that segments 18 to 25 (Red circle) have less inflow than expected and segments 5 to 7 (Blue circle) have slightly higher, when comparing the actual PLT results with a static reservoir model with 0 skin along the entire wellbore. A better match was achieved as seen in Figure 6b (yellow and brown bars and lines) with a skin of -5 in segment 5 to 7 and a very high skin (between 20 to 60) in segment 18 to 25. It should however be noted that the well was in a late transient phase during the PLT-logging, due to changing rates, so there is some uncertainty connected to the results, but this evaluation gives an idea of the functionality of the ICD completion.

cleanup effect. After four hours, the well was re-logged at the high rate traversing all but the last 50 ft of production interval (Figure 5, Brown solid line). For cleanup verification the log was finally repeated at the lower rate (Figure 5, Green solid line) and a permanent change in profile was noted. This effect has also been inferentially observed in other wells. When a well is logged at two different PLT rates, occasionally when correlating a static simulation model to actual PLT results, the simulations will not match both rate curves. This can occur for one of two obvious reasons: 1) Either the simulation is simply invalid due to insufficient or invalid inputs, or 2) the production profile changed in the time it took to log the two rates. The results of the sandstone trial test in Figure 5 indicate that unloading at high rate can result in rapid wellbore cleanup; therefore, the latter condition 2), i.e. production profile changes due to wellbore cleanup, are evident. When this occurs, the utility of the


Petrotech Journal December Issue 2009

lower rate PLT dataset is greatly diminished; therefore when logging a passive ICD well, it is recommended to log the high rate first, preferably for as long as possible. Then log the lower rate afterwards. Calculating the well PI at the sandface (annulus) based on the PLT-log results indicate clearly that the well performance improved during PLT-logging (Table 1) and that the actual well PI is approaching the theoretical well PI estimated from Eq. 3. The numbers for the Pwf from PLT are here marked with blue and are the same number for the rate variations during the PLT, because of uncertainty during the stationary readings. The well PI estimated from the static reservoir model is assuming a skin of 0 along the entire wellbore and the performance according to the Pwf is in good agreement with the actual measured Pwf; however the well PI at sandface shows that the static reservoir modeling is over predicting the PI for the low rate, which is not that odd, since the initial low rate PLT-log did not perform very well. At the high

Once the static reservoir model with the ICD completion matches the actual PLT-log performance at the high rate with less than 5% difference, then standard procedure is to simulate how the well would have performed if the well was completed with a screen completion instead. Note: The simulation of the screen is assuming a perfectly performing conventional screen completion, and does not take into consideration the risk of improper well cleanup of the toe as we saw from the PLT-log, and which we cannot predict if the well was only having screens. The simulation of the ICD well matching the PLT-log results is shown in Figure 7a (Match model). Comparing this case with a standard screen completion, the well is very fortunate to have an ICD completion. The ICD completion has decreased the influence of inflow from the negative skin segments to half (Blue circle) and increased contribution from the high skin segments with about 4 times (Red circle). The well will therefore not suffer remarkably from the skin effects and the ICD completion will ensure good sweep efficiency of all zones.

For the case with skin 0 along the entire well path, the simulations of the standard screen completion in Figure 7b (Pink line) shows a remarkable heel-toe effect, with almost twice as much inflow for the first compartments (Black circle) which could potentially cone in gas or water within a very short timeframe. Also the screened well in this case is leaving the toe part with about 20% lesser inflow while the ICD completion has decreased the inflow in the heel from about 11 STB/D/ft to about 6 STB/D/

ft and increased the contribution from the toe; confirmed by the PLT-log.

Carbonate Reservoir Trial Well The carbonate well was completed during June 2006 and put on production in May 2007 (Figure 8). The objectives of the ICD completion in the carbonate reservoir were to restrict inflow from the three last compartments, due to expected higher reservoir pressure towards the toe. Additionally, the toe part of the well was close to the

Fig. 7: Static modeling of ICD (Blue lines) and standard screen completion (Pink lines): a) Match model. b) Static model skin 0.

gas-oil contact. The PLT-logging did not indicate a significant pressure gradient or free gas. Furthermore, there was no loss of circulation during drilling, which usually indicates severe fracture zones. The PLT loggings were first performed at the high choke and then at a lower choke size (Figure 9a), to ensure that well had been properly cleaned up before the logging. Since the three last compartments have fewer ICD units, the well has an artificial heel-toe inflow profile. Also there was measured crossflow of 1000 RB/D during shut-in of the well which indicated a pressure gradient of about 2 psi decreasing towards the heel.

Fig. 8: Carbonate ICD completion with 5 packers and 6 compartments

The high rate was then matched in the static reservoir model (Figure 9b) and required a manipulation of the permeability data. The well was initially designed based on an average permeability of 500 mD however the average permeability had to be increased to about 590 mD. Also the well had a higher GOR than expected, which was accounted for in the matching process.

Fig. 9: Inflow per segment and cumulative rate: a) PLT results at high and low chokes b) Match of PLT results with static model adjusted permeability.

The well PI during the PLT-logging was measured to 110 STB/D/psi and when excluding the pressure drop across the ICD units the well PI in the annulus is about 500 STB/D/psi. This annulus well PI measurement is in good agreement with the theoretical horizontal well PI calculated from Eq. 3 and therefore the well has no indications of formation damage. This is a remarkable result, since the well was shut-in for almost 10 months. Once the passive ICD completion model correlates to the actual PLT-log performance, standard procedure is to simulate how the well would have performed if the well was open hole (OH). The passive ICD static simulation is then juxtaposed against the OH simulation to compare oil flux per compartment (Figure 10a) and pressure along the well bore (Figure 10b). Note: This should be considered as an optimistic evaluation, because the OH would most likely not have been able to perform as predicted in the passive ICD static reservoir model. Specifically, the OH well would have higher Petrotech Journal December Issue 2009


Fig. 10: Flux and pressure comparison OH vs. ICD: a) Oil flux per compartment; comparison between ICD (Blue line) and OH completion (Pink line). b) Pressures along well bore; ICD annulus (Blue), ICD tubing (Pink), OH (Green) and P reservoir (Orange).

Fig. 11: Oil rate and GOR as a function of gas saturation: a) OH completion, Oil rate (Black lines) and GOR (Dashed Black line). b) ICD completion (Blue line) and GOR (Dashed Blue line).

Fig. 12: Static modeling of ICD and standard screen completion, Rate 10,300 STB/D (Blue lines) Rate 15,000 STB/D (Pink lines): a) Oil flux for screen cases b) Oil flux for ICD cases

skins in the toe due to non-uniform unloading; however, for comparative analysis, the skins in the two simulation scenarios are treated as identical and zero in both cases. The modeling results show that the pressure across the ICD completion is about 80 psi, which is a substantial pressure loss in the system. The reason for having such a high additional pressure would be to eliminate any unforeseen events caused by fracture systems which could cone gas and cause excessive gas production. Figures 11a and 11b show the results of the open hole and ICD static reservoir simulations, evaluating the potential GOR decrease with the ICD completion if gas breaks through in the last compartment in the toe. As the gas saturation increases from 0 to 40% the GOR in the OH completion increases from the initial of 1000 SCF/STB to 40,000 SCF/ STB, while the ICD well is predicted to maintain a GOR of only about 4200 SCF/STB. These remarkable results have however not yet been verified in true field trial wells.

Lessons Learned and Future Completion Designs

Fig. 13: Static modeling of a longer well with ICD: a) Oil flux for 2700ft and 10,300 STB/D b) Oil flux for 3300ft and 12,000 STB/D

Fig. 14: Synthetic permeability log (Pink) and an upscaled Average Perm log (Blue).

Matching the PLT-log to a static reservoir simulation for the sandstone well, then removing the ICD completion and replacing it with a conventional screen completion, the model shows the theoretical performance of the well without ICD. When the rate is increased to 15,000 STB/D for a standard screen completion, the well suffers from extreme heel-toe effect with the toe only contributing 1/4th that of the heel (Figure 12a). Increasing the rate from 10,300 to 15,000 STB/D for the ICD completion shows better balancing of the inflow including higher contribution from the toe (Figure 12b). Clearly, the sweep efficiency of the ICD completion is improved over the conventional screen completion, deferring gas or water breakthrough and draining the reservoir layers in a more balanced way. Taking the next step by looking at new options to utilize the advantages of the ICD completion, the wells can


Petrotech Journal December Issue 2009

Table 2: Comparison of OH Completion and ICD completions with different packer densities Completion Type OH. Synthetic Perm log OH. Average Perm log Packers per 3 Joint ICD. Synthetic Perm log ICD Aberage Perm log Packers per 12 Joint ICD Synthetic Perm log ICD Average Perm log Packers per 3 Joint

Oil rate Gas rate (STB/d) (MMSCF/d)

Water rate (STB/d)


WCUT (%)

BHP (Psi)

2135.3 2140.6

1.296 1.298

2437.1 2431.1

606.1 606.3

53.30 53.18

3097.9 3100.2

3544.7 3538.3

2.051 2.050

575.5 581.1

578.6 579.2

13.97 14.11

3011.1 2999.8

2914.5 2954.2

1.678 1.628

1459.8 1511.4

575.6 551.0

33.37 33.85

3024.1 3016.6

ICD Variable Synthetic Perm log







ICD Variable Average Perm log







ICD Variable, Syntnetic Perm log







ICD Variable Averrage Perm log







Packers per 12 Joint

Fig. 15: Static modeling of perm variations with packers (Black lines) for every 3rd joint; OH (Blue lines), ICD (Pink lines) and ICD variable (Orange lines): a) Oil flux for Synthetic Perm log and b) Oil flux for Average Perm 120ft

Fig. 16: Static modeling of perm variations with packers (Black lines) for every 12th joint; OH (Blue lines), “ICD” (Pink lines) and “ICD variable” (Orange lines); a) Oil flux for Synthetic Perm log and b) Oil flux for Average Perm 120ft

easily be extended without compromising the balancing effect, thus expanding the drainage area resulting in an increase of well reserves (Figure 13a represents 2700ft and 10,300 STB/D and Figure 13b represents 3300 ft and 12,000 STB/D). The well PI for the 3300ft well is increased

from about 1300 to 1360 STB/D/psi. As a result, fewer numbers of wells are needed to drain the reservoir volumes; however, it is recommended to perform dynamic reservoir simulation evaluations to establish a drainage strategy for the entire reservoir with the longer ICD wells.

For carbonate wells with very low PI, the potential for enhancing the well life by using ICD completions is best illustrated by simulating water breakthrough in fractures for two cases with different packer density. In this case, a sensitivity of synthetic low permeability and the impact of upscaling the magnitude of this log (Figure 14) have been performed to study the difference in the static reservoir modeling results. Additionally, this well has a large pressure differential along the wellbore of about 300 psi, being high at heel and lower at toe. This gradient is caused by pressure support from water injectors and low connectivity between the reservoir layers. The ICD completion simulations are performed with two sets of different nozzle sizes in Figure 15 and 16 respectively. The “ICD” simulations have the same nozzle size along the entire wellbore and the “ICD variable” simulations have different sizes to balance the inflow according to the large pressure differential in the reservoir. The average pressure drop across the nozzle-based ICD units is initially only half of the previous carbonate well (about 40 psi in these cases), which should be sufficient for the ICD completion to achieve the upside potential for maintaining oil production at low water cut. It should however be noted that this pressure drop is designed specifically for this well to achieve good well performance, and should not be considered as a standard ICD unit pressure for low permeability reservoirs as a generality. Simulation sensitivities are run for different packer spacing, based on both synthetic permeability logs (Figure 15a and 16a), and an average permeability (Figure 15b and 16b). In the first set of sensitivities (Figure 15), packer spacing is located every 120 ft (every 3rd joint). Figure 16 shows sensitivities for packer spacing every 480 ft (every 12th joint = four compartments). The impact on the simulations is noticeable when simulating is based on the upscaled permeability along the wellbore instead of using the log data. Figure 16a (Orange line), clearly shows that the ICD solution with four compartments is not able to capture high inflow from the high Petrotech Journal December Issue 2009


Nomenclature A Bo Cu Cv Cx h ICD J kH and kV Lw LWD ∆PF

= = = = = = = = = = = =



∆pFi ∆pNi

= = = = = = = =

Pwf PLT re, rw ρ μ


inflow area nozzles, sq.ft [m^2)] oil volume factor, RB/STB [Rm^3/Sm^3] units conversion constant dimensionless flow coefficient for nozzle units conversion constant reservoir height, ft [m] inflow control device productivity index (PI), STB/D/psi [Sm^3/d/bar] horizontal and vertical permeability, D [m^2] well length, ft [m] logging while drilling pressure drop from reservoir pressure to Pwf for a conventional completion, psi [bar] total pressure drop from reservoir pressure to Pwf for an ICD completion, psi [bar] pressure drop from formation into annulus, psi [bar] pressure from the annulus to the tubing pressure across nozzle based ICD unit flowing bottom hole pressure, psi [bar] production logging tools external boundary radius and wellbore radius, ft [m] density, lb/cf [kg/m^3] viscosity, cP [Pa*sec]

permeability layers towards the toe, which is much better captured with a packer on every third joint (Figure 15a, Orange line). Table 2 shows the results after simulating water breakthrough in 3 fractures in the heel. It is how much the ICD effectively decreases the water cut when water breaks through. If the well has “ICD variable” (designed accordingly to pressure differentials) and packers every third joint the water cut is estimated to be about 7% compared to an OH completion, which may be suffering from water cut of about 53%. This is substantial water cut decrease, which could remarkably extend the well life. The ICD solution with 4 compartments showed the water cut of 22%.

studies would likely indicate that the additional expenditure is justifiable.




Recommendations for future design workflow: 1) To propose the best ICD completion design for future wells, the field or the development area should to be evaluated as a whole. 2) The final ICD design of the completion should be performed based on LWD data and pressure gradients along wellbores. This means that drilling measurements are important to refine the ICD completion design. 3) If the well has severe pressure differentials, then firm operation guidelines for production rates should be established in order to avoid crossflow.

has increased the contribution for those zones by 2/3rd. Consequently better sweep efficiency is expected. Carbonate reservoir PLT evaluation: There are no indications of formation damage in this well, because the well PI of about 500 STB/D/psi is as predicted for an ideal horizontal well PI. For correlation purposes, perform PLT-logging at high rate first and low rate afterwards to ensure that well cleanup does not alter the rate-based inflow profiles while collecting data. Conclusively the nozzle-based ICD completion have several advantages: a. The ICD unit is integrated with a screen, designed to exclude abrasive particles above 45 μm, securing a long lifetime without plugging and erosion risk of the nozzles and the ICD unit. b. The ICD unit is equipped with at least 2 or more nozzles, so at least one nozzle will be exposed to inflow of fluid, making the system reliable even if the well has been left with solids-laden fluids down hole for a longer period before the well is put on production. Recommendations for future completion design options: a. Explore options of drilling and completing longer horizontal wells. b. Evaluate using annular packers more extensively in order to ensure a proper cleanup process and decrease gas or water rates when breaking through.

Acknowledgement We would like to thank Saudi Aramco and Schlumberger for the great team work leading to the success of these two trial wells and permission to publish the results.

References Conclusions

With respect to the number of packers to deploy, there is a cut-off limit as how much water cut or GOR decrease will economically justify the increased quantity of packers. To accurately assess the economics, dynamic modelling is recommended, which is beyond the scope of this paper; however, inferentially even the simplest


Petrotech Journal December Issue 2009

• 1) All completion and production objectives are met with the nozzlebased ICD completions. 2) Sandstone reservoir PLT evaluation: The well had initial indications of formation damage due to higher skin at the toe. After cleanup at higher rates, the ICD completion

SPE 85332 “New Technology Application to Extend the Life of Horizontal Wells by Creating Uniform-Flow-Profiles: Production Completion System: Case Study” H.A. Asheim 1997. Compendium: “Horizontal Well Inflow Performance.” Norwegian University of Science and Technology (NTNU)


Paving Grade Bitumen New opportunities in India Sonal Maheshwari, Biswanath Saha, P. Senthivel and N. V. Choudary Corporate R&D Centre, Bharat Petroleum Corporation Limited, Greater Noida

Dr. Biswanath Saha Sonal Maheshwari

Sonal is a Senior Research Engineer at Corporate R&D Centre of Bharat Petroleum Corporation Ltd., India. She is having 6 years of experience specializing in the development of bitumen products and processes, Resid Upgradation , processes in Crude areas. She has authored or co-authored technical publications on product developments for bitumen and modified bitumen in RTM, PetroTech, Asphalt Rubber, Chemcon etc. She holds a masterâ&#x20AC;&#x2122;s degree in chemical engineering from Indian Institute of Technology (IIT-Delhi, India) and having valuable experience in the area of bitumen and crude oils.

Biswanath is a Senior Research Scientist at Corporate R&D Centre of Bharat Petroleum Corporation Ltd., India, He has two years of R&D experience in Bitumen product & process development, Characterization, Rheological study using DSR and resid upgradation. He did his doctoral study in chemical engineering from Indian Institute of Technology (IIT- Guwahati, India) and having valuable experience in the area pyrolysis and gasification processes. He has publications of 11 international journals and 6 technical publications in conferences like PetroTech, ISFL, and Chemcon etc. Dr. N. V. Choudary

Dr. P. Senthivel

Senthivel received his doctoral degree in chemistry from Indian Institute of Technology, Madras in 1996. He was a research associate at University of Hyderabad (1997-98) before he joined as a research officer in IOCLR&D centre, Faridabad (1998-2007). He moved to BPCL-Corporate R&D Centre and presently holds the position of Manager-R&D (2007till date). Has about 10 years of research experience in lubricants. Currently pursuing research in the area of Bitumen and CO/CO2 conversion (Valorization). He is a member in Bureau of Indian Standards (Bitumen and their products committee).

Dr. N. V. Choudary is presently working as Chief Manager at Corporate R&D Centre, Bharat Petroleum Corporation Ltd., India. He has over 25 years of research experience in petroleum refining and petrochemicals. He holds MSc., and Ph.D., degrees in Chemistry from Shri Venkateswara University, Tirupati. He has filed about 40 patents and published over 60 papers in international journals. He has also presented about 70 papers in various conferences.

Bitumen- Background Nomenclature

According to the Oxford English Dictionary, asphalt is ‘‘A bituminous substance, found in many parts of the world, a smooth, hard, brittle, black or brownish-black resinous mineral, consisting of a mixture of different hydrocarbons; also called mineral pitch, Jew’s pitch and in the Old Testament ‘slime’,’’. The Oxford English Dictionary defines Bitumen as, ‘‘originally, a kind of mineral pitch found in Palestine and Babylon, used as mortar, etc. It also provides the following more scientific definition, ‘‘In modern scientific use, the generic name of certain inflammable substances, native hydrocarbons more or less oxygenated, liquid, semi-solid, and solid, including naphtha, petroleum, asphalt, etc Elastic Bitumen: Mineral Caoutchouc or Elaterite.’’ Today, both these words are used to describe the same class of materials, asphalt being the word of choice in the United States and bitumen in the European and Eastern countries. Concerning the controversies surrounding the usage of the word asphalt and bitumen in the United States and Europe, we refer the reader to the book by Jaccard and the discussion related to the usage of these words in the review by Peckham. According to the Permanent International Association of Roads Congress, the following are the definitions for Bitumen, Asphaltic Bitumen, Asphalt, and Tar. Bitumen: Mixtures of natural or pyrogenous origin or combination of both frequently accompanied by their nonmetallic derivatives, which can be gaseous, liquid, semisolid or solid, and which are completely soluble in carbon disulphide. Asphaltic Bitumen: Natural or naturally occurring bitumen or bitumen prepared from natural hydrocarbons by distillation or oxidation or cracking; solid or viscous, containing a low percentage of volatile products; possessing characteristic agglomerating properties, and substantially soluble in carbon disulphide. Asphalt: Natural or mechanical mixtures in which the asphaltic bitumen is associated with inert matter.


Petrotech Journal December Issue 2009

Tar: A bituminous product, viscous or liquid resulting from the destructive distillation of carbonaceous materials. The American Society for Testing and Materials (ASTM) in its standard ASTM D 8-97 has promulgated the following definitions for asphalt and bitumen. Bituminous materials (Relating in general to bituminous materials): a class of black or dark-colored (solid, semi-solid or viscous) cementitious substances, natural or manufactured, composed principally of high molecular weight hydrocarbons, of which asphalts, tars, pitches, and asphaltites are typical. Relating specifically to Petroleum or Asphalts: Asphalt, a dark brown to black cementitious material in which the predominating constituents are bitumen which occur in nature or are obtained in petroleum processing.

was important beginning at the end of the New Kingdom (after 1100 BC)--in fact the word from which mummy is derived ‘mūmiyyah’ means bitumen in Arabic. The La Brea Tar Pits in California is one place where a smelly oily bitumen lake experienced first hand. Bitumen was used as a sealant, as an adhesive, and filler in building construction in the early civilizations of Babylonia, Sumeria, Assyria, Egypt, India, China, and Greece. Bitumen was widely used in ancient times as a preservative. Burning asphalt was used as a weapon; firebrands with burning asphalt were hurled at one’s enemies. Bitumen was also used for decorative purposes and as jewelry. Necklaces comprising of bitumen beads dating back to 500 BC have been found as also inlays of precious stones in bitumen. Another important use of bitumen was as a source of energy. Bitumen was used as a fuel for lamps. Source

As per Indian Standards (IS 334:2002), the term bitumen is defined as “a black or dark brown non-crystalline solid or viscous material having adhesive properties derived from petroleum either by natural or refinery processes and substantially soluble in carbon di-sulphide”. Bitumen in ancient times

The earliest known use of bitumen was by Neanderthals, some 40,000 years ago. Bitumen was found adhering to stone tools used by Neanderthals at sites such as Hummal and Umm El Tlel in Syria; it was probably used to fasten a wooden or ivory haft to the sharp edged tools. During the late Uruk and Chalcolithic periods at Hacinebi, in Syria, bitumen was used for construction of buildings and water proofing of reed boats, with among other uses. Some of the bitumen in Syria was found to have originated from the Hit seepage on the Euphrates River in southern Mesopotamia. The earliest reed boat discovered yet was coated with bitumen, at the site of H3 at AsSabiyah, about 5000 BC. And, one of the myths of the Mesopotamian Sargon the Great of Akkad was that as an infant he floated in a bitumen-coated reed basket down the Euphrates River. The use of bitumen in Egyptian mummies

Bitumen was available in abundance naturally in seas, lakes, ponds, and rivers, on mountainsides, in coal pits and iron mines; practically in all forms of flora and fauna. This made it possible to put it to diverse use from times immemorial. Bitumen seems to have been available naturally aplenty. Agricola remarks, ‘‘Liquid bitumen, if there is much floating on springs, streams, and rivers, is drawn up in buckets or other vessels; but, if there is little, it is collected with goose wings, pieces of linen, ralla, shreds of reeds, and other things to which it easily adheres, and it is boiled in large brass or iron pots by fire and condensed.’’ Nowadays, bitumen is primarily obtained as a by-product during the process of distillation of petroleum. Chemical composition and structure

Based on solubility and polarity, bitumen can be divided into three parts: asphaltene, resin, and maltene. Among them, asphaltene is the most viscous and most polar. Maltene is mainly composed of aliphatic molecules and is nonpolar and the least viscous. Resin polarity and viscosity is in between that of asphaltene and maltene. Although bitumen is a mixture composed of hundreds of organic compounds. It is not yet established the exact model for bi-

Figure 1: Possible structure of Bitumen

Filled hexagons: Asphaltenes Open hexagons: Aromatics Hollow circles: Aromatic naphthenic Rod like structures: Mixed naphthenic-aliphatic Dashes: Aliphatics

tumen. Most popular model is colloidal model (Pfeifer and Saal (1940)). Bitumen is visualized as colloidal system, with asphaltenes forming the centers of micelles and having a more pronounced aromatic nature, the asphaltenes were assumed to be surrounded by lighter constituents of less aromatic nature, and there were no distinct interphases between the micelles and the medium surrounding it. Refining process

Traditionally bitumen is processed from crude using any of the following four processes: vacuum distillation, atmospheric distillation, solvent refining and air blowing. Each method is quite complex and there are major technical issues related to them. For instance, in solvent refining, propane deasphalting and ROSE supercritical process are employed. Propane deasphalting results in a mixture of asphaltene and resins called PDA pitch or PDA tar having low penetration grade (less than 12) with a very high viscosity at 60o C of around 200,000 Poises. This PDA pitch is typically blended with heavy extracts and vacuum residue to result in bitumen of suitable penetration grade/ viscosity grade. Similarly in the case of air blowing, there are various issues such as temperature of blowing, batchwise blowing or continuous blowing, catalytic/non-catalytic blowing etc. Bitumen may be prepared by any of these routes depending on the crude type. If the crude permits, straight reduction to required bitumen grade is possible (normally with bituminous crudes). Blending or mixing the crude feed is one route often selected. If two or more crudes were processed separately with one yielding low viscosity residue and other yielding a high viscosity residue, the residues can be blended. If only a low viscosity residue was made, it

could be blended with a precipitated bitumen or air blown. If only a high viscosity type residue was made, it could be regulated to asphalt during distillation or it could be blended back with gas oil or a similar fraction. Thus refiners have several choices, but choice is dictated by the crude type/crude mix and to some extent type of refining process being used. Hence it is quite possible that VG-10 bitumen produced in any two refineries will have different crude source and would have been processed by different method. Different processes for obtaining bitumen is illustrated by the flow diagram given below. Air Blown Bitumen

As mentioned earlier, various issues are associated with air blowing process (eg. temperature of blowing, air flow rate). Conventional bitumen blowing unit has typical disadvantages like non-uniform reaction, air and water pollution associated with bitumen off gas venting in spite of scrubbing the same with caustic and water

washing. In addition to this, unpleasant smell in the surroundings of this unit is inevitable. Biturox® process is one of the advanced technologies for blowing bitumen and is proprietary technology of M/s Porner Gruppe, Austria which represents the modern and proven solution to produce top quality bitumen from a great variety of raw materials. Both refineries (Mumbai and Kochi) of BPCL have acquired this technology to produce paving grade bitumen and few other Indian refineries have also acquired the same. It is to be highlighted that BPCL-Kochi refinery is the first refinery in India to adopt off gas treatment plant to make the ‘Biturox’ unit ‘environmental friendly’. The core piece of the biturox process is the unequalled loop reactor. In this reactor the thermo-chemical conversion of selected raw material blends by air-oxygen takes place continuously and under repeatable conditions. The process allows controlling all important process parameters (pressure, temperature, flow rate, residence time, etc) with high accuracy. The valuable aromatic components are formed and preserved in the reaction mixture and at the same time the degradation of organic compounds to coke and the build up of deposits is minimized. The major advantages in physico-chemical properties of bitumen processed thru Biturox process compared with other processes are given below.

C/H ratio: Blown <SR<SDA

Figure 2: Various manufacturing methodology for Bitumen

Petrotech Journal December Issue 2009


Fraass Breaking point: Blown <SR<SDA • Ductility: Blown <SR<SDA • Aging character: Blown <SR<SDA (excellent durability) Refining Process: Blown: air blown, SR: Straight run, SDA: Solvent deasphalt

PPP in road development. In the event of above development there is massive requirement for bitumen.The projected bitumen demand-supply by 2009-10 is around 6000 TMT and the supply would be around 5100 TMT. More over, the projected bitumen demand in India by 2011-21 is expected to grow to 13500 TMT.

Paving grade bitumen Bitumen producers in India Indian Road Network and government policy

After liberalization, India is witnessing significant growth in every sector which is evident by rapid growth in infrastructure developments. This momentous change has brought a continuous increase in traffic volume, load conditions, etc and therefore binder required for road construction is necessarily should possess higher service life and better performance characteristics. To have a sustained growth rate of about 9% per annum, a good road network has a commanding position and is the life line of country’s economy. In 1951, total road laid in India was about 0.32 million KM which has increased to 3.38 million KM in 2002 out of which only 16.04 Lac Km road is surfaced. Presently, India is building a huge network of highways and rural roads. The nationwide highway network is expected to be completed by 2011, and the next phase would be linking up smaller towns and villages through a high quality road network, which would continue up to 2020. National Highways has been entrusted to NHAI (National Highways Authority of India), which is already in process under National Highway Development Programme. This programme (NHDP: I to VII) is scheduled to be completed at a cost of Rs. 2,20,000 crores by 2012. Most of these investments are expected to be realized through Public Private Partnerships (PPP) in the form of Build-operate-transfer (BOT) projects. PPPs have the added advantage that they themselves have a control over a clear identification of the levels of service quality based on benchmarks that have been achieved elsewhere. The balance of the national highways, major district and ordinary district roads are entrusted to state PWDs or allied agencies. Modernizing the state level net work is equally important and many states are exploring the scope of


Petrotech Journal December Issue 2009

There are total 12 refineries in India which produces paving grade bitumen. Of which, eleven are PSU companies and one private company. Bitumen production capacities and production volume during 2008-09 from these Indian refineries is given in table-1.

Paradigm shift in specifications Grading of bitumen

Bitumen is a thermoplastic material, that is, its stiffness is dependent on its temperature. Its stiffness decreases with increase in temperature. This temperature versus stiffness relationship is different for different bitumen based on the origin of the petroleum crude and/ or method of refining. Therefore, it is obvious we should define a test temperature at which the grading will be done and compare the quality of bitumen products.

century. Experienced bitumen inspectors used the technique for testing and accepting bitumen for paving. Obviously, the test temperature was 98.6 F (37 oC) equal to the average human body temperature. Penetration Grading

Grading of bitumen by penetration test at 25 oC was adopted by the American Society for Testing and Materials (ASTM) Committee D04 on Road and Paving Materials in 1903, about 100 years ago. Figure 3 shows the schematic of the penetration test, in which a needle loaded with 100 grams is allowed to penetrate the bitumen maintained at 25 oC temperature in a water bath, for 5 seconds. The resulting penetration is measured in mm; 1 penetration unit = 0.1 mm. The greater the penetration, the softer is the bitumen. ASTM Standard D946 specified five penetration grades where as IS specifies six grades for bitumen:

ASTM D 946 40-50 60-70 85-100 120-150

IS:73 (1992)* 30-40 (hardest bitumen grade) 40-50 50-60 60-70


80-100 175-225 (softest bitumen grade)

* Obsolete

Grading by Chewing

Chewing in mouth was the first mode of testing to determine stiffness (hardness) of bitumen during the late 19th

So far, the 100-year old penetration grading system has been used in India with 60-70 penetration grade being

Table 1: Bitumen capacity and production by the Indian refineries during 2008-09 REFINERY




Bitumen blowing unit*



400 600 1000 200 550 750 500 60 500 600 750 500 2910 500 1000 6160

325 523 847 197 465 662 493 15 495 596 723 380 2702 248 125 4584

Yes –

* Biturox® Process

Yes Yes Yes – – Yes Yes – Yes –

Figure 3: Schematic of penetration test

most widely used. The softer 80-100 penetration grade has been used for low-volume roads and spray applications (such as in surface dressing) in India. Limitations with the Pen grade System

• • •

This gradation is based on an empirical property; it doesn’t give any relevance with field performance of the sample. Two samples having same pen value may show different behavior at high and low temperatures. Pen graded bitumen can’t be effectively used for modification purpose (eg. PMB). No bitumen viscosity is available near asphalt mixing and compaction temperatures for the guidance of contractors. Penetration grading doesn’t control the temperature susceptibility of bitumen. Highly temperature susceptible bitumen is not desirable as they are very soft at high service temperature and very stiff at low service temperatures.

60 oC (near the maximum pavement temperature during summer) and its measurement unit is poise. The test equipment for measuring viscosity both at 60 oC and 135 oC is simple and is available in most bitumen testing laboratories in India because these tests were already specified in IS 73:1992. ASTM Standard D 3381:95 specified six asphalt cement (AC) –viscosity grades and IS:73 (2006) specifies only four grades for paving grade bitumen Low viscosity grades such as AC-2.5 and AC-5 were used in cold climate of Canada. AC-10 was used in the northern tier states of the US, AC-20 was used in most of the US, and high viscosity AC-30 was used in southern states such as Florida, Georgia, and Alabama with hot climate and rainfall similar to that of India as in table 2. Advantages of the viscosity grading system for bitumen:

• •

Viscosity Grading

Viscosity grading at 60 oC was introduced in the Unites States during 1970s to address construction problems (tender mixes which could not be rolled without the mix pushing and shoving under the roller) and high temperature performance (rutting during hot summer) as mentioned earlier. The 60-70 penetration grade bitumen most widely used in the US prior to 1970s was significantly variable in terms of resistance to rutting. Some 60-70 penetration bitumen also had very low viscosity at 135 oC, which caused tender mix problems. Viscosity grading is based on a fundamental, scientific viscosity test, which is conducted at

In recent past, worldwide Bitumen specifications are getting upgraded to meet the growing demands of customers. After liberalization, India is witnessing significant growth in every sector; this momentous change has brought a continuous increase in traffic volume, load conditions, etc and therefore binder required for road construction is necessarily should possess high service life and better performance characteristics. In view of this, new standards, test methods, techniques are being developed and validated by carrying out conventional and complex evaluation. It is to be highlighted that India recently shifted from pen grading to viscosity grading. Need for Superpave Performance Grading

Pavement grade bitumen specifications have undergone significant change worldwide and in particular USA and Europe. Most of the developed countries have phased out penetration grade specifications and switched over to viscosity grade and finally to ‘performance grade’. Though viscosity grading enables customer/end user to get better quality pavement bitumen, it has certain limitations namely it fails to provide any information related to rutting, fatigue, and brittle fracture of the bitumen in the field. Looking at these limitations, it is imperative that one has to adopt the performance grad-

VG system is based on fundamental properties not on empirical correlation Viscosity is measured at 600C and 1350C which takes care of both low and high temperature susceptibility of the binder which is not possible with Penetration value @250C. Hence VG system provides ease of understanding the performance in the Table 2: Viscosity Grades and IS:73 ASTM D:3381 (1995) IS:73 (2006) field. Abs viscosity at Abs viscosity at IS 73-2006 has only Grade Grade 60°C, Poises 60°C, Poises 7 tests to evaluate a AC-2.5 (softest) 250 +/50 VG 10 >800 sample compared AC-5 500 +/100 VG 20 >1600 to 12 tests in pen AC-10 1000 +/- 200 VG 30 >2400 grade system. Only AC-20 2000 +/400 VG 40 >3200 four viscosity grades AC-30 3000 +/600 are being followed AC-40 (hardest) 4000 +/- 800 (VG10,20,30&40) in India Figure 4: Three 60-70 penetration grade bitumen Same VG bitumen gives similar rutting with different stiffnesses at high and low service performance unlike temperatures Penetration grade. Ease of handling to the customer as viscosity values at two different temperatures are available, which can be used to measure accurate mixing and compaction temperature. Petrotech Journal December Issue 2009


ing system, which gives more and dependable information about the field performance of the sample. Strategic Highway Research Program (SHRP), USA introduced this new Performance Grading system based on fundamental properties & performance characteristics, where binder is being classified by two numbers e.g. PG 46-34, PG52-28 etc. The Superpave performance grade (PG) bitumen is based on climate. For example, PG 64-22 bitumen is suitable for a project location, where the average 7-day maximum pavement temperature is as much as 64 oC, and the minimum pavement temperature is –22 oC. It should be mentioned here that inline with international practice, in India the shift towards VG now is one step towards the development of performance grading system. Aging tests: All bitumen undergoes a more or less rapid change with aging that appears to be due to two possible causes. One is the surface hardening, which is likely to occur due to oxidation, and possibly to the volatilization of some light oils. It begins at the surface and gradually extends into the entire bitumen. The other is hardening of the entire mass, evidently due to condensation of molecules. Short term aging: Bitumen ages during mixing, placement and compaction. This aging is called short-term aging. Thin film oven and Rolling thin film oven aging provide simulated short term aged asphalt binder for physical property testing. In this test bitumen binder is exposed to elevated temperatures to simulate manufacturing and placement aging. The TFO/RTFO also provides a quantitative measure of the volatiles lost during the aging process. Long term aging: During the service bitumen becomes brittle with the time. This long term aging also can be simulated in the lab by using PAV. In PAV bitumen is exposed to heat and pressure to simulate in-service aging over a period for about 7-10 years. All samples obtained after RTFOT and PAV test are subjected to DSR (Dynamic Shear Rheometer) for there performance evaluation. DSR is used to measure the high temperature performance of both unaged and aged bitumen samples as per AASHTO T315 method. This stan-


Petrotech Journal December Issue 2009

dard contains the procedure to measure the complex modulus (G*) and phase angle (δ) of a bitumen sample using a parallel plate geometry. The test temperature for this is related to the temperature experienced by the pavement in a particular geographical area. The instrument measures the complex modulus (G*) of the sample which is an indicator of the stiffness or resistance to deformation of the bitumen under load. The complex shear modulus and phase angle define the resistance to shear deformation of the bitumen sample in the linear visco-elastic region. The complex modulus (G*) and phase angle (δ) are used to calculate the performance related criteria in accordance to AASHTO M 320. Specifications of Paving grade bitumen – A comparison (Pen Vs VG vs PG )

Worldwide, paving grade bitumen is either “penetration” or “viscosity” graded until SHRP introduces the PG grading system. The major issue with the former grades are that they are

based on empirical tests. Empirical specifications rely solely on practical experience and observations without regard for pavement performance theory. Therefore, the specification is based on the results from a given situation. Once the conditions change, the results may no longer be the same. No tests are performed in both these specifications to simulate in-service aging, which occurs when the bitumen reacts with the oxygen in the atmosphere by oxidation. PG specification uses tests to measure physical properties that can be directly related to field performance by engineering principles. PG binders are tested under conditions that are similar to the three critical stages of a binder’s life viz, a. transport, storage, and handling, b. mix production and construction and c. in-service aging. The physico-chemical properties of binder as per three grading (Pen, VG & PG) are compared in the table 3. As mentioned earlier, paving grade bitumen needs to be assessed by phys-

Table 3: Comparison of Penetration, Viscosity and Performance Grading Systems Penetration Grade

Viscosity Grade

IS 73: 1992 #(Pen 60-70)

IS 73 : 2006 (VG 30)

Performance Grade AASHTHO M320 /ASTM 6373-1999(PG 64-22)


Specific Gravity at 27 oC (0.99 Min)

Abs Viscosity at 60oC, Poises (2400 Min)

Flash Point , COC, 0C (≥ 230)


Water % by mass, (0.2 Max)

Kinematic Viscosity at 135oC, cSt (350 Min)

Rotational Viscosity at 135oC (≤ 3 Pa. s)


Flash Point, COC, oC (220 Min)

Flash Point , COC, oC (220 Original Binder, G*/Sin, using DSR at 64oC (≥ 1.0 kPa) Min)


Softening Point, oC (45-55)

Softening Point, oC (47 Min)

RTFO aged Binder, G*/Sin, using DSR at 64oC (≥ 2.2 kPa)


Penetration at 25oC 100g, 5s, dmm (60-70)

Penetration at 25oC 100g, 5s, dmm (50-70)

PAV Aged Sample G*XSin, using DSR at 22oC (≤ 5000 kPa)


Penetration Ratio (35 Min)

Matter soluble in TCE, % (99 Min)

PAV aged sample using BBR, at -22oC, Stiffness (≤ 300 MPa), (m≥ 0.3)


Ductility at 25oC, cm (75 Min)

Tests on Residue from TFOT, Viscosity Ratio at 60oC (4.0 Max)


Paraffin Wax, % by mass (4.5 Max)

Ductility at 25oC, cm after TFOT (40 Min)

9 Fraass Breaking Point, oC (-6 Max) 10(i) Loss on heating, TFOT (1 Max) 10(ii)

Retained PEN after TFOT, 25oC, 100g, 5s, dmm, % of original, (52 Min )


Matter soluble in TCE, % (99 Min)


Viscosity at a) 60oC, Poises (2000±500) b) 1350C, cSt (300 Min) # Obsolete * Specification limits for each property is given in ( ) for the chosen grade

ical-chemical properties that can be directly related to field performance by engineering principles. More number of tests as well as mere empirical test data is not helpful in assessing the performance of binder material.

Innovations in Paving grade bitumen Need for bitumen modifications

As a visco-elastic material, bitumen plays a prominent role in determining many aspects of road performance. For example a bituminous mixture (asphalt) needs to be flexible enough at low service temperatures to prevent pavement cracking and to be stiff enough at high service temperature to prevent rutting. These functional properties are required to enable pavements to accommodate increasing traffic loadings in varying climatic environments. Unfortunately asphalt containing conventional bitumen does not always perform as expected. Pavement performance is affected by the properties and behavior of sub-grade soil, the granular sub base, base layers and the asphalt concrete layer. Several properties of asphalt concrete layer affect pavement performance. These include fatigue cracking, rutting, hardening of the bitumen binder and temperature cracking potentials. To improve the properties of bitumen, several types of modification have been investigated. It includes modification using additives, polymers and by chemical materials. In general, addition of polymers to asphalt concrete mixtures enhances the resistance of asphalt concrete to fatigue cracking, rutting, temperature cracking and stripping. In polymer modification various types of additives are incorporated such as rubber latex, crumb rubber, virgin polymers, recycled plastics, etc. Indeed polymer modified bitumen is emerging as one of the important construction materials for flexible pavement. Schuler et al carried out investigations on indirect tensile test using AC-5 and SBS (styrenebutadiene-styrene) polymer as one of the modifiers. SBS modified AC-5 exhibited superior fatigue properties. Denning etal reported that asphalt concrete with polyethylene as modifier is more resistant to rutting during elevated temperature. The use of ethylene vinyl acetate (EVA) as a binder

Table 4. Types of Polymer modifiers Type Plastomeric

Polyethylene, Ethylene vinyl acetate (EVA), polypropylene, Ethylene butyl acrylate (EBA) Ethylene ter polymer, Ethylene propylene diene (EPDM) etc


Styrene isoprene styrene (SIS), styrene butadiene styrene block polymer(SBS), etc.

Synthetic polymers

additive produced highest fatigue life improvement. There are many reports which highlight the improvement of binder properties by using several of thermoplastic and thermoelastic type polymers. Selected polymers are listed in the table 4. Advantages of modified bitumen are,

• • • • • • •

Chemical name

Lower susceptibility to daily and seasonal temperature variation Higher resistance to deformation at elevated pavement temperature Better age resistance properties Better adhesion between aggregate and binder High fatigue life of mixes Delay of cracking and reflective cracking Overall improved performance in extreme conditions and under heavy traffic conditions

Specification requirements of modified bitumen

Conventional test methods would not provide sufficient inference about the critical properties namely thermal susceptibility, elastic behaviour, aging characteristics, storage stability, etc of modified bitumen. There are different advance test equipments available to evaluate these properties.

Each critical test has its own significance in evaluating the performance of the modified binder. For example, purpose of elastic recovery is to assess the degree of modification of bitumen by polymer additives; similarly separation difference provides the relative separation properties between bitumen modifier and bitumen. Complex modulus (G*) and phase angle (δ) are used to measure the temperature experienced by the pavement in the geographical area for which the use of binder is intended. Complex modulus and phase angle have the direct correlations with the resistance to deformation of the binder (rutting behavior) in the viscoelastic region and used to evaluate the performance aspect of modified bitumen where elastic recovery is insignificant. Increase in softening point and elastic recovery after aging helps to understand the performance of modified bitumen after aging. Table 5 given below compares tests for conventional and modified bitumen products. Testing on mixes include Marshall, gyratory compactor, failure analysis of permanent deformation, rutting resistance (rut wheel tester), tensile creep testing, stiffness modulus, etc. Specialty grade

The requirements for physico-chemical Due to increasing volume of load and properties of polymer and rubber modtraffic, customer requirement is also ified bitumen for use in pavement conchanging with time. Hence, there is an structions are given in IS 15462:2004. urge to develop customized product to From this specification, it can be obmeet customer’s stringent specificaserved that some critical properties tion requirement. In addition to modinamely, elastic recovery (before and fied bitumen, foam bitumen, bitumen after aging test), Table 5. separation differTests on conventional bitumen Test on modified bitumen ence, complex modPenetration Penetration ulus and increase in Softening point softening point after Softening point Viscosity (U-tubes) Elastic recovery TFOT (Thin Film Fraass breaking point Complex modulus (DSR) Oven Test), etc of modified bitumen Bending beam and direction tension Storage stability (separation test) are assessed through standard tests which Thin film oven test (aging simulation) Rolling thin film oven test* Pressure aging vessel test* is in addition to the *aging simulation conventional tests. Petrotech Journal December Issue 2009


emulsion, modified bitumen emulsion, fuel resistant bitumen, colored bitumen, polypacked bitumen, plant based binders, etc are classified as specialty grade bitumen products. Some of them are briefly explained in the following section. Bitumen Emulsion: Bitumen emulsions are made up of three componentsBitumen, water and emulsifier. It is a two phase system consisting of two immiscible liquids. The emulsifying agents maintain the bitumen droplets in stable suspension and control the breaking time (time taken for the water phase to separate from bitumen phase and evaporate) of the emulsion. By proper selection of emulsifying agents and other manufacturing controls emulsified bitumen are produced in several types and grades. Major types are Anionic, cationic and non-ionic bitumen emulsion. Polymer modified bitumen emulsion is receiving growing attention nowadays because of many salient features. Bitumen emulsion products find wide use in pavement applications such as microsurfcaing, tack coat, penetration macadam, pothole repair, surface dressing, fog seal, slurry seal, crack seal, etc. Specification requirements and standards tests for bitumen emulsion (cationic type) is given in IS 8887: 2004 Colored bitumen: This is specialty grade bitumen which is prepared by adding modifiers (inorganic material, synthetic resins & dyes) and can be used primarily for the areas where there is requirement of distinguishing the one track from the other such as in airfield, athletic areas, parking lots, highways etc. This product shows performance similar to that of modified bitumen. Fuel Resistance Bitumen (FRB): Lighter petroleum based fuel spillage is common in areas like airport (parking bay/fuel loading locations), fuel depots, bus-stop, taxi stand etc. Since bitumen is also a hydrocarbon material, it can easily be soften when mixed with petroleum based fuels, which are chemically compatible with the bitumen. Hence, the spillage leads to permanent deformation and pavement failures. To overcome this issue, bitumen possessing superior quality and high resistance to fuel spillage is required. In general, modified bitumen containing specific


Petrotech Journal December Issue 2009

Fig 5: Colored bitumen in roadways.

additive components are used as fuel resistant bitumen. One of the most critical properties of this product is fuel soaking test (ATF, Diesel etc). Figure 6 given below illustrates fuel soaking test of fuel resistant bitumen. Polybag packed bitumen: This is a new patented technology developed by M/s Bharat Petroleum Corporation Ltd which replaces the (packed) metallic drum bitumen. In this technique, unmodified bitumen is packed in polybags. The advantages of polypacked bitumen are i. ease of handling (easy to lift and carry),ii. Disposable packpackaging material (polybag) gets dissolved along with bitumen which in turn improves quality of bitumen for eg. Increase in softening point and reduction of pen value and iii. Environment friendly product- since no hassle of managing/disposing drums.

Figure 6: Before and after fuel soaking test in Diesel for both FRB and VG 30 bitumen

(a) Before soaking test

(b) Fuel resistant bitumen

Conclusions Based on IS 73:2006 Paving Bitumen – Specification (Third Revision) issued in July 2006, India has recently been shifted to Viscosity graded system for paving bitumen. The viscosity grading system replaces a 100-year old penetration grading system. This paper provides an overview of the history of bitumen, its chemicals composition and refining processes. The sequence of grading systems: grading by chewing, penetration grading, viscosity grading, and Superpave performance grading, has been briefly covered with their respective advantages and disadvantages. In this post liberalization scenario, there is a rapid growth in infrastructure developments in every sector, which puts

(c) VG 30 Grade bitumen Figure 7: Polypacked bitumen

tremendous pressure on Indian road network. Currently most of the completed NHDP projects will require performance monitoring and in the next 10 years, several additional thousands of kilometers are going to be laid with bitumen as the binder. Therefore, to keep country’s network at satisfactory serviceable condition, it is imperative that good amount of effort required to be put to develop better mix design, newer and high performance binders, specifications and standard test methods and also it is equally significant to develop better refining process methods.

References • Connan J (1999), Use and trade of bitumen in antiquity and prehistory: molecular archaeology reveals secrets of past civilizations, Philos. Trans. R. Soc. London, Ser. B 354, 33–59. • Yen TF (1990), Asphaltic materials, Encyclopedia of Polymer Science and Engineering, Index Volume, A, 1–10, John Wiley and Sons, New York. • Richardson C (1912), Minority report of committee D-4 on standard tests for road materials, ASTM Proc, XII, 75–77. • Whiteoak D (1990), The Shell Bitumen Handbook, Shell Bitumen, United Kingdom • Hackford JE (1924), Discussion on ‘‘the constitution of asphalt,’’ by FJ Nellensteyn, J. Inst. Pet. 10, 717– 719. • Kalichevsky V and Fulton SC (1931), Chemical composition of asphalts and asphaltic materials, National Petroleum News 23 (51), 33– 36. • U. Isacsson and X.Lu, Materials and structures 28 (1995) p.139 • Rajiv Sharma, “Indian market-Supply/Demand overview”, 5th Asian Bitumen conference, Singapore, 1920 Nov 2009

• IS:1201 to 1220-1978, “Methods for testing tar and bituminous materials”, Bureau of Indian Standards, New Delhi • IS 73:2006: “Paving bitumen specification”, Bureau of Indian Standards, New Delhi • Book of AASHTO standards, “Standard Specifications for Performance Graded Asphalt Binder ”, AASHTO M320-02 • Annual book of ASTM standards, (2002), “Standard Test Method for Accelerated Aging of Asphalt Binder Using a Pressurized Aging vessel (PAV),” ASTM: D 6521-00, Vol. 04.03 • AASHTO Designation TP5: “Standard method of test for determining the Rheological properties of asphalt binder using dynamic shear rheometer (DSR)’. Washington D.C.1994 • Kandhal, P.S. “ An Overview of the Viscosity Grading System Adopted in India for Paving Bitumen” Indian Roads Congress, Indian Highways magazine, April 2007 • Maheshwari S, Saha B, Senthivel P, Choudary N V, “Assessment of Bitumen according to Performance Grading System”, P544 , Petrotech2009 , New Delhi • Maheshwari S , Rao PVC , Choudary NV,(2007), “Optimization of Process Parameters for the Production of Visco Grade (VG) Bitumen from Deep Cut SR Using Slop”, Refinery Technology Meet-2007, Kovalam • Saha B, Maheshwari S, Senthivel P, Choudary NV and Krishnan JM, (2009), ” Steady Shear Properties of Crumb Rubber Modified Bitumen”, Asphalt Rubber Conference, 2-4 Nov 2009,Nanjing(China) • Biswanath. S, etal, “Crumb Rubber Modified Bitumen (CRMB) Compositions And Process Thereof” Indian patent, File no. 2871/ MUM/2009

• IRC:SP53-2002, ‘Guidelines on use of Polymer and rubber modified bitumen in road construction”, New Delhi • IS 15462:2004, “Polymer and rubber modified bitumen-Specifications”, Bureau of Indian Standards, New Delhi • J. H. Denning and J. Carswell, “Improvements in rolled asphalt surfacing by the addition of organic polymers”, Dept of Transport, Report LR 989. Transportation Road Research Laboratory (TRRL), Crowthrone, 1981 • Y. C. Gokhale, Sunil Bose and P. K. jain, “Engineering evaluation of polymer rubber – bitumen blends for use in road construction”, IRMRA, 13th Rubber conference, Bombay, 1985,p.213 • R.J. Salter and F. Rafati-Afshar, “Effect of additives on bituminous highway pavement materials evaluated by indirect tensile test”, Transportation Research Record, 1115, 1987, p 183 • N Little, J. W. Button, R. M. White, E. K. Ensley, Y. Kim and S. J. Ahmed, “Investigation of Asphalt additives”. Report A/RD-87/001 FHWA. U.S Department of Transportation (1987) • J.L. Goodrich, “Asphalt and polymer modified asphalt properties related to the performance of asphalt concrete mixes”. Proc., association of the Asphalt Paving Technologists, Vol.57,1988. • Sunil Bose and P. K. Jain, Sangita and I. R. Arya, “Characterization of polymer modified asphalt binders for roads and air field surfacing, polymer modified asphalt binders”, ASTM:STP:1108, American Society of Testing Materials, Philadelphia, USA, 1992, p 331 • Thorat. T. S etal, “ Bitumen Packaging and Method” Indian Patent No WO2006067805

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Nanotechnology Application Potentials in Petroleum Industry Dr. S K Hait, Dr. D K Tuli and Mr. Anand Kumar Indian Oil Corporation Ltd., Research & Development Center, Faridabad

Dr. D K Tuli Mr. Anand Kumar

Mr Anand Kumar is a Chemical Engineer and after a brief stint of teaching, joined India Oil in 1974. He has undergone specialized training in Petroleum Refining Engineering from IIP and Refinery Planning and Economics from Oxford Petroleum School, besides having attended management development programmes at MDI and IIM-A and business school in Europe and USA. He has a rich experience of 30 years, in various areas of oil refining viz Process Engineering, Projects, Supply Chain Management and Human Potential Management and has served at all major refineries of Indian Oil including Port Harcourt Refinery of NNPC, Nigeria, where he left behind a distinct mark in commissioning and operating the refinery and setting up related system training and improving of Refinery profitability. An Environmentalist to the core, he developed one of the countryâ&#x20AC;&#x2122;s best ECO-PARK at Barauni, which became an important bird spot and he is also credited with the first experimentation of biodegradation of menacing oily sludge process. Currently he is Director (R&D), IndianOil Corporation Ltd. He is an active member of many forums, associations and professional bodies and has presented papers at various national and international forums on various management and refinery issues.

Dr. D.K. Tuli hold Ph.D. in Synthetic Chemistry with over two decades of rich and varied experience in research and development in the hydrocarbon industry with a special interest in synthetics and biotics. Dr. Tuli has to his credit, 12 U.S. patents, two European patents and over 20 Indian patents. He has published over 50 research papers in professional journals. He has guided students from various Indian Universities for their Ph.D. thesis. Dr. Tuli was also a SERC post-doctoral fellow at the University of Liverpool, Robort Robinson Laboratories, England during 1979-81 and 1987-89 and carried out advance research in the areas of new synthetic and analytical methods. Since July 2003, Dr. Tuli is the Chief Executive Officer of IndianOil Technologies Limited, a subsidiary of Indian Oil Corporation, and presently he is GM (PC & Alternate Energy) at IOCL-R&D.


ess than two decades ago, it was not possible to manipulate single atoms or molecules because they were too small for the tools available. However, we know that the laws of physics do not limit our ability to manipulate single atoms or molecules but it was lack of appropriate methods of doing so .With the advances in science & technology, there was advent of “ Nanotechnology”. A new branch of science emerged in the field of applied science, which focuses on the design, synthesis, characterization, and application of materials and devices on the nanoscale. Thus, nanotechnology is an extension of existing sciences in Chemistry, Physics, Biology and other fields into the nano-scale. The rapid progress in nanotechnology is apparent by increasing appearance of the prefix “nano” in scientific journals and in the news. The primary purpose of this article is to very briefly, review the basics of nanotechnology, how it is different from existing material science, what methodologies are available to create nonmaterial and how to characterize these materials. Some applications, only restricted to the petroleum sector, have been reviewed. Considering the tremendous volume of scientific literature, especially in last four years, this paper at best is a very general treatise of the vast subject. In a recent article, Prof. C.N.R. Rao, Chairman of the Prime Minister’s Scientific Advisory Council has observed that though India missed the semiconductor revolution in early 1950’s, but in nanosciences we can be on equal footing with the rest of the world. India has several units of nanosciences and nanotechnology. The major nanotech centers are in IISc, Bangalore, IIT’s and Jawahar Lal Nehru Centre of Advanced Scientific Research (JNCASR). “The Indian researchers can make any Nano-materials at any form required but the biggest challenge lies in assembling of these Nano-materials. We are still looking at technologies to assemble these Nano-materials to make final commercial products. There is a huge demand for Nano-materials globally. India should be ideally catering to this global demand in the years to come”, said Dr. C.N.R. Rao.

What is nano-scale? A nanometer (nm) is one billionth of a meter (10-9 meter) and for a comparison one human hair is about 80,000 nm thick & placing 10 hydrogen atoms side-by-side is roughly 1 nm. Broadly, nanotechnology includes creating materials / structures below 100 nm scale. A number of physical phenomena become noticeably pronounced as the size of system decreases. These include mechanical properties, thermal properties and quantum mechanical effects. Substances in nanoscale can exhibit new properties such as electrical & thermal conductivity, elasticity, greater strength, much enhanced chemical reactivity than what they exhibit at micro or macro scale. The vastly increased ratio of surface area to volume opens new possibilities in surface based science. When the size of a material is decreased then only up to a certain stage the fragmented matter retains the properties of the original material. However, when the size is reduced to nano scale, the quantum behaviour of the material becomes increasingly important as the band structure of the material changes. Therefore, at nanoscale the electrons in the system show confinement and as a consequence behaviour of the material changes. This also explains the transition in physical properties of the material. In nano cluster materials, the surface atoms are highly unsaturated and have free

valances; therefore their behaviour as compared to atoms present in the bulk system is different.

Methodologies of producing nano-materials For generating particles of nano size, two general methodologies are adopted. One approach is a “bottom–up” method where the materials and devices are built atom-by-atom. The second, more commonly employed, approach is “top-down ” where nano materials are synthesized by stripping bulk materials to nano size. Synthesis strategies accommodate precursors from liquid, solid, or gas phase. One may employ chemical or physical deposition approaches; and also rely on either chemical reactivity or physical compaction to integrate nanostructure building blocks within the final material structure. The “bottom-up” approach first forms the nanostructured building blocks and then assembles them into the final material. An example of this approach is the formation of powder components through aerosol techniques and then the compaction of the components into the final material. These techniques have been used extensively in the formation of structural composite materials. The “top-down” approach begins with a suitable starting material and then “sculpts” the functionality from the material. Mostly used top-down apPetrotech Journal December Issue 2009


proach is “milling,” which is simply formation of nanostructure building blocks through controlled, mechanical attrition of the bulk starting material. These nano building blocks are then subsequently assembled into a new bulk material. High energy ball milling, the only top-down approach for nanoparticle synthesis, has been used for the generation of magnetic, catalytic, and structural nanoparticles. The technique, which is already a commercial technology, has been considered dirty because of contamination problems from ball-milling processes. However, the availability of tungsten carbide components and the use of inert atmosphere and / or high vacuum processes have reduced impurities to acceptable levels for many industrial applications. Many current strategies for material synthesis integrate both synthesis and assembly into a single process. Major efforts in nanoparticle synthesis through bottom up approach can be grouped into two broad areas: gas phase synthesis and sol-gel processing. Nanoparticles with diameters ranging from 1 to 10 nm with consistent crystal structure, surface derivatization, and a high degree of monodispersity have been processed by both gas-phase and sol-gel techniques. Initial development of new crystalline materials was based on nanoparticles generated by evaporation and condensation (nucleation and growth) in a subatmospheric inertgas environment. The following schematic figure depicts the variety of techniques covering Bottom up & top down approaches.


Petrotech Journal December Issue 2009

Characterization of Nanomaterials The characterization of nanoparticles can be done by size & component evaluation. In addition to these basic instrument several microscopic (Scanning electron microscope, transmission electron microscope, Atomic Force Microscope, Scanning Tunneling Microscope) & spectroscopic (Auger Electron Spectroscopy, Electron Energy Loss Spectroscopy) instruments are used as secondary chracterization techniques in solution phase synthesis approach. During scaling up & production of nanoparticles stringent quality control of nanoparticles is essential & online characterization can be done throgh lased based spectroscopy & mobility analyzers etc.

Applications of Nano-Technology in Petroleum Sector Even before the term nano -technology was coined, petroleum refining industry has been a major benS. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14

eficiary of the nano -sciences. The popular FCC catalyst of zeolite type have the reactive sites in the pore which fall in nano-range. These zeolites are synthesized by design so that the pores have narrow size distribution which allows only desired hydrocarbon molecules to get in for cracking. Petroleum industry, especially in refining & lubricant sectors has sufficient knowledge of the bulk materials which they usually handle. However, in order to generate “know-why” in addition to “Knowhow” there is a strong need to understand the behaviour of materials at the nano-scale. For example, friction reducing lubricant additives act on the metallic rubbing surfaces (gears, pistons). Knowledge of the nanostructured lubricant layers existing under extreme pressure conditions would be helpful in designing long life lubricants. Some specific examples from hydrocarbon industry where nano -sciences made significant contributions or where developments are taking pace are briefly discussed here.

Application of Nanotechnology in Lubricant Research Reports are available for lab scale & pilot scale study to product commercialization of nano additives in lubricant system having more overbasing capability, efficient load bearing capability, more higher thermal diffusivity, better anti oxidant & anti wear properties. There are reports on development and commercial use of nano size additives in lubrication systems & Nanofluids. Details of them are given in the Table.

Name of nano Additive

Reported in system

Molybdenum disulfide Graphite Molybdenum & tungsten chalcogenides Multi walled carbon nanotube Bismuth Diamond (known as Diamondids) Boric acid Chopped Carbon Nano Fiber (SWNT) Nanofluids Cu Al2O3 CuO BN Molybdenum-sulphur-iodine nanowires

Grease Grease Automotive Oil Automotive Oil Automotive Oil Lube Oil additives Motor Oil Compressor Oil, transformer Oil Coolant Heat transfer fluid Heat transfer fluid Heat transfer fluid Lube Oil Lube Oil

Nano tribology for lubricant development Boundary lubrication involves extreme temperature and pressure conditions on the metallic mating surfaces and the lubricant layer thickness in these conditions is of the order of few nanometers. Advances in nano-tribology has made it possible to study the behavior of lubricant additives in the boundary lubrication conditions and by using grazing angle FTIR, AFM and nano indenter, these nano layers can be characterized.

Application of Nanotechnology in Fuel Research Nanotechnology can also help in the crisis of fuel by increasing the fuel efficiency of engines by dispersing nano fuel additive. These nano fuel additives can make the engine clean in addition to its ability to burn fuel completely, so that the vehicle can emit less carbon dioxide & nitrogen oxides to atmosphere. Dispersant-coated nano cerium oxide (mixed with transition metal oxides) can increase fuel efficiency & it is already in commercial trial by some MNCs worldwide. Microemulsion based fuel additives are also able to increase the fuel efficiency of engine by ability to mix fuel & air more efficiently before combustion & make the engine clean. Carbon nanotubes (CNTs) have welldefined hollow interiors and exhibit unusual mechanical and thermal stability as well as electrical & tribological. This opens intriguing possibilities to introduce other matter into the cavities, which may lead to nanocomposite materials with interesting properties or behavior different from the bulk. A striking enhancement of the catalytic activity of Rhodium & iron particles confined inside nanotubes for the conversion of carbon monoxide & hydrogen to ethanol had been reported by some researchers in Labscale.

Cerium based fuel additives as combustion catalyst Fuel combustion improvers are under intense focus for the obvious reasons i.e. for enhancement in fuel economy & to reduce the pollution load. If these additives are in nano -size they offer

extremely large area to affect oxidative reactions increasing their efficacy at a very low ppm dosage. A diesel oxidation catalyst based on nano-cerium oxide particles has been developed & extensively tested. It helps to enhance fuel efficiency by complete burning of unburnt hydrocarbons & soot generated during the combustion cycle and in the process lowers the amount of carbon monoxide emissions. Neuftec & Envirox had reported to be developed commercial cerium nano -additives which deliver fuel economy by two separate mechanisms. Cerium oxide as a redox catalyst helps to provide an optimum amount of oxygen within the combustion chamber, leading to a more complete and cleaner burn and increased power. In addition, it significantly lowers the temperature at which carbon deposits are burnt off allowing the potential to restore and retain the engine as clean as possible. Envirox has successfully been tried in buses in Hong Kong covering 12 million kilometres. Stagecoach, a bus company from Scotland, is also testing Envirox in about 1000 of their dieselfuelled vehicles. The catalytic activity of cerium oxide is strongly dependent on particle size and surface area. The carbon combustion activation temperature is reduced from approximately 700ºC for micron sized material to 300ºC as the surface area of the material is increased by a factor of 20. Oxygen vacancy atomic point defects are formed more easily on the surface of cerium oxide than in the bulk material and hence high surface area material has a substantially higher catalytic

activity than bulk. A high surface area is the key factor which allows ceramic based catalyst systems to compete with metals such as Platinum or Palladium as combustion catalysts. The efficacy of cerium oxide as a catalyst is related to its ability to undergo a transformation from the stoichiometric CeO2 (+4) state to the Ce2O3 (+3) valence state via a relatively low energy reaction & it may be used as an oxygen storage material in catalysis.

Zeolitic Materials Aluminosilicates (e.g., zeolites) are crystalline porous nanostructures with long range crystalline order with pore sizes which can be varied from about 4 Å to 15 Å (0.4 to 1.5 nm) in conventional zeolites. In 1992, a new family of aluminosilicates (M41S) with pores sizes between 20 and 100 Å in diameter were reported by Mobil researchers. One such material of particular interest is MCM-41, which consists of hexagonal arrays of uniform 2 to 10 nanometer-sized cylindrical pores. Not only can such materials be synthesized, but novel structures such as “tubules-within-a-tubule” have been fabricated as mesoporous molecular sieves in MCM-41.

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In situ synthesis/generation of nano transition metal sulfide either unsupported or supported on matrix (alumina, zeolites) will give more efficient catalyst systems for upgrading of heavy residues in to value added products. There is an increased interest in the synthesis of zeolite nanoparticles (<100nm) due to high external to internal surface ratios resulting in increased resistance to deactivation and for enabling catalysis with large molecules that are unable to enter the zeolite pores. Short channel length zeolite nano crystals provides for fast diffusion times and therefore an increased catalytic activity. Another important feature of nano crystalline zeolites are their ability to form stable suspensions in liquid media, which can have tremendous impact in the preparation/processing of zeolite additives. Nanomaterials are expected to create new opportunities for applications in the fields of separations sciences, for use directly as molecular sieves or as new molecular sieving sorbant materials in catalysis, as heterogeneous catalysts; and as supports for other catalytic materials as well as other novel applications. Another approach to synthesizing large pore and large single crystals of zeolytic materials is being pioneered by Geoffrey Ozin and his group at the University of Toronto, who have demonstrated that crystals as large as 5 mm can be synthesized . The ability to synthesize such large crystals has important implications for discovery of new sensors (selective chemical adsorbants) and membrane devices (selective transport of molecular species), since large single crystals can now be available to the researchers to carry out fundamental studies of adsorption and diffusion properties with such materials.

Carbon Nanotubes (CNT) for hydrogen storage Materials with higher hydrogen storage per unit volume and weight are considered by many to be an enabling technology for vehicular fuel cell applications. Scientists at Los Alamos National Laboratories, US A have developed an approach that enables materials such as Mg to be used for hydrogen storage. Magnesium is of interest because it can store about 7.7


Petrotech Journal December Issue 2009

wt % hydrogen, but its adsorption/ desorption kinetics are slow, i.e., the rate of charge (hydrogen dissociation and hydride formation) is much slower than in metal hydrides. At Los Alamos, high surface area mixtures of nanoscale Mg and Mg2Ni particles are produced by mechanical means & by ball milling. Carbon nanotubes have the interesting property that they could either be semiconducting or conducting (metallic), depending on the chirality and diameter of the nanotube. CNT are associated with extreme mechanical strength & also display highest thermal conductivity. Porous carbons are of interest as molecular sieve materials, both as sorbants and as membranes, or as nanostraws for filtration. One of the major research objectives is to develop materials or structures with exceedingly high storage capacity per unit volume and weight, for gases such as H2 or CH4 so as to become an economic source of combustion fuel or a means to power fuel cells for ultra low-emission vehicles or for electric power generation. CNT are being researched as a possible hydrogen storage media for use in fuel cells. CNT, e.g. can adsorb 10% wt of hydrogen at room temperature as compared to just 5.3 wt % by activated carbon and that too at much lower temperature (77 K). Microporous hollow carbon fibers have exhibited high permeance and high selectivity as hydrogen selective membranes, and development is now

underway to scale up these membranes to commercial levels.

Nanotechnology in E&P Sector Drilling fluids having nano sized superfine powders suspended in conventional drilling fluids have been reported. These materials lead to massive quantitative improvements in the drilling processes. Drillings bits require extreme hardness and nano silicon carbide coated layer on the drilling bits offer advantages for deep drilling in rocky areas. In deep water exploration, nano sensors are under development, which can with stand extreme pressure conditions. Consortium of energy companies is putting millions of dollars into the development of new micro- and nanosensor technologies. The seven companies that make up the Advanced Energy Consortium (AEC), includes BP America, ConocoPhillips, Marathon Oil Company, Occidental Oil & Gas Corporation, Shell International E & P, Schlumberger Technology Corporation and Halliburton Energy Services, will put up $21 million in total to fund the research. The aim of the project is to develop subsurface sensors that can be used to improve both the discovery and the recovery of hydrocarbons. Richard E. Smalley Institute for Nanoscale Science and Technology at Rice University, in Houston is a technical partner to the consortium. Another partner in the project is electrical engineering and

computer science at the University of California, Berkeley. Currently, even with the most advanced recovery techniques, only about 40 percent of the oil and gas in reservoirs can be recovered. The hope of new technology is that by injecting novel sensors into these reservoirs, it will be possible to more accurately map them in 3-D, increase the amount of fuel extracted, and minimize the environmental impact. The financial investment equivalent to $1 million per year from each oil company for three years had already sanctioned.

Potential Health Risks of nano– materials New technologies often introduce new occupational health and safety hazards and nanotechnology is no exception. Materials and devices of nano materials are being built but our current understanding of the health related risks is severely limited. Though the importance of nanotechnology to economy and to our future well-being is established but there is an equally strong need to study the potential adverse impacts of these materials. There are basically two major types of nano structures (i) Nano structured surfaces, nano components (electrical, optical and sensors) where the nano particles are incorporated into the substance or into a device and (ii) Free nano particles, in which at some stage in production or use, the individual particles are present. The first type (fixed) is not at that immediate concern as is the case with free nano particles. Free nano particles can enter into the body when inhaled, swallowed or absorbed through skin. How these particles would behave inside the organism is a big issue, which needs to be researched and resolved. The behaviour of nano particles is a function of their size, shape, surface area and reactivity with the surrounding tissue. These particles may affect regulatory mechanism of enzymes and other proteins. Prof Ken Donaldson, a lung toxicology expert has called for a new discipline – nano toxicology to address the gaps in our knowledge to develop safe nanotechnology. Cerium can affect the respiratory tract and associated lymph nodes (inhalation exposure) and once in the circulatory system it can partition to the skeleton, liver, kidney and spleen.


Corporate News

Nanotechnology promises breakthroughs that will have a fundamental impact on many sectors of economy, leading to new products, businesses, new jobs & new industries. Nanotechnology derives its strength from the fact that vastly increased ratio of surface area to volume opens new opportunities in surface based science, such as catalysis. Petroleum industry, which is already using nanotechnology in some forms, will probably be only next to pharma industry to adopt advances in nano -saciences. The important areas of nanotechnology intervention in the energy sectors are related to enhancing the efficiency of existing systems, new and renewable sources of energy, energy generation, energy storage and energy conservation systems. The characteristic features of nanotechnology intervention / priority in the energy is summarized as follows:

ONGC awards USD 162-million contract to UAE firm Dubai

• • •

The Efforts are Unfocussed and Scattered. The academic institutions are not in a position to provide trained manpower and break through research in the near term. The Efforts Scanty In Comparison To Promising Benefits and requirements Efforts Mainly Based On Individual Efforts And Intuitional Efforts At Inception Stage Efforts Not Coordinated Among Those Initiating Studies

Dec 27 (PTI) India’s oil exploration firm ONGC has awarded an USD 162-million (over Rs 753 crore) engineering and constrution contract for an oil well plateform project at the Mumbai High field to Abu Dhabi based National Petroleum Construction Company (NTPC), UAE’s official news agency wam has said.

Seminar on Hydrocarbon Industry Growth: “Prospects & Challenges in North East” Petrotech Society in association with Numaligarh Refinery Ltd organized a two days seminar on ‘Hydrocarbon Industry Growth: Prospects & Challenges in North East” on 8th & 9th December 2009 at Numaligarh Refinery Township. The seminar was inaugurated by Dr B K Das, Managing Director (Technical), NRI & Mr D K Ghosh, GM (Ops), NRL delivered keynote & welcome address respectively. Mr J L Raina, Secretary General & CEO proposed a vote of thanks. The 2 days seminar was attanded by 30 professors from Technical Institutes in North East.

Suggested Further Readings 1. Nano: The Emerging Science of Nanotechnology, Springer Handbook of Nanotechnology; Bhushan, Bharat (Ed.); 2nd ed., 2007, 2. Micromanufacturing and Nanotechnology; Mahalik, N.P. 2006, Dekker Encyclopedia of Nano Science and Nano Technology 3. Introduction to Nanoscale Science and Technology Series: Nanostructure Science and Technology; Di Ventra, Massimiliano; Evoy, Stephane; Heflin Jr., James R. (Eds.) 2004 4. Encyclopedia of Nanoscience and Nanotechnology; Edited by Hari Singh Nalwa. Editor-in-Chief Journal of Nanoscience and Nanotechnology

Four Maharatnas! ONGC, IOCL, SAIL, NTPC Petrotech Journal December Issue 2009



Nanotechnology Energy and Environment Madhur Sharma, Sangeeta Nagar, Avni Jain, Sachit Goyal, Bhushan Shinde, Maneesha Pande and Ashok N. Bhaskarwar Department of Chemical Engineering, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110 016

Ashok N. Bhaskarwar

Professor Ashok N. Bhaskarwar obtained his Ph.D. from Indian Institute of Science, Bangalore, in 1987 and later had post-doctoral assignments at the State University of Gent, Belgium, and at the I.I.Sc., Bangalore, before joining I.I.T., Delhi, in July 1990. He had been awarded the prestigious INSA Medal for Young Scientist in 1991 and received the BOYSCAST award of Department of Science and Technology, Government of India, in 1994. He had been a Visiting Professor at the famed Department of Chemical Engineering and Materials Science, University of Minnesota, U.S.A., during 1995-96. He had been a member of the Editorial Advisory Board of the international journal "ACH -Models in Chemistry" for several years. More recently, he has been inducted into the advisory and editorial boards of several international journals spanning a wide range from biological and medical sciences to fuel cells. He is an active reviewer for leading international journals like Chemical Engineering Science, AIChE Journal, Applied Catalysis B: Environmental, etc. Professor Bhaskarwar's research interests include reaction and reactor engineering, heat-transfer augmentation, interfacial engineering, flow of fluids through porous media, and pollution-preventing technologies especially the novel printing inks, paints, fuels, and lately development of multifunctional nano-constructs for targeted drug-delivery systems

Abstract The present era is witnessing phenomenal growth in knowledge-based sectors such as science and technology. However, the ever increasing population and the consequent looming danger of depletion of the natural resources such as fossil fuel, clean air, and fresh water, combined with issues like global warming have prompted the need for tapping the potential of this growth in science and technology for developing energy efficient, non-polluting, and as far as possible renewable “clean energy” sources which do not depend on fossil fuels and have a tolerable environmental impact. Concurrently, reliable ways of storage and transmission of energy also need to be developed. Whereas the progress in science and technology, on one hand, has resulted in rapid industrialization, on the other hand, it has also raised issues like air pollution and increased pollution of ground water. The dire health-related and environmental consequences of such pollution need to be addressed by way of developing newer technologies for effective and efficient treatment of ground water to make it safe for drinking and use. Fortunately, nanotechnology seems to have the capacity to provide many breakthroughs, including those in the energy and environmental sciences. This article provides an overview of the long (and also short) strides that nanotechnology has already taken in the fields of energy and environment, promising the future generations a cleaner and safer environment to unfold their potentialities in. Keywords: Photovoltaic cells, thermal batteries, quantum dots, supercapacitors, nanowires, hydrogen storage, fuel cells, carbon nanotubes, carbon nanohorns, aerogels, biofuel cells, nanostructured membranes, nanoreactive membranes, bimetallic nanoparticles.

Introduction Most of the present world’s energy supply comes from fossil and nuclear sources. Though there is no imminent danger of depletion of fossil fuel resources, the fact that it is non-

renewable invariably implies that it cannot last indefinitely. Andrew Moore has stated in his article “Short circuiting our fossil fuel habits” that over a period of 400 years we would have liberated most of carbon stored as fossil fuel, again as carbon dioxide [1] . This carbon dioxide cannot be recycled back into organic matter fast enough to prevent global warming. Besides this, the problem of generation of green house gases from use of fossil fuel is an added cause of concern. Therefore, it is our obligation to the posterity that we use the time that we have before the present reserves of fossil fuel start getting scarce, to develop alternative “clean energy” sources which are preferably renewable and do not depend, in turn, on fossil fuels for their generation. The present non-polluting alternative to fossil fuel is electricity. However, two-thirds of this is generated from fossil fuel. An additional problem with the use of electricity is the storage of electric power. As yet, no battery that has an energy density equivalent to that of petrol exists. Recharging of batteries is also far slower as compared to refilling of petrol tanks. An improvement in the lifetime of batteries and lighter nontoxic materials of construction are representative aspects that need to be addressed before contemplating upon these as alternatives to fossil fuels. Concomitant with these improvements, any alternative energy technology would need to be efficient in energy transmission also. In essence, the main challenges that the energy sector faces are efficient optimized techniques of energy-source utilization, energy conversion, energy distribution and energy storage. Simultaneously, the technology addressing the above issues must also be cost effective. Nanotechnology has the potential to positively impact all the above areas and to provide an immense value addition in all the known alternative energy resources by exploiting the three fundamental sciences, viz. Physical, Chemical, and Biological Sciences. In the present article, we provide an overview of nanoenergy spanning across the whole breadth of science and also touch upon some of the environmental aspects.

Nanotechnology and Energy Nanoenergy and the Physical Sciences

The rapid progress of research in nanotechnology has resulted in the development of a variety of nanomaterials with physical and chemical properties entirely different from those of the bulk materials. These nanomaterials are being exploited for their potential in the areas of energy generation, distribution, and storage. These materials have been successfully used for value additions in the existing capacities of photovoltaic cells and the conventional Li-ion batteries, enhanced hydrogen storage capacities, development of supercapacitors, etc. Besides these new materials, developments of hybrid technologies for energy generation have also been made possible. Some of the recent developments in these areas are described in the following sections. Nanotechnology in Solar Energy Conversion

The most abundant and “perennial” source of energy as an alternative to fossil fuels is SUN. Solar energy has already been exploited in a number of ways so that it approaches the fossil fuels as closely as possible. The main impediments in exploiting the solar energy as an alternative energy source is the conversion efficiency and difficulties related to its storage. Nanotechnology has potential solutions to both these issues. Presently, amorphous silicon solar cells have been developed for conversion of solar energy into electricity. One of the biggest problems with a-Si solar cells is the material used for its semiconductor. Silicon is not always easy to find on the market, where demand often exceeds supply. Secondly, the a-Si cells are not particularly efficient. Theoretically, the maximum efficiency for silicon-wafer cells is about 50 percent, meaning that half of the energy striking the cell gets converted into electricity. In reality, silicon-wafer cells achieve, on an average, 15 to 25 percent efficiency. Thirdly, a-Si solar cells suffer significant degradation in power output when exposed to the sun. Thinner a-Si cells overcome this problem, but thinner layers absorb sunlight less efficiently. Taken together, these qualities make a-Si Petrotech Journal December Issue 2009


Figure 1. CIGS-on-foil photovoltaic cell

A copper indium gallium deselenide (CIGS) solar cell using foil

cells great for smaller-scale applications such as calculators, but less than ideal for larger-scale applications like solar-powered buildings. Promising advances in non-silicon thinfilm photovoltaic (PV) technologies are beginning to overcome the issues associated with amorphous silicon. The newer generation cadmium telluride (CdTe) and copper indium gallium deselenide (CIGS) semiconductors seem to be acceptable alternatives. Thin film solar cells

A CIGS thin film solar cell has been developed by Nanosolar, a company based in San Jose, California. It is laid in the form of a film of an ink containing nanoparticles of the four elements. These individual nanoparticulate elements self-assemble in a uniform distribution, ensuring that the atomic ratio of the elements is always correct. Two types of CIGS thin-film PV cells have been developed; the CIGS on glass and CIGS on foil. Figure 1 shows the various layers in a CIGS-on-foil solar cell and the technique used to lay the solar-energyabsorbing ink onto a conductive metal foil. The conjugated polymers in the thin film CIGS solar cells are able to absorb a photon and generate an exciton that can dissociate into an electron– hole pair under the strong electric field found at polymer/metal interfaces. The


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Laying of solar absorbing nanoink on a conductive metal film

most efficient design of organic solar cells uses a bulk heterojunction composite of a conjugated polymer with nanoscale electron acceptors forming a percolating network through the thin film. The CdTe thin film solar cells are simillar to CIGS solar cells except that these have CdTe and CdS as the n-p type semiconductor material and SnO2/CdSnO4 and carbon paste infused with Cu as the electrode material [2]. The efficiencies of the thin film solar cells have not yet reached those of the currently available silicon based PV cells. The cost reduction is however one tenth of the current silicon solar cells. Secondly, a problem with the use of cadmium in thin film solar cells is that cadmium is a highly toxic substance and can accumulate in food chains, causing a serious health concern. No technology having such a drawback can claim to be a part of the “green” revolution. However, more research in this area is expected to remove these shortcomings. Already, the National Renewable Energy Laboratory and several other agencies and companies are currently investigating cadmium-free thin-film solar cells.

crystalline silicon substrate of a photovoltaic (solar) cell. This increases voltage output, by as much as 60%, by fluorescing the incoming light prior to capture. The use of nanowires for quick and efficient electron transport is also being explored. Dye-sensitized solar cells

Dye-sensitized solar cell technology, invented by Michael Grätzel at EPFL in the 1990s, shows a great promise as a cheap alternative to the expensive silicon solar cells. Dye-sensitized cells imitate the way that plants and certain algae convert sunlight into energy. The cells are made up of a porous film of tiny (nanometer sized) white pigment particles made out of titanium dioxide. The latter are covered with a layer of dye which is in contact with an electrolyte solution. When solar radiation hits the dye, it injects a negative charge in the pigment nanoparticle and a positive charge into the electrolyte resulting in the conversion of sunlight into electrical energy. These cells are inexpensive, easy to produce and can withstand long exposure to light and heat compared with the traditional silicon-based solar cells. New efficiencies are being benchmarked by such cells [3]. Bifacial photovoltaic cells

Other developments in this area include use of ultra-high purity silicon nanoparticles in the form of silicon nanoparticle quantum dots on the poly-

Bifacial PV cells with increased efficiencies have recently been developed where the dye-sensitized solar cells are placed in front of a white semitrans-

Figure 2. A schematic diagram of a dye-sensitized solar cell operating in bi-facial mode in front of a white reflector.

Figure 4. Fabrication of the nanocomposite paper units for supercapacitor and battery. (a) Schematic diagram of the supercapacitor and battery assembled by using nanocomposite film units. The nanocomposite unit comprises RTIL ([bmIm][Cl]) and MWNT embedded inside cellulose paper. A thin extra layer of cellulose covers the top of the MWNT array. Ti/Au thin film deposited on the exposed MWNT acts as a current collector. In the battery, a thin Li electrode film is added onto the nanocomposite. (b) Photographs of the nanocomposite units demonstrating mechanical flexibility. Flat sheet (top), partially rolled (middle), and completely rolled up inside a capillary (bottom) are shown. (c) Cross-sectional SEM image of the nanocomposite paper showing MWNT protruding from the cellulose–RTIL thin films. (Scale bar, 2 μm.) The schematic diagram displays the partial exposure of MWNT.

parent reflector so that the cells collect sunlight from both sides, i.e. the light coming from the front and that reflected by the reflector [4]. Figure 2 shows a schematic diagram illustrating the working of this type of cells. Hybrid nanowire dye-sensitized solar cells

Here the traditional nanoparticlesbased film is replaced by a dense array of oriented crystalline nanowires, and the efficiencies depend on the surface area of the nanowires. Though the hybrid solar cells have low conversion efficiencies, these are some of the most stable solar cells [5]. Schematic diagram of this type of solar cells is shown in figure 3.

in LiSi/FeS2 thermal batteries. With the same weight, the nanostructured cathode pellets are 23% thinner than their conventional counterparts resulting in an increase in pellet density by about 31%. The volume of the battery Nanostructured thermal batteries with can be reduced significantly. Owing to high power density the nanostructure, the electrode maNanostructured FeS2 has been syntheterials of these thermal batteries react sized and used as the cathode material more rapidly and completely during the discharge resulting in a Figure 3. Schematic diagram of a nanowire dyeremarkable increase in ensensitized cell. Light is incident on the bottom ergy output [6]. electrode.

Nanostructured lithium-ion batteries

Lithium-ion batteries are one of the great successes of modern materials electrochemistry. A lithium-ion battery can provide about 300 Watt-hours per liter. Recent research involves electrodes made of nanomaterials. The advantages

of using nanomaterials for electrodes in such batteries are: i) better accommodation of the strain of lithium insertion/removal, thus improving cycle life; ii) new reactions not possible with bulk materials are realized with these nanomaterials iii) higher electrode/electrolyte contact area leading to higher charge/discharge rates; iv) short path lengths for electronic transport (permitting operation with lower electronic conductivities or at higher power); and v) short path lengths for Li+ transport (permitting operation with lower Li+ conductivities or at higher power). Nanotechnology has enabled the integration of an electrode, separator, and electrolytes in a single paper thin unit which can serve as a building block for a variety of mechanically flexPetrotech Journal December Issue 2009


ible energy storage devices. A paper thin lithium-ion battery incorporating multiwalled carbon nanotubes has been developed [7]. Figure 4 shows the construction components of such a nanocomposite paper battery. The two essential materials, viz. cellulose and carbon nanotubes, provide inherent flexibility and porosity to the system. From nano-optics to street lights

Nanocrystal quantum dots (NQDs) are nanometer-scale particles that are known to be very efficient light emitters, whose wavelength and colour can be controlled through their size. NQDs possess good chemical and luminescent stability and are relatively easy to produce. The major drawback of using them as a light source is the difficulty of exciting them electrically owing to the fact that each quantum dot has an insulating layer of organic molecules on its surface. Klimov et al. [8] proposed a unique structure for the proposed light emitting device (figure 5). A semiconductor quantum well (purple) is electrically excited through the correspondingly doped layers (ndoped indicated by the minus signs and p-doped by plus signs). The injected electron and hole carriers in the quantum well form pairs indicated by ± signs and recombine. The released energy is non-radiatively (by Förster mechanism) transferred to the NQDs (red spheres) at the top of the system. The NQDs are covered by a stabilizing layer of organic molecules shown Figure 5. Quantum dot based light emitting device.

as white cones. The transferred energy is released mostly as optical radiation, shown as the red glow, whose frequency is tunable by the size of the quantum dots.

deposition methods (figure 6). Ultrahigh-power electrochemical double layer capacitors can be engineered using these hybrid nanowires, resulting in a very high power density [10].

Nanomaterials for energy conversion and storage

Nanotechnology in hydrogen storage

The increased surface area of nanoparticles makes it possible to achieve higher storage capacities in relatively small volumes. This has led to the development of supercapacitors. Supercapacitors

Supercapacitors are of key importance in supporting the voltage of a system during periods of increased loads in everything from portable equipment to electric vehicles. Recent trends in supercapacitors involve the development of high-surface-area activated carbon electrodes to optimize the performance in terms of capacitance and overall conductivity. Attention has been focused on nanostructured carbons such as aerogels, nanotubes, and nanotemplates [9]. The advantages of carbon aerogels lie mainly in their low ionicand electronic-charging resistances and in their potential use as binderless electrodes. Replacing the standard carbon fibre with carbon aerogel electrodes improves both capacitance and cyclability. Hybrid nanowire arrays as high-power supercapacitor electrodes

Arrays of multi-segmented hybrid nanostructures of carbon nanotubes and gold nanowires have been synthesized using a combination of chemical vapour deposition (CVD) and electro-

Storage of hydrogen is currently the greatest obstacle in the way of its feasible and commercial use. It is therefore a topic of considerable contemporary research the world over. Carbon nanomaterials, particularly carbon nanotubes, have been found to have an immense capacity to accept and release substantial quantities of hydrogen via physisorption and chemisorption. Nanomaterials studied for this purpose are carbon nanotubes as such, and with different additives incorporated like Ti doped single-walled nanotubes (SWNTs). Metal organic frameworks (MOFs), graphite nanofibres, nanohorns , graphitic carbon inverse opal (GCIO - a new class of microporous carbon material), and mesoporous carbon, to name a few, are the other nanomaterials studied [12] . Figure 7 presents a comparison between the storage capacities of carbon nanotubes and other conventional hydrogen storage systems [11]. Piezo-electric nanogenerators

Piezo-electric nanogenerators consist of tiny nanowires composed of zinc oxide which are grown on gallium arsenide, sapphire, or a flexible polymer substrate. A zigzag silicone electrode containing thousands of nanometer-scale tips, made conductive by platinum coating, is lowered over these nanowires which are vertically aligned about half a micron

Figure 6. Schematic diagram showing the supercapacitor device with CNT/ AuNW electrodes. The Au segment of each electrode in contact with the Cu layer acts as the current collector.


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Figure 7. Comparative storage capacities of carbon nanotubes and other conventional H2 storage materials.

layered silicon substrate. The top layer consists of thin film solar cell embedded with dye coated zinc oxide nanowires. On the underside of the silicon is a jagged array of polymer-coated zinc oxide nanowires in a toothlike arrangement. When the device is exposed to vibrations, these “teeth” scrape against an underlying array of vertically aligned zinc oxide nanowires, creating an electrical potential. The solar cell and the nanogenerator are electrically connected by the silicon substrate itself, which acts as both the anode of the solar cell and the cathode of the nanogenerator. Thus, one is light active and the other can work in the dark [14]. Nanoenergy And The Chemical Sciences Fuel cells

apart. The space between the nanowires is just enough for them to be able to flex within the gaps created by the electrodes. Mechanical movements such as vibrations of the whole set-up causes the nanowires to intermittently brush over the electrode tips, transferring their electrical charge to the tips, and sending a stream of electrons through the system. A schematic representation of such a nanogenerator is shown in figure 8. Currently, a single nanowire is capable of producing only picoamps of current. This is expected to increase to 20-80 milliwatts per square meter of the “fabric”. With better techniques of controlling growth, density, and uniformity of the nanowires, the current generated by these nanogenerators could be as much as 4 watts of energy per cubic centimeter, which could be enough to serve low-

power applications like micro-surgical implants. This technology further holds a promise of affording decentralized energy sources like personal energy nanogenerators where the vibrational energy generated by people walking above could be transformed into electrical energy (piezo-electric treadmills), or generation of electricity from the constant swaying of tall buildings. A hybrid nano-energy harvester

Recently, researchers have combined a nanogenerator with a solar cell to create an integrated mechanical- and solar-energy-harvesting device (figure 9). This hybrid generator is the first of its kind and might be used, for instance, to power airplane sensors by capturing sunlight as well as engine vibrations. It consists of zinc oxide nanowires in a

Fuel cells promise an energy capacity at least ten times greater than that of conventional batteries. Whereas lithium-ion battery can provide 300 watthours per liter, the methanol in a fuel cell has a theoretical capacity of up to 4800 watt-hours per liter. Imagine your laptop running for a full day without needing to recharge! Industry leaders such as Toshiba, IBM, and NEC have been pouring funds into fuel-cells research because of their very high potential of generating increased capacity compared to conventional batteries [16]. Different types of fuel cells, suited for different applications, have been developed: Figure 9. Nano-hybrid energy harvester: A dye-sensitized solar cell (top) and a nano-generator (bottom) sit on the same substrate in the new device.

Figure 8. Piezoelectric nanogenerator. Adapted from [13

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Polymer electrolyte membrane fuel cell (PEMFC): transportation applications

Figure 12. A block of an aerogel.

Solid oxide fuel cell (SOFC): largescale stationary power generators Alkaline fuel cell (AFC): space applications Molten-carbonate fuel cell (MCFC): large stationary power generators Phosphoric-acid fuel cell (PAFC): small stationary power-generation systems Direct-methanol fuel cell (DMFC): low-power portable applications. Catalytic surface areas and various techniques to increase surface areas

The capacity of fuel cells is based on the fact that more the fuel you can bring into contact with the catalyst, the more is the current that can be drawn from the cell. Thus, a high catalytic surface area is the key to efficiency. Considering the rapid developments in nanotechnology, nanoparticles and nano-structured materials offer new avenues for controlling the catalytic activity. A number of nanoparticles have been used for the purpose. To compress more power into smaller volumes, researchers have begun to build fuel cells on the fuzzy frontier of nanotechnology. Techniques such as silicon etching, evaporation, and other processes borrowed from chip manufacturers have been used to create tightly packed channel arrays to guide the flow of fuel through the cell. Research efforts are towards pack-

ing a large catalytic surface area into a wafer-thin volume. This approach is expensive as well as inherently limited by its two-dimensional nature [16]. Other techniques are also being developed for increasing the surface area of a catalyst. Carbon nanohorns (CNHs) which form a spherical aggregate structure with many horns projecting (figure 11), seem to be suitable for supporting fine platinum-catalyst particles with good dispersion, resulting in increased power density [18]. Aerogels, a honeycomb of very small nanoparticles, all joined up to form something that is almost as light as air (these actually contain about 99% air) can be a good catalyst with a large surface area (figure 12 ) [19].

Figure 11. 3D-distribution of electrons in carbon nano-horn

Lanthanum nanoparticles, cerium nanoparticles, strontium carbonate nanoparticles, manganese nanoparticles, manganese-oxide nanopowder, nickel-oxide nanopowder, and several other nanoparticles are finding application in the development of small cost-effective solid oxide fuel cells (SOFCs). The winner amongst electrocatalysts

A major hurdle to the commercial use of direct ethanol fuel cells is the molecule's slow, inefficient oxidation, which breaks the compound into hydrogen ions and electrons that are needed to generate electricity. At Brookhaven, scientists have found a winner. Made of platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles (figure 10), the research team's electro-catalyst is capable of breaking carbon bonds at room temperature and efficiently oxidizing ethanol into carbon dioxide as the main reaction product. Other catalysts, by comparison, produce acetaldehyde and acetic acid as the main products, which make them unsuitable for power generation [17]. Adding fire to the fuel

It is known that nanoparticles can improve the performance of solid fuels. This has been extrapolated to liquid fuels by Patrick Phelan and co-workers (2008) to get similar results. They reported that adding aluminium and aluminium-oxide nanoparticles to liquid diesel fuel can cause it to ignite more


Petrotech Journal December Issue 2009

Figure 10. Model of a ternary electro-catalyst for ethanol oxidation consisting of platinumrhodium clusters on a surface of tin oxide.

easily. High surface-area-to-volume ratio and small inter-particle distances between nanoparticles can significantly improve radiative and heat/mass transfer, thereby reducing the time it takes for the fuel to ignite. This finding is expected to have a great impact on the efficiency and emission levels of diesel engines [15]. The capture of nanoparticles from the exhaust would however still be a challenge to overcome. Nanoenergy (and Nanotechnology) and the Biological Sciences

Much may be learnt from nature, if not even more from living in tune with it! Life and living processes always have a lot to teach us, if and if only we have the sensitivity and wisdom to learn, the two qualities human beings seem to have conspicuously lacked ever since the dawn of industrial revolution. Judicious choice of research directions enabled by biological sciences may pave the way to meet our present and future energy needs without jeopardizing our existence on this unique planet. In this section, we touch upon the major developments in nanoenergy generation which the knowledge in biological sciences has guided. Photosynthesis for generation of energy

Photosynthesis generates a remarkable 90 terawatts of power with proteins such as Photosystem I. These proteins could be harnessed to generate electricity as a final product rather than the chemical energy. These naturally massproduced, biological light-harvesting

complexes could be integrated with non-biological materials. For this purpose, biomimetic photoenergy conversion systems are being devised which make use of photo- active protein complex Photosystem I (PS I), immobilised on the surface of nanoporous gold leaf (NPGL) electrodes, by which photoinduced electric current is driven through an electrochemical cell [20]. PS I, extracted from spinach and algae, has been used for the purpose. Chlorophyll in marine algae living 20 m deep may be better than spinach at capturing solar energy [21].

Instead of chlorophyll, synthetic pigments embedded in crystalline metal-oxide membranes have attracted interest to produce electricity from sunlight. In yet another development, to produce solar electricity, novel organic solar cells have been constructed by quaternary self-organization of porphyrin and fullerenes with gold nanoparticles. Figure 13 shows such a porphyrin-fullerene-gold nanoparticle electrode based photo-electrochemical cell. Composite cluster electrode, when illuminated by visible light, produces photocurrent with an incident photonto- photocurrent efficiency (IPCE) as high as 54% [22]. Bio-fuel cells

conversion of bio-fuel into electric current. Enzyme based bio-fuel cell: This uses redox enzymes for conversion of biofuels into electric current. These enzymes are usually immobilized on a suitable membrane for the purpose. Membraneless bio-fuel cell: Here, direct electron transfer occurs between the active site of the enzyme and the electrode via a mediator based molecule. The power density, lifetime, and operational stability of these bio-fuel cells are far below those of the chemical fuel cells. There has been a lot of improvement in performance of bio-fuel cells during the last decade. Charge densities of less than a tenth of a mWm-2 in the year 2000 have shown an increase to tens of Wm-2 by the year 2008. However, this is still lower than what is supplied by fuel cell technology or that required by a cardiac pacemaker or for power supply to an electric grid [23]. The current research efforts are expected to further increase this performance, especially with the recent rapid developments in nanotechnology. The main potential of nanostructures lies in providing a high surface area to the electrodes and an improved capacity of attaching, stabilizing, and activating enzymes which is well beyond that of traditional immobilization techniques. The resulting increased enzymes loading would lead to improved power densities.

A bio-fuel cell is a bio-electrochemical system that drives a current by mimicking bacterial interactions found in nature. There are presFigure 13. Porphyrin-C60-gold electrode in a photoently three types of electrochemical cell biofuel cells: Microbial bio-fuel cell: A microbial fuel cell (MFC) is a bioreactor that converts chemical energy in the chemical bonds in organic compounds into electrical energy through catalytic reactions of microorganisms under anaerobic conditions. This uses whole microbes including viruses for Petrotech Journal December Issue 2009


Nanoparticles for enzyme immobilization

Figure 15. Nanofibres as rolled up mats.

The nanostructures used for immobilization of enzymes are mesoporous media, nanoparticles, nanofibres, and nanocomposites [24]. Figure 14 shows the different techniques used for immobilization of enzymes on different types of nanostructures. Figure 14.1. Different types of attachments on mesoporous silica achieved for development of stable enzyme system

A. Adsorption B. Covalent attachment C. Partial closure of mesopore inlets D. Nano-composite shell on particle surface E. Crosslinked enzyme aggregates via ship-in-a-bottle approach. Figure 14.2. Enzyme immobilization on nanofibres

Figure 14.3. Immobilization of SENs on nano-structured matrices such as well aligned carbon nanotubes and nano-porous media.


Petrotech Journal December Issue 2009

Nanoparticles have an obvious advanbio-fuel generator to break down motage of greater enzymes loading due lecular hydrogen in-vitro in presence to increased surface area. However, of SWNTs (figure 16) [27]. recovery of nanoparticle-attached enzymes from reaction solution for reNanotechnology and Environment use is difficult. The solution to this problem is offered by combining the Nanotechnology for water purification and waste treatment enzymes with magnetic nanoparOne of the serious repercussions of cliticles (eg. lipase attached to γ-Fe2O3 mate change and other direct instances nanoparticles via covalent bond).The of human recklessness, and a serious enzyme-bound magnetic nanoparticles cause of concern, is the ever-reducing can be separated from the reaction mesupply of fresh water. The increasing dium simply by applying a magnetic pollution of ground water and surface field. Alternately, nanofibres or carbon water, due to increased use of fertiliznanotubes can be used for this purpose. ers and pesticides and contamination Electro-spun nanofibres are becoming with chemicals, detergents, heavy metvery popular because they have better als, etc. because of inadequate indusmass-transfer capacities due to their trial wastewater disposal procedures, is reduced thickness. Secondly, recovery expected to have an immense adverse for reuse is easier, and thirdly, these impact on environment/eco-systems, can be further processed into strucand public health. It is therefore imtures such as woven mats, rolled-up perative that newer technologies be mats (figure 15) [26], well-aligned arrays, or membranes. The electro-spinning procedure Figure 16. Model of a CaHyd I protein bound to a for their preparation is also single walled carbon nanotube very simple [25]. Biotechnology combined with nanotechnology

Escherichia coli recombinant technology was used to overexpress a gene (CaHyd I) from anaerobic bacterium Clostridium acetobutylicum that codes for protein hydrogenase I. This protein is used as a

developed for efficient treatment of the groundwater to make it safe for drinking. A number of nanotechnology based products and processes are being developed for improving the quality of water to a potable level.

Figure 18 . Multi-branching molecules like this dendrimer may one day be used to capture uranium in contaminated water

Nanotechnology in water treatment

Water treatment and remediation involves the removal of impurities in water through advanced filtration methods to enable greater recycling and reuse. The first generation techniques were sedimentation, flocculation and coagulation processes which were gradually replaced by membrane based processes such as microfiltration, ultrafiltration, nanofiltration, and nanofiltration with reverse osmosis. Use of nanotechnology based membranes is now being explored for this application [28]. These membranes may be either nanostructured membranes such as based on carbon nanotubes (figure 17) with a water-repellant inner surface through which only water can pass while viruses, bacteria, toxic metal ions and other organic molecules are kept out [29], or nanoreactive membranes which have a functionalized surface for adsorption of the impurities present in water. Figure 17. Carbon nanotubes for wastewater treatment.

Table 1 gives examples of the various membranes that are being developed. In addition to the nanoparticles mentioned in the table, multi-branching molecules like dendrimers could clean up fluorides, chlorides, nitrates, bromides, phosphates and, in particular, perchlorates which are responsible for hypothyroidism, from water and environment (figure 18).

has been exploited lately, and a number of consumer products containing silver nanoparticles have entered the market. Socks containing silver nanoparticles designed to inhibit the notorious odorcausing bacteria have been introduced; washing machines that disinfect clothes by generating silver nanoparticles have also been developed. That should let many of us breathe easier too! Silver nanoparticles are however also extremely toxic. They have been found to destroy even the benign species of

This modified dendrimer tailored to capture aromatics was patented at the end of the year 2008. Subsequently, a dendrimer Figure 19. Dendrimer enhanced filtration and enhanced ultrafiltration pro- recovery of dendrimers for reuse. cess has been reported by Diallo et al. [30,31], wherein Poly(amidoamine) dendrimers are used for recovery of metal ions from aqueous solutions. The metal ion laden dendrimers can then be regenerated by decreasing the solution pH to 4.0, enabling recovery of the bound copper ions and recycling of the dendritic polymer for further use (figure 19). Silver has been known to have the ability to kill harmful bacteria. This knowledge Petrotech Journal December Issue 2009


Table 1. Examples of nanostructured and nanoreactive membranes used in water filtration. Adapted from [28]. Membrane


Nanostructured membranes Carbon nanotubes Nanoreactive membranes

Bacteria and viruses

Alumina membranes functionalized with poly (styrene sulfonate) Divalent cations or poly(allylamine hydrochloride) Silica and cellulose-based membranes functionalized with amino Metal ions acid homopolymers Polycarbonate track-etched membranes functionalized with amino acid homopolymers

Metal ions

Pt/Fe laden cellulose acetate film Zero-valent Fe laden cellulose acetate membrane

Trichloroethylene (TCE) TCE

Ni/Fe or Pd/Fe laden polyacrylic acid/polyether sulfone composite TCE membranes Ni/Fe laden cellulose acetate membrane Alumina or polymeric membranes with gold nanoparticles Polymer-impregnated ceramic TiO2 filters Polymer-impregnated ceramic alumina and silicon-carbon filters

bacteria that are used for wastewater treatment [32]. Product designs would therefore need to address the fact that the nanoparticles are not let loose. The most recent development in the area of water purification is Tata group of companies’ low cost water filter “Swach” which combines ingredients like rice-husk ash with superior nanotechnology-based ingredients like silver nanoparticles to create a water filter which meets international waterpurification standards. Figure 20 shows a schematic diagram of the original filter design and the recently launched water-filter unit which is capable of

TCE 4-nitrophenol Polycyclic aromatic hydrocarbons (PAHs) Trihalogen methanes, PAHs, pesticide

producing 3000 L of clean safe water without the requirement of electricity or running water. Rice-husk ash is impregnated with silver nanoparticles which consequently acquires the capacity to kill bacteria and disease-causing organisms [33]. Nanotechnology for water remediation

The industrial effluents contain innumerable contaminants which include heavy metals, toxic chemicals, detergents, pathogenic micro-organisms, etc. Nanomaterials can play an important role in removal of such contaminants from wastewater efficiently and rapidly because of their enhanced re-

Figure 20. Low-cost water filter based on rice-husk ash impregnated with silver nanoparticles.

activity, high surface areas and strong sequestration characteristics. Aggressive research efforts are underway for affording increased affinity, capacity, and selectivity to the plethora of existing nanomaterials. Table 2 lists the different nanomaterials at various stages of development for effective treatment of industrial effluents, ground water, surface water, and drinking water. In the backdrop of these research efforts, the work done by Zhang et al. [34] needs a special mention. They have developed zero-valent nanoscale iron particles for in-situ clean-up of ground water. Bimetallic particles (Pd/Fe, Pd/Zn, Pt/Fe, Ni/Fe) are even more reactive than plain iron powder for removal of chlorinated aromatic compounds [35]. Table 3 gives a list of environmental contaminants that can be removed by iron nanoparticles. The laboratory studies, followed by field studies, demonstrated that these nanoparticles could be injected directly into contaminated aquifers to form an in-situ system for removal of a number of contaminants from the ground water (figure 21). The disadvantage of metallic/bimetallic nanoparticles is that they tend to aggregate and adhere to the soil surfaces. Mallouk’s group at Pennsylvania State University has explored use of carbon/hydrocarbon nanoparticles which could be used as support for the metallic/bimetallic nanoparticles, importantly preventing aggregation [36]. Hydrophobic and hydrophilic carbon supports could be used to enhance the time-scale of suspension and permeability of the nanoparticles in the ground. Nanomaterials in photo-catalysis of degradation of pollutants in wastewater

a. Schematic diagram of the original filter design


Petrotech Journal December Issue 2009

b. Actual filter

Rapid developments of industries at all scales and fast increase in population densities of cities have unfortunately witnessed a variety of toxic and hazardous substances, especially organic pollutants, constantly being discharged into natural water bodies often without adequate treatment. Photo-catalysis has gained a lot in importance for wastewater treatment because it can completely degrade the organic pollutants into relatively stable inorganic substances (such as CO2, H2O,etc.) under moderate conditions, without causing serious secondary pollution. It is well known that nano TiO2 is one of the suitable

Table 2. Variety of nanomaterials, in various stages of R&D, each possessing unique functionalities for remediation of industrial effluents, ground water, surface water and drinking water. Adapted from [28]. Nanopaticle/Nanomaterial


Nano-crystalline zeolites

Toluene, nitrogen dioxide

Carbonaceous nanomaterials Activated carbon fibers (ACFs) CeO2-carbon nanotubes (CNTs)

Benzene, toluene, xylene, ethyl-benzene Heavy metal ions

Carbon nanotubes CNTs functionalized with polymers CNT functionalized with Fe Single-walled carbon nanotubes Multi-walled carbon nanotubes

p-nitrophenol benzene, toluene, dimethylbenzene, Heavy metal ions Trihalomethanes (THMs) Heavy metal ions THMs Chlorophenols Herbicides Microcystin toxins

Self-assembled monolayer on mesoporous supports (SAMMS) Anion-SAMMS Thiol-SAMMS HOPO-SAMMS

Inorganic ions, Heavy metal ions Actinides and lanthanides


Heavy metal ions

Zero-valent iron nanoparticles (nZVI)

Polychlorinated biphenyls (PCBs) Inorganic ions, Chlorinated organic compounds, Heavy metal ions

Bimetallic nanoparticles Pd/Fe nanoparticles

PCBs Chlorinated ethene Chlorinated methanes

Ni/Fe nanoparticles Pd/Au nanoparticles

TiO2 photo-catalysts Nanocrystalline TiO2, Nitrogen (N)-doped TiO2, Fe(III)-doped TiO2, Supported TiO2 nanoparticles, TiO2-based p-n junction nanotubes

Table 3. Common environmental contaminants that can be transformed by nanoscale iron particles. Adapted from [36] Chlorinated methanes Carbon tetrachloride (CCl4) Chloroform (CHCl3) Dichloromethane (CH2Cl2) Chloromethane (CH3Cl)

Chlorinated benzenes Hexachlorobenzene (C6Cl6) Pentachlorobenzene (C6HCl5) Tetrachlorobenzenes (C6H2Cl4) Trichlorobenzenes (C6H3Cl3) Dichlorobenzenes (C6H4Cl2) Chlorobenzene (C6H5Cl)

Other polychlorinated Pesticides DDT (C14H9Cl5) Lindane (C6H6Cl6)

Organic dyes Orange II (C16H11N2NaO4S)

TCE and PCBs, Dichlorophenol, Triclorobenzene, Chlorinated ethane, Brominated organic compounds (BOCs), TCE

Heavy metal ions, Azo dyes, Phenol, Aromatic pollutants, Toluene

Figure 21. Nanoparticle based in-situ system for transformation/detoxification of common groundwater contaminants. Adapted from [36]

Chrysoidine (C12H13ClN4) Tropaeolin O (C12H9N2NaO5S) Acid Orange Acid Red

Heavy metal ions Mercury (Hg 2+) Nickel (Ni 2+) Silver (Ag +) Cadmium (Cd 2+)

Trihalomethanes Bromoform (CHBr3) Dibromochloromethane (CHBr2Cl) Dichlorobromomethane (CHBrCl2)

Chlorinated ethenes Tetrachloroethene (C2Cl4) Trichloroethene (C2HCl3) cis-Dichloroethene (C2H2Cl2) trans-Dichloroethene (C2H2Cl2) 1,1-Dichloroethene (C2H2Cl2) Vinyl chloride (C2H3Cl)

Hydrocarbons PCBs Dioxins Pentachlorophenol (C6HCl5O)

Other organic contaminants N-nitrosodimethylamine (NDMA) (C4H10N2O) TNT (C7H5N3O6)

Inorganic anions Dichromate (Cr2O2  7 ) Arsenic (AsO3  4 ) Perchlorate (ClO 4 ) Nitrate (NO 3 )

semiconductors for photo-catalysis. Therefore, a composite reactor with nano TiO2 (excited by uv energy) as photocatalyst, in which H2O2 is used additionally, for degradation of organic pollutants has been devised for polluted water treatment [37]. Nanotechnology for environmental clean-up

The destruction of sulfur-dioxide (DeSOx) is a very important problem in environmental chemistry. Sulfurdioxide is frequently formed during the combustion of fossil-derived fuels in factories, power plants, houses, and automobiles. Annual negative effects of acid rain (main product of the oxidation of SO2 in the atmosphere) on the ecology and corrosion of monuments or buildings are incalculably large. Thus, new environmental regulations emphasize the need for more efficient technologies to destroy the sulfur-dioxide formed in the combustion processes. Presently, titania is the most common catalyst used in the chemical industry and oil refineries for the removal of SO2. Different approaches are being tested for improving the performance of titania in DeSOx operations. The addition of gold to TiO2 produces desulfurization catalysts with a high efficiency for the cleavage of S-O bonds. In this respect, the Au/TiO2 system is much more active chemically than either pure titania or gold. The deposition of Au nanoparticles on TiO2 produces a system with an extraordinary ability to adsorb and dissociate sulfur-dioxide [38]. Petrotech Journal December Issue 2009


Green nano-materials

Ru nanoparticles supported on CNTs can be used as highly efficient catalyst for generation of COx-free hydrogen from ammonia [39]. Cadmium-rich CdSe nano-crystals below a critical size, under illumination, catalyze CO2 fixation [40].

Organic disinfectants are being replaced by nano-materials like nanoTiO2 to keep surfaces of buildings, glass etc. clean. TiO2 photochemistry also breaks down the particulates pres-

Table 4. Examples of the toxic effects of nano-materials in in-vivo studies. Adapted from [28] Nano-material

Dose and Exposure route


0.1 or 0.5 mg; Intratracheal instillation


56% mortality in 0.5 mg dose. Weight loss, lung lesions in 0.5-mg group, necrosis, granulomas, interstitial and peribronchial inflammation


2-mg implant; Subcutaneous implantation


Activation of the histocompatibility complex in CD4+/ CD8+ T-cells.

Intact or ground MWCNT

0.5, 2 or 5 mg; Intratracheal instillation


Intact MWCNT induced collagen-rich granulomas and surrounding alveolitis. Ground MWCNT induced inflammatory and fibrotic responses.


12.5 mg; IntratraGuinea pigs cheal instillation

Pneumonitis and pulmonary lesions.

Ultrafine TiO2

0.5, 2 or 10 mg/ml; Aerosol inhalation

Pulmonary particle overload and inflammation in rats and mice exposed to 10 mg/ml. Inflammation included increased number of macrophages and neutrophils, progressive fibrosis in rats, elevated protein and lactate dehydrogenase levels.

TiO2 particles, nanoscale rods or dots

1 or 5 mg; Intratracheal instillation


Mice, rats, hamsters



TiO2 rods or dots produced transient inflammatory and cell injury effects, and were not different from the effects of larger sized TiO2 particles.

Table 5. Examples of the toxic effects of nano-materials in in-vitro studies. Adapted from [28] Nano-material





HEK cells in culture 0.06–0.24 mg/ml (Human epidermal keratinocytes)


Human HEK293 (HuInhibition of cell, proliferation and cell 0.78–200 mg/ml man embryo kidney apoptosis was induced. cells)



TiO2 nanoparticles, (Anatase form, 10 or 20 nm; Rutile form, 200 nm)

Cells showed a dose-dependent decrease in viability. Oxidative stress indicated.

MWCNT present within cytoplasmic vacuoles of HEK cells, initiated irritation response and release of the proinflammatory cytokine interleukin-8.

0.1–0.2 mg/ml


40–400 μg/ml

Dose- and time-dependent decrease in cell viability, and induced cell apoptosis. Only oxidized MWCNT induced an Human T lymphocytes increase in tyrosine phosphorylation. Oxidized MWCNT more toxic than pristine MWCNT.

10 mg/ml

BEAS 2B (Human bronchial epithelial cells)

Anatase forms caused DNA damage, lipid peroxidation and micronuclei formation. Rutile form was generally much less toxic.

TiO2 nanoparticles (anatase form, 30-40 5 mg/ml nm)

Aggregates of nanoparticles present in the cells. Red cell morphology was not Human red blood cells generally affected, suggesting that the red cells were not damaged.

TiO2 nanoparticles (different sizes in both 3–30 mg/ml anatase or rutile form)

A549 cells (Human lung epithelial cells)


Petrotech Journal December Issue 2009

Cells showed a dose-dependent decrease in viability. Interleukin-8 was induced at highest doses.

ent on such surfaces. Nano-TiO2-coated windows could eventually clean a city’s air. Thus, nano-materials might make it possible to tackle seemingly intractable contaminants, such as PCBs (polychlorinated biphenyls). The materials can be recyclable, tailored to specific purposes, and are relatively cheap and easy to make. Newly discovered properties of nano-materials could lead to less chemical use and permit more chemical clean-up in industrial settings. However, there may be a trade-off. Nanoparticles, being washed-off these windows and other coated surfaces into storm drains, streams, and rivers might pose problems for aquatic and marine life. Like any other technology, therefore, the advantages and perils of this new technology need to be very carefully weighed before large-scale use of nanotechnology-based products for various applications is made. There is a remarkable increase in nanotechnology-related products and technologies. According to Lux Research, a firm that tracks about 300 companies working on nano-materials for wind power, photovoltaics, packaging materials, batteries for efficient and compact energy storage, and a number of other products or components in different sectors, states the the market, that was almost nonexistent 5 years ago, for a broad range of products containing emerging nanotechnologies increased to $147 billion in 2007. Overall, established “nanoenabled” products held a market share of $1.7 trillion in 2008. “Green Nano” or nanotechnology for environmental clean-up is just beginning to be introduced. Issues such as eco-toxicology, scale-up, cost benefits etc. would have to be critically reviewed before nanotechnology solutions are generally accepted by industry, judiciary, and governments [41].

Nanotechnology and Safety Concerns The very attributes of small size, increased surface area, and increased reactivity that are central to the benefits of nano-materials, are responsible for concerns regarding their toxicity. The

waste generated during the production and use of nanoparticles will eventually appear in various environments and subsequently be inhaled, ingested, or absorbed to varying extents, into all living organisms. The small size of nanomaterials makes their clearance from the body a very complex issue. Prolonged circulation in the body could lead to a number of toxic effects which need to be evaluated. A number of in-vitro and in-vivo toxicity studies have been done for carbon nanotubes and some selected inorganic nanoparticles [35]. The results of these studies have been summarized by Theron et al. (2008). These are represented in tables 4 and 5. The toxic effects of other nanoparticles are also being extensively studied by the research community. More nano-materials must undergo such toxicity studies before they are accepted in the mainstream technologies at large.

Conclusions Nanotechnology is without doubt, the technology of the future. The pace of research in this field promises more and more novel products and processes, along with an ever expanding scope of their applications. In this article, we have presented only a small fraction of the spectrum of applications of nanotechnology. For any technology to be acceptable at large, despite the benefits it may provide, it is however imperative that it is safe over a long run. The progress in nanotechnology, with respect to its applications, needs to go hand in hand with the safety considerations. Unbalanced promotion of the benefits of nanotechnology without assessing the risks involved could be disastrous. With nanotechnology already touching upon a large diversity of areas, there is an urgent need for an organized framework to understand the short-term and long-term impacts of the novel nanomaterials on human and animal health, in particular, and on the environment and eco-systems in general. Wisdom demands this of us; lest, we become victims of our own creation!

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Maiti A., 2002. Activation of gold on titania: Adsorption and reaction of SO2 on Au/TiO2, J. Am. Chem. Soc., 124, 5242-5250. 39. Yin S-F., Xub B-Q., Nga C-F., Aua C-T., 2004. Nano Ru/CNTs: A highly active and stable catalyst for the generation of COx-free hydrogen in ammonia decomposition, Applied Catalysis B: Environmental, 48, 237–241. 40. Wang L. G., Pennycook S. J., Pantelides S. T., 2002. The role of the nanoscale in surface reactions: CO2 on CdSe, 89, 7, Physical Review Letters, 075506-1-4. 41. Lubick N., 2009. Promising green nanomaterials, Environ. Sci. Technol., 43, 1247–1249.

International Oil Scenario - Extracts

Published by Energy Information Administration (EIA), USA Forecast global oil demand is estimated at 86.3 mb/d in 2010. Globle oil supply (OPEC) rose to 29.1 mb/d, its highest level in a year largely as a result of lower nonOPEC supply prospects for 2010. Forecast 2010 (Non – OPEC supply) is revised to 51.6 mb/d, with North American supply now lower. Projected Global 1Q10 crude throughput is seen rising to 72.7 mb/d, but OECD crude runs are expected to fall, given weak refining margins.


Petrotech Journal December Issue 2009

Crude oil futures prices traded in a higher $75-80/ bbl range in November before weakening in early December on fears that the recovery in the global economy could be shallower and slower than expected, especially in the key US market. A Medium – term market update sees upward revisions for demand (largely non – OECD Asia) outstripping those for supply (Russia, OPEC NGLs and Nigerian and Iraqi capacity). Yet higher OPEC capacity ensures similar market outlooks – tightening under the higher GDP case, but remaining comfortable under lower GDP growth or faster efficiency gains.

Human Resources

Excellence Creating organizational collectively Ashis Sen Chief Manager, Balanced Scorecard, Hindustan Petroleum Corporation Limited

Ashis Sen

Ashis Sen was the Lead Coach in this Organizational Change initiative at Hindustan Petroleum Corporation Limited, and can be reached on or . He is presently working as Chief Manager Balanced Scorecard at the same organization. He is also the India Coordinator for Society for Organizational Learning (Chair of Sol is Dr. Peter Senge, Faculty at MIT) Shri Sen has received appreciation for his work from faculty at MIT, Boston, A&M University, Texas, Harvard Business School amongst many others. He is a prolific writer and speaker on subjects like organizational change, strategy, scenario building Balanced Scorecard and Emotional Intelligence. He is also the Vice-Chairman of Forum for Emotional Intelligence Learning (


rganizational change for impact should be a vector rather than scalar. Change must have velocity rather than mere speed. Often organizations caught in the trap of the change vortex of shifting customer aspirations, demanding vendors, coupled with dynamic changes in regulatory structures indulge in knee jerk reaction. Lacking long term direction some of the initiatives severely impair longterm growth and competitive edge. Reactive and Responsive action can become habitual schedule, often euphemistically termed by executives as adaptation to ruthless business demands. They even have a terminology for such acts, christened ‘pragmatic and practical action’. On the other hand, organizations working towards achieving co-created aspirational objectives create new market realities and opportunities. In fact, this article would deal with some of the counter-intuitive steps taken by Hindustan Petroleum during trying and difficult times including those in the recent economic downturn to illustrate this point. In 2003 faced with liberalization and globalization forces in the petroleum marketing sector the top Management Team at Hindustan Petroleum corporation consisting of the Chairman, Functional Directors and SBU Heads co-created a vision called the HPCL Vision 2006. This is reproduced below:

• • • •

The process of creating this collective aspiration or shared vision was a journey of discovery of what each of the individual members of the top team desired for the future of HPCL. After collective and extensive discussions they articulated the co-created HPCL vision. The process ensured individual commitment with collective and mutual accountability The vision reflected both individual and collective desire. Thereafter exhaustive conversations were structured on building shared understanding on critical themes of the vision. Some of the important questions raised were: 1. What is customer delight? 2. How do we define an environment of trust, pride and camaraderie? 3. How would we define a learning organization? 4. What do we mean by cost effective and how does it help the customer? 5. How do I contribute to achieve the vision? Shared meanings on these themes emerged from the interaction of view and opinions of individuals and thus became group asset demanding directional and synergistic action. This process released huge energy in the

top management. But an important realization also dawned. They realized that to create intrinsic motivation and meaningful work they would need people participation in vision building. This led to a process of covering more than 4000 people in defining the HPCL Vision. The process took years and still continues. The question how do I contribute to achieve the vision kindled an inner calling to act. In 2004 hundreds of our front line officers from cross functional teams comprising of Engineers, MBAs and Chartered Accountants travelled, lived and conversed with our various segments of customers like truckers, rural people and urbanites. This gave them deep insights into customer needs. Many marketing initiatives which gave us leadership position in market growth over the years emanated from this process. One of the initiatives designed by the cross functional was opening outlets in rural areas which would cut down wasteful travel and associated expenses. Also, it would help the rural customers to get quality and quantity fuel eliminating unlicensed traders who charged premium and did not guarantee quality and quantity.

Figure 1: Model of Excellence: Designed by Ashis Sen

HPCL delights customers by superior understanding and fulfilling their stated and latent needs with innovative product and services. HPCL commands highest reputation and is known for its sensitivity and responsiveness for concerns of its customers and other stakeholders. HPCL always acts faster than the competitors in the most cost effective way. HPCL is the highest performer in Rate of Growth and Return on Investment HPCL is a Learning and Innovative Organization HPCL provides an environment of trust, pride and camaraderie Petrotech Journal December Issue 2009


This proposal seemed rather utopian since opening outlets were expensive propositions and rural volumes rarely justified large investments. But then the commitment of the employees helped. They proposed low cost outlets at a fraction of the cost of regular outlets which were expected to meet the ROI norms. The results were spectacular and we have today around 1500 such outlets have given us competitive edge and the ROI has been far superior to that expected. Also, the officers felt a personal sense of victory and achievement when the villagers all over the country thanked them for this initiative. When organizational objectives become personal milestones miracles can be achieved. The model of excellence as discovered by us is schematically depicted as in figure 1. After years into the process we now know: 1. The act of vision creation seeds commitment and achievement orientation

2. Shared understanding on strategy and vision brings synergistic action 3. Strategy Implementation without the participation in vision and strategy formulation may ensure some compliance but would lack commitment and initiative by employees. You cannot outsource thinking and expect discretionary effort towards a strategy and vision drafted by external consultants. 4. The process was facilitated at HPCL by a group of Internal Coaches drawn from different disciplines in the organization and who were trained extensively on Change Management and coaching by some of the leading experts in the world. Their work has received recognition from Faculty at MIT Boston, Harvard Business School, A&M University Texas, IIMs and Practitioners across the Globe. Internal consultants aware of the mindsets and the culture in the organization facilitate to leverage the strengths and aspirations of the people and can create an environment of trust and faith. They also are focused to a process which ensures result orientation.

5. Working towards a shared vision helps people find meaning in their work and is a source of joy and happiness. This process changes employees into entrepreneurs. 6. Employees learn and develop competencies when they work for an aspiration they helped create. These competencies are vision and strategy need focused. 7. To make our growth sustainable we needed to recruit people and even when recession was its peak and immediate market growth in the industry unattractive, we continued to recruit large number of employees from the best management and technical institutes. This is today enabling us to take up expansion of our facilities across the country more effectively. In fact, recession enabled us to attract the best talent and also keep them. An enabling and empowering environment ensures very high rate of retention. The Model of Excellence as discovered by me is schematically shown below. It is replicable, but building faith in this process would mandate that each organization experiment and explore the model.

We will miss him Mr Subir Raha, an Electronics Engineer, went on to complete his MBA from LEADS University, UK. He had over 38 years experience in the oil & gas sector having started as a trainee in IOCL to become their Director (HR & Business Development), before taking over as CMD of ONGC and chairman of ONGC Group of Companies. As Chairman, Petrotech Society he guided the activities of the Society so as to benefit the hydrocarbon sector. He will always be remembered as a pillar of the Petroleum Industry.


Petrotech Journal December Issue 2009

Mr Subir Raha (28-8-1948 — 1-2-2010)


Isotopic Composition Of coalbed methane desorbed from barakar coals of damodar valley gondwana coalfields and its implication Malay Rudra and P N Hajra CBM Block, ONGC, 41 J L N Road, Kolkata

Abstract Stable Carbon Isotopic composition is long been used as a very important tool for finding out the genesis of natural gas. In this paper this tool is used to find out the genesis of CBM of Barakar Coals of Damodar Valley Gondwana Coalfields and its implication. The factors those control the Stable Carbon Isotopic composition of coalbed methane are: i) rank or maturity ii) organic composition of the coal. iii) biogenic activity More than 100 number data of Stable Carbon Isotopic composition of methane had been generated on desorbed gas from Barakar coal of the four coalfields viz. viz. Jharia, Raniganj, Bokaro and North Karanpura Coalfields. The data shows Stable Carbon Isotopic composition of methane value of this parameter is mainly controlled by maturity or rank of coal except in case Raniganj Coalfield. In Raniganj the Boreholes drilled in the northern part of coalfield has shown some biogenic signature. In Jharia, no biogenic signature has been observed in any of the coal gas studied so far. And in case of Bokaro and North Karanpura coalfield, in very shallow coalseam some biogenic signature is observed, which

may be due to influx from surface. And gas from deeper coal follows the maturity trend. In case of Raniganj Coalfield in very matured coal the gas bears biogenic signature. It appears the coalseams were uplifted post maturation which left the coals to be degassed and simultaneous surface influx has left some biogenic signature in the coal seam gas. Apart from control of Stable Carbon Isotopic composition of methane due to rank or maturity of coal this study also covered other factor viz. maceral composition of coal which affect the Stable Carbon Isotopic composition of methane. It is seen that the results are in the expected line. It already established maceral with higher hydrogen content produce gas with lighter Carbon Isotopic composition of methane compared to oxygen rich maceral. The same is observed in coal gas from these four coal fields. An effort is made in this paper is made to draw general inference about the origin of the gas and also implication involved thereof.

Durgapur Depression of Raniganj Coalfield.. During this period ONGC was primarily active in four Damodar Valley Gondwana Coalfields viz. Jharia, Raniganj, Bokaro and North Karanpura Coalfields (fig.1). In this exploration campaign ONGC has drilled more than 32 Boreholes and 10 full diameter Exploratory wells. In this process ONGC has generated a treasure trove of CBM specific data. These data have been used to define & decipher the characteristic of these Barakar coals. This in turn has helped in defining the prospectivity of these coal as CBM target. Use of Stable Carbon Isotopic Composition in quest of genesis of the natural gas is well known in industry. Methane Isotopic composition is often used as lead to identify source or route through which it is generated. Present study covers only the desorbed coal gas those were collected from drilled coalholes & exploratory wells in Jharia ,Bokaro Raniganj & North Karanpura coal fields. The Barakar formation coals, from where these gas samples were studied, are of Permian age.

Introduction Methodology ONGC is engaged in CBM exploration for more than a decade, since 1996, when first CBM well was drilled in

The data used in this paper is collected from both primary and secondary sourc-

es for the four coal fields viz. Jharia, Bokaro, Raniganj and North Karanpura Coalfields. Petrographic data of approximately 300 samples (165 through present study and rest collected from other sources) have been used to find out the trend of maceral distribution in each of this four coalfields. Data of Isotopic composition of desorbed gases collected from different coreholes and exploratory wells drilled in the above four coal fields during CBM exploration campaign of ONGC in last few years since 1996 are obtained from various internal reports and integrated in the study. More than 100 number of methane Isotopic value has been used along with other data to arrive at the inference.

Maturity & Isotopic Composition It is well known that Isotopic composition becomes heavier with increase in maturity. The vitrinite reflectance value range from 0.83 to 1.69% and 0.58 to 1.32% for Barakar coal seams of Jharia and Raniganj respectively. For Barakar coals of Bokaro and North Karanpura the range of vitrinite reflectance is 0.73 to 1.69% and 0.53

to 1.13% respectively. The volatile matter on dry ash free basis indicate that the Barakar coals of Jharia and Bokaro are high volatile ‘A’ bituminous to low volatile bituminous in rank and Barakar coals of Raniganj and North Karanpura are of high volatile ‘B’ bituminous to medium volatile in rank. In the eastern part of Raniganj Coalfield the coals of Raniganj formation are sub bituminous ‘A’ to high volatile ‘C’ bituminous in rank. For the four areas viz Jharia, Bokaro, Raniganj and North Karanpura the plot of distribution of D13C1 value along the depth (fig No. 2,3,4 & 5) it can be seen that uniform increasing trend is observed in the Jharia & Bokaro. Whereas, in Raniganj there is some dispersal of data is there which can be ascribed to extensive intrusive intrusion in that area and thus changing the normal maturity trend. Also, immatured sample at about 1500m from eastern Raniganj can be seen. In the case of North Karanpura though there is normal increasing trend beyond 550m, but in the shallow part there is some erratic show of heavier

gas than its immediate lower coals. Some mixed signature is also observed in some shallow coalseam in North Karanpura. In Bokaro as well, in very shallow coal seam of less than 200m depth some coal shown biogenic signature which can be explained to surface influx, also the same seams are being mined nearby area. But in Raniganj at about 650m or more distinct biogenic signature has been observed in gas desorbed from coal. Interestingly this coal are having very low gas content but very good coal maturity of the order of Vro 1.16 (ref. 7 & 8).To understand this phenomenon further investigation is required. So, it can be inferred that the methane isotopic value in case Jharia & Bokaro is mostly maturity controlled, which is also valid to some extent for North Karanpura coals. But Raniganj coal, the methane isotopic composition shows normal maturity trend is disturbed. Figure 2: Jharia: Depth vs d13C1

Figure 1: Location Map of Four Damodar Valley Gondwana Coalfields

Figure 3: Bokaro: Depth vs d13C1


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Organic matter quality & Isotopic Composition Maceral composition of coal reveal the original organic matter input that has contributed to composition of coal. Our earlier study (ref no.9 ) revealed that Indian Gondwana coal are of humic origin and vitrinite-inertinite type with vitrinite maceral often ranging from 40 to70%. The distribution of macerals of the coals of Barakar Formation of Jharia, Bokaro, Raniganj, and North Karanpura Coalfields are depicted in ternary diagrams (Fig.6,7,8 and 9 respectively). The Vitrinite macerals are dominant in the shallower coals of Barakar Formation (Lower Permian) and range from 40 to 80% and from 50 to 70% for Jharia and Raniganj coalfields, exinite content vary in the range of 1 to 4%, 1 to 7%. As the depth increases, in general it has been observed that ash content increases with consequent decrease in vitrinite content and increase in inertinite content for the Barakar coals of Jharia and Raniganj Coalfields. This trend is also visible in North Karanpura. The range of inertinite content for deeper coals in Jharia is from 35 to 80% and vitrinite content range from 20 to 62%.The deeper Barakar coals of Raniganj, similarly has the inertinite and vitrinite content in the range of 40 to 82% and 13 to 54% respectively. For Bokaro coalfield the general range of vitrinite content is 30 to 80 % , liptinite 1 to 14 % and inertinite 21 to 77 %.

In the case of North Karanpura coalfield the range of vitrinite is 38 – 76%,liptinite 2 –27% and inertinite 22-56%. Earlier worker has found that gases generated from coals with oxygen rich kerogen(mostly Vitrinite) are found to be isotopically heavier than gases produced from hydrogen rich kerogen (liptinite and and some hydrogen rich vitrinite) (ref 3 & 10). The data from four coalfield was plotted in 3d plot with d13C1,Vro & Vitrinite in three different axis (fig.10) & d13C1,Vro & liptinite/exinite in three different axis (Fig 11). It is clearly evident that the vitrinite rich coal is producing iso-topically heavier gases compared to exinite rich coal which is producing iso-topically lighter gases.

Biogenic Activity Biogenic activity enriching the CBM gas resource is reported from different areas worldwide. The prospective coal seams for methane production in Australia range from Jurassic to Permian in age with ranks varying from subbituminous to low volatile bituminous coal. It is reported (ref 6).that these coals contain mixed gas compositions comprising mainly methane and carbon dioxide with subsidiary amounts of ethane and higher hydrocarbons. It is reported that Geochemical data

for gases and coal indicate extensive microbial activity, especially in coal seams shallower than about 600 m. Microbial activity possibly occurred subsequent to uplift of the eastern Australian basins during the Late Cretaceous and Tertiary. The author indicated that such microbial activity has contributed to considerable volumes of methane presently stored in the shallow coals of these basins It is reported (Ref 6) that the origin of CBM in the Powder River Basin ( coal rank reaching upto high Volatile C-Bituminous )is the result of microbial processes (biogenic methanogenesis d13C1 value ranges from -60.0to-56.7 ‰) ( Ref. 11) As mentioned earlier biogenic & mixed signature has been observed from desorbed gases in shallow seams(<200m) in Bokaro & North Karanpura area, which can be ascribed to surface influx. In Jharia in only one borehole where coal suffered extensive thermal stress and most of the coal turning to “Jhama”, registered biogenic signature in shallow depth. However, in northern part of Raniganj biogenic signature is observed at a depth of 650m. Further study is required to understand this phenomenon of presence of deep seated biogenic gas. Moreover, though the gas content in the shallow seam is good in Bokaro & North Karanpura i.e enrichment of

Figure 6: Maceral Composition, Barakar Fm, Jharia

Figure 8: Maceral Composition, Barakar Fm, Raniganj

Figure 7: Maceral Composition, Barakar Fm, Bokaro

Figure 9: Maceral Composition, Barakar Fm, North Karanpura

Figure 4: Raniganj Depth vs d13C1

Figure 5: North Karanpura: Depth vs d13C1

Petrotech Journal December Issue 2009


Figure 10: Dependence of d13C1 with Vitrinite & VRo

Figure 11: Dependence of d13C1 on Liptinite content & VRo

to some extent in Bokaro isotopic composition is lighter compared to similar coal having same maturity in other coal fields in the study are. 3. Possibility of using biogenic strains found at depth of 650m in North Raniganj area or more requires further study for application in microbial enhanced Coalbed methane in India.


CBM has resulted due to biogenic activity. But in Raniganj the coal in question though had adequate maturity was found to have very low gas content. A number of authors has reported enrichment of CBM by biogenic activity even in high rank coal in laboratory condition (Ref. 1, 2). It may be possible to generate methane in coal seams by manipulating microbiological processes (Ref 5, 12,13). This in situ gasification of coalbeds may be able to enhance CBM production from existing fields and could enhance the gas reserves in coal fields that do not currently hold CBM. To maximize CBM production, the whole process of microbial process in prevailing set up(low permeability) in Indian Gondwana Coal beds is required to be understood. The Methanogens artificially introduced into a coal deposit could microbially increase the CBM content as well as enhance permeability as well, by removing poreplugging waxes in cleats. The microbial strain observed at depth of 650mt ( at a reservoir temperature of about 50 -55 oC, assuming surface temperature of 30 oC and temperature gradient of 3 oC per 100m) can be identified & developed for microbial enhanced CBM from existing CBM blocks as well as abandoned coal mines.

Author is grateful to ONGC management for permitting publication of this paper. The contributions made by the colleagues of ONGC, starting from drill sites to laboratories for generation of reliable and quality data are gratefully acknowledged. The views expressed in this paper reflect the views of the authors and not necessarily that of ONGC.


Conclusion Based on discussion above following inferences can be drawn: 1. Heavier isotopic composition observed in some of the coalfields viz. Jharia, Bokaro and Raniganj Coal can be ascribed to high vitrinite maceral content of the coal. 2. Due to higher lipnitic content in Barakar coal of North Karanpura &


Petrotech Journal December Issue 2009

• Biswarup Mukhopadhyay “Methanogenic Archaea,Coalbed Methane and Mycobacteria” Research Report-Virginia Tech, https://www. annual_report /2005/ annual_report_2005_sci_11_mukhopadhyay.pdf . Dariusz Stra˛poc´,1* Flynn W. Picardal,2 Courtney Turich,3† Irene Schaperdoth,3 Jennifer L. Macalady,3Julius S. Lipp,4 Yu-Shih Lin,4 Tobias F. Ertefai,4 Florence Schubotz,4 Kai-Uwe Hinrichs,4 ,Maria Mastalerz,5 and Arndt Schimmelmann1 “Methane-Producing Microbial Community in a Coal Bed of the Illinois Basin” APPLIED AND ENVIRONMENTAL MICROBIOLOGY, Vol. 74, No. 8 Apr. 2008, p. 2424–2432. Galimov, E M, 1988, Sources and mechanisms of formation of gaseous hydrocarbons in sedimentary rocks,Chemical Geology,V71,p77-96. John Wheaton , “Investigation of Coalbed-Methane Microbes in the Powder River Basin, Montana” Montana Bureau of Mines and Geology Biennial Report of Activities and Programs, July 1, 2004–June 30, 2006, http://www.mbmg.mtech. edu/biennial-2006/toc_br-2006.pdf Karen Budwill, “Role of Biogenic Gas Generation for Sustainable

CBM Production” Alberta Research Council,Edmonton, Alberta, Canada, Williston Basin Petroleum Conference May 7-9, 2005, Minot, ND Mohinudeen Faiz and Phil Hendry “Significance of microbial activity in Australian coal bed methane reservoirs — a review” http:// content/abstract/ 54/3/261, Bulletin of Canadian Petroleum Geology; September 2006; v. 54; no. 3; p. 261-272; DOI:10.2113/gscpgbull.54.3.261© 2006 Canadian Society of Petroleum Geologists. P N Hajra, Malay Rudra et al “Geochemical Characterization of Coalbed gas of Jharia & Raniganj Basins and its implications” Presented in First Association of Petroleum Geologists (APG) Conference & Exhibition, Mussoorie,28th & 29th September, 2002. P N Hajra, Malay Rudra et al “A Geochemical assessment of CBM Potential of North Raniganj area” Presented in PETROTECH-2003,January 9-12, 2003, New Delhi. P N Hajra, Malay Rudra et al “ Petrographical Characteristics of Indian Gondwana Coals and its Implications on CBM Prospectivity” Presented in 10th Annual Indian Oil and Gas Review Symposium (IORS -2003) & International Exhibition, September 8-9, 2003, Mumbai. Rice, D.D.,1993: Composition and origin of coalbed gas : in Hydrocarbons from Coal; AAPG studies in Geology #38 ; Law, B.E. and Rice, D. D., eds., Published by AAPG, Tulsa, Oklahama; p. 159-184. Roger Tyler,WA Ambrose,A R Scott and W R Kasiser, Dec 1991. “Coalbed methane potential of greater Green River,Piceance,Powder river and Raton Basin” GRI,Coalbed Methane Technology.Page125-130. Scott, Andrew R,1999, ”Improving coal gas recovery with microbially enhanced coalbed methane” in Coalbed Methane: Scientific, Environmental and Economic Evaluation, Kluer Academic Publishers. Dordrechi,Netherlands Page No. 89 -110. methane_extraction.pdf


Geologic & Engineering Controls The Energy Resource Potential of Gas Hydrates T. S. Collett U.S. Geological Survey, Denver Federal Center, MS-939, Box 25046, Denver, Colorado, 80225, U.S.A.

Abstract Researchers have long speculated that gas hydrates could eventually be a commercial energy resource yet technical and economic hurdles have historically made gas hydrate development a distant goal rather than a near-term possibility. This view began to change in recent years with the realization that this unconventional resource could possibly be developed with existing conventional oil and gas production technology. The most significant development was gas hydrate production testing conducted at the Mallik site in Canada’s Mackenzie Delta. The Mallik gas hydrate production project has yielded the first modern, fully integrated field study and production test of a natural gas hydrate accumulation. BP Exploration (Alaska) Inc. with the U.S. Department of Energy and the U.S. Geological Survey have successfully cored, logged, and tested a gas hydrate accumulation on the North Slope of Alaska known as the Mount Elbert Prospect. The Mallik project along with the Mount Elbert effort has for the first time allowed the rational assessment of the production response of gas hydrate. Marine gas hydrate research drilling, coring, and logging expeditions launched by

the National gas hydrate programs in Japan, India, China, and South Korea have also contributed significantly to our understanding of how gas hydrates occur in nature and provided a much deeper appreciation of the geologic controls on the occurrence of gas hydrates. With an increasing number of highly successful gas hydrate field studies, significant progress has been made in addressing some of the key issues on the formation, occurrence, and stability of gas hydrates in nature. This report deals with the assessment of the geologic and engineering factors that control the ultimate resource potential of gas hydrates. This assessment will be conducted mainly though the examination of several of the more successful International gas hydrate research efforts.

Introduction Gas hydrates are naturally occurring “ice-like” combinations of natural gas and water that have the potential to provide an immense resource of natural gas from the world’s oceans and polar regions. Gas hydrates are known to be widespread in permafrost regions and beneath the sea in sediments of outer continental margins. It is generally accepted that the volume

of natural gas contained in the world's gas hydrate accumulations greatly exceeds that of known gas reserves. There is also growing evidence that natural gas can be produced from gas hydrates with existing conventional oil and gas production technology (Moridis et al., 2008; Dallimore et al., 2008; Yamamoto and Dallimore, 2008). This review of natural gas hydrates is intended to provide an up-todate analysis of the geologic controls on the occurrence of gas hydrates in nature with a focus on understanding the energy resource potential of gas hydrates. The results of some of the more important international gas hydrate research projects are discussed.

Occurrence of Gas Hydrates As shown in Figure 1, gas hydrates have been recovered at about 40 locations throughout the world. However, only a limited number of gas hydrate accumulations have been examined and delineated with data collected by deep scientific drilling operations. Included in the following discussion are descriptions of several of the best known drilled marine and onshore permafrost-associated gas hydrate accumulations in the world.

Gulf of Mexico

The occurrence of gas hydrates in the Gulf of Mexico was confirmed during DSDP Leg 96 when numerous gas hydrate samples were recovered from sub-bottom depths ranging from 20 to 40 mbsf in the Orca Basin (Sites 618 and 618A), which is located about 300 km south of Louisiana beneath about 2,000 m of water. Near-surface (0-5 m) marine sediment coring has also recovered numerous gas hydrate samples on the Louisiana continental slope. In 2005, the Chevron-led Gulf of Mexico Gas Hydrate Joint Industry Project (JIP), conducted scientific drilling, coring, and downhole logging to assess hydrate-related hazards in fine-grained sediments with low concentrations of gas hydrate (Claypool, 2006). This expedition targeted two deep-water locations in the Atwater Valley and Keathley Canyon areas of the Gulf of Mexico. Although gas hydrate was not physically recovered from the Keathley Canyon core hole, other indicators of gas hydrate, such as elevated downhole measured electrical resistivities, suggests the probable occurrence of gas hydrate in the KC151-2 well. Analysis of downhole measured resistivities and resistivityat-the-bit (RAB) images from the KC151-2 hole revealed the occurrence of fracture filling gas hydrate at relatively high concentrations. The analysis of downhole well log data from the two JIP Atwater Valley wells shows little evidence of significant gas hydrate occurrences, other than several thin, possibly stratigraphically controlled gas-hydrate-bearing intervals. The next phase of the Gulf of Mexico JIP is being extended to coarsergrained sediments with much higher expected gas hydrate concentrations. In the winter to early spring of 2009, the Gulf of Mexico JIP expects to conduct exploratory drilling and logging to better understand gas-hydratebearing sands in the deepwater Gulf of Mexico. Also in the Gulf of Mexico, at the Alaminos Canyon 818 site (AC818), gas hydrate is interpreted to occur within the Oligocene Frio volcaniclastic sand at the crest of a fold that is shallow enough to be in the hydrate stability


Petrotech Journal December Issue 2009

zone (Smith et al., 2006). Examination of the well log data obtained from the Frio section of the Chevron Tiger Shark well drilled in AC818 indicates approximately 18 m of sand (3,209 to 3,227 m drilling depth) with porosity of about 30% and downhole measured resistivity in the range 30 to 40 ohmm. Initial volumetrics derived from downhole log data show very high gas hydrate saturations (up to 80% of available pore volume). Alaska North Slope

Before the recently completed coring and downhole-logging operations in the BP Exploration (Alaska) Mount Elbert well in Milne Point, the only direct confirmation of gas hydrate on the North Slope was obtained in 1972 with data from the Northwest Eileen State-2 well located in the northwest part of the Prudhoe Bay Field. Gas hydrates are also inferred to occur in an additional 50 exploratory and production wells in northern Alaska based on downhole log responses calibrated to the known gas hydrate occurrences in the Northwest Eileen State-2 well. Most of the well-log inferred gas hydrates occur in six laterally continuous sandstone units; all are geographically restricted to the area overlying the eastern part of the Kuparuk River Field and the western part of the Prudhoe Bay Field. The volume of gas within the gas hydrates of the Prudhoe Bay-Kuparuk River area, which has come to be known as the Eileen Gas Hydrate Accumulation, is estimated to be about 1.0 to 1.2 trillion cubic meters. Under the Methane Hydrate Research and Development Act of 2000 (renewed in 2005), the DOE has funded field research on both Arctic and marine gas hydrates. Among the current Arctic studies, BP Exploration (Alaska), Inc. (BPXA) and the DOE have undertaken a project to characterize the commercial viability of gas hydrate resources in the Prudhoe Bay, Kuparuk River, and Milne Point field areas on the Alaska North Slope. As part of this effort, the Mount Elbert Gas Hydrate Stratigraphic Test Well was completed in February 2007 and yielded one of the most comprehensive datasets yet compiled on naturally-occurring gas hydrates (Boswell et

al., 2008). In 2005, extensive analysis of BPXA’s proprietary 3-D seismic data and integration of that data with existing well log data (enabled by collaborations with the USGS and the BLM), resulted in the identification of more than a dozen discrete and mapable gas hydrate prospects within the Milne Point area. Because the most favorable of those targets was a previously undrilled, fault-bounded accumulation, BPXA and the DOE decided to drill a vertical stratigraphic test well at that location (named the “Mount Elbert” prospect) to acquire critical reservoir data needed to develop a longer-term production testing program. Gas hydrates were expected and found in two stratigraphic sections. An upper zone, (Unit D) contained ~14 m of gas hydrate-bearing reservoir-quality sandstone. A lower zone (Unit C), contained ~16 m of gas hydrate-bearing reservoir. Both zones displayed gas hydrate saturations that varied with reservoir quality as expected, with typical values between 60% and 75%. The Mount Elbert gas hydrate stratigraphic test well project included the acquisition of pressure transient data from four short-duration pressure-drawdown tests with Schlumberger’s wireline MDT (Boswell et al., 2008). These tests were conducted in open-hole, and were designed to build upon the knowledge gained from cased-hole MDT tests conducted during the Mallik 2002 testing program. The MDT and NMR log data from the Mount Elbert well also confirmed the presence of a mobile pore-water phase even in the most highly gas-hydrate saturated intervals. Gas hydrate dissociation and production was confirmed in the later stages of each test in which the pressure was drawn down below gas hydrate equilibrium conditions. Additional work anticipated within this effort includes a long-term production testing program designed to determine reservoir deliverability under a variety of production/completion scenarios. Mackenzie River Delta – Mallik

The JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well, drilled in 1998 near the site of the Mallik L-38 well, included extensive scientific studies designed to investigate the occurrence of in-situ natural gas hydrate

Figure 1. Locations of sampled and inferred gas hydrate occurrences in oceanic sediment of outer continental margins and permafrost regions. Most of the recovered gas hydrate samples have been obtained during deep coring projects or shallow seabed coring operations. Most of the inferred gas hydrate occurrences are sites at which BSRs have been observed on available seismic profiles. The gas hydrate occurrences reviewed in this report have also been highlighted on this map.

in the Mallik field area (Dallimore et al., 1999). Approximately 37 m of core was recovered from the gas hydrate interval (878-944 m) in the Mallik 2L-38 well. Pore-space gas hydrate and several forms of visible gas hydrate were observed in a variety unconsolidated sands and gravels interbedded with non-hydrate bearing silts. Because of the success of the 1998 Mallik 2L-38 gas hydrate research well program, the Mallik site was elevated as an important gas hydrate production test site with execution of two additional gas hydrate production research programs: (1) The Mallik 2002 Gas Hydrate Production Research Well Program, and (2) 2006-2008 JOGMEC/NRCan Mallik Gas Hydrate Production Research Program.

In June of 2005, the partners in the Mallik 2002 Gas Hydrate Production Research Well Program publicly released the results of the first modern, fully integrated field study and production test of a natural gas hydrate accumulation (Dallimore and Collett, 2005). During the Mallik 2002 testing program, the response of gas hydrates to heating and depressurization was evaluated. The results of three short duration gas hydrate tests demonstrate that gas can be produced from gas hydrates exclusively through pressure stimulation. Thermal stimulation experiments were designed to destabilize gas hydrates by using circulated hot water to increase the in-situ temperature. Gas was continuously produced throughout the test at

varying rates with maximum flow rate reaching 360 cubic meters per day (Dallimore and Collett, 2005). The total volume of gas flowed was small reflecting that the test was a controlled production experiment rather than a long duration well test. It also demonstrated the difficulty of heating a relatively large rock mass by conductive heat flow alone. As described by Dallimore et al., (2008) and Yamamoto and Dallimore (2008), the 2006-2008 JOGMEC/ NRCan Mallik Gas Hydrate Production Research Program was designed to build on the results of the Mallik 2002 project with the main goal of monitoring long term production behavior of gas hydrates. The primary Petrotech Journal December Issue 2009


objective of the winter 2006-2007 field activities was to install equipment and instruments to allow for long term production gas hydrate testing during the winter of 2007-2008. After completing drilling operations, a short pressure drawdown test was conducted to evaluate equipment performance and assess the short term “producibility” of the gas-hydratebearing section. During the most successful 12.5 hours of the test, at least 830 m3 of gas were produced. The test results verified the effectiveness of the depressurization method even for such a short duration. The following winter (2007/2008) the team returned to the site to undertake a longer term production test with the implementation of countermeasures to overcome the problems encountered in the previous year’s program. The 2007/2008 field operations consisted of a six day pressure drawdown test, during which “stable” gas flow was measured at the surface. The 2007/2008 testing program at Mallik established a continuous gas flow ranging from 2,000 to 4,000 m3/day. Nankai Trough

The presence of extensive BSRs in the Nankai Trough was confirmed with seismic surveys carried out as a part of METI’s domestic geophysical survey program. The 1999/2000 Nankai Trough drilling and coring program targeted an area of a prominent BSR located about 50 km from the mouth of the Tenryu River in central Japan at a water depth of 945 m (Takahashi and Tsuji, 2005). This drilling project, consisting of a pilot well and three post survey wells, confirmed the existence of gas hydrate in the intergranular pores of turbiditic sands based on the analysis of downhole-logging data, and observations from both conventional and pressure cores. Gas hydrate was determined to fill the pore spaces in these deposits, reaching saturations up to 80% in some layers. Individual hydrate-bearing sand layers were less than 1-m-thick, with the cumulative thickness of the hydrate-bearing sands totalling about 12 to 14 m. A multi-well drilling program titled “METI Toaki-oki to Kumano-nada” was successfully carried out in early 2004 (Takahashi and Tsuji, 2005).


Petrotech Journal December Issue 2009

A total of sixteen sites were drilled at water depths ranging from 720 to 2,030 m. Based on the analysis of the both the available downhole log data and core observations, three different types of gas hydrate occurrences were identified: (1) sand with pore-filling hydrate, (2) silt with pore-filling hydrate, and (3) nodular or fracturefilling massive hydrate in fine-grain sediments. Analysis of pressure cores and downhole log data indicate that average gas hydrate saturations in the cored sand layers ranged from 55 to 68%, with the average sediment porosities ranging from 39 to 41%. India NGHP Expedition 01

NGHP Expedition 01 was designed to study the occurrence of gas hydrate off the Indian Peninsula and along the Andaman convergent margin with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. During its 113.5-day voyage (April 28 – August 19, 2006), the research drill ship JOIDES Resolution (JR) cored or drilled 39 holes at 21 sites (one site in Kerala-Konkan, 15 sites in KrishnaGodavari, four sites in Mahanadi and one site in Andaman deep offshore areas), penetrated more than 9,250 m of sedimentary section and recovered nearly 2,850 m of core. Twelve holes were logged with logging-while-drilling tools and an additional 13 holes were wireline logged. NGHP Expedition 01 was among the most complex and comprehensive methane hydrates field ventures yet conducted. All of the primary data collected during NGHP Expedition 01 are included in either the NGHP Expedition 01 Initial Reports (Collett et al., 2008a) or the NGHP Expedition 01 Downhole Log Data Report (Collett et al., 2008b); which were prepared by the USGS and published by the DGH on behalf the MOP&NG. NGHP Expedition 01 established the presence of gas hydrates in KrishnaGodavari, Mahanadi and Andaman basins. The expedition discovered one of the richest gas hydrate accumulations yet documented (Site 10 in the Krishna-Godavari Basin), documented the thickest and deepest gas hydrate stability zone yet known (Site

17 in Andaman Sea), and established the existence of a fully-developed gas hydrate system in the Mahanadi Basin (Site 19). For the most part, the interpretation of downhole-logging data and linked imaging of recovered cores, analyses of interstitial water from cores, and pressure core imaging from the sites drilled during NGHP Expedition 01 indicate the occurrence of gas hydrate is mostly controlled by the presence of fractures and/or coarser grained (mostly sand-rich) sediments (Collett et al., 2008a). China Drilling Expedition GMGS-1

In June of 2007, a deep water gas hydrate drilling and coring program was successfully completed by the Guangzhou Marine Geological Survey (GMGS), China Geological Survey (CGS) and the Ministry of Land and Resources of P. R. China (Wu et al., 2008). Drilling expedition GMGS1 was carried out from April to June 2007 in the Shenhu Area on the north slope of South China Sea. During Expedition GMGS-1, eight sites were drilled in water depths of up to 1,500 m. Each site was wireline logged to depths of up to 300 mbsf with a set of high-resolution slim wireline tools. Five of the eight sites occupied during the expedition were cored. Gas hydrate was detected at three of the five core sites. The sediments were predominantly clay, with a variable amount of silt-sized particles including foraminifera. The sediment layers rich in gas hydrate were about 10 to 25 m thick and were found just above the base of the predicted gas hydrate stability zone (BGHSZ) at all three sites. Analysis of pressure cores confirmed that the gas hydrate occurred within fine-grained foraminifera-rich clay sediments, with gas hydrate saturations ranging from 20 to 40%. South Korea Drilling Expedition UBGH1

In November of 2007 South Korea completed its first large-scale gas hydrate exploration and drilling expedition in the East Sea: Ulleung Basin Gas Hydrate Expedition 1 (UBGH1). Leg 1 of UBGH1 included the drilling of five logging¬while-drilling holes in the Ulleung Basin, which was used to select a sub-set of three sites that were more likely to contain gas hydrate for Leg 2 drilling and

coring operations. Coring during Leg 2, at water depths between 1,800 to 2,100 m, confirmed the presence of gas-hydrate¬bearing reservoirs up to 150 mbsf (Park et al., 2008). Gas hydrate was recovered at all three core sites, occurring as veins and layers in clay-rich sediments, and as porefilling material within the silty/sandy layers. At one site, a 130-m-thick hydrate-bearing sedimentary section of interbedded sands and clays was penetrated. Analysis of pore-water freshening revealed average gas hydrate saturations of about 30% for the hydrate-bearing sand layers.

Summary There are numerous research projects underway to investigate the geological origin of gas hydrate, their natural occurrence, the factors that affect their stability, and the possibility of using this vast resource in the world energy mix. We have seen highly successful cooperative research projects, such as various phases of the Mallik effort that has for the first time tested the technology needed to produce gas hydrates. We have also seen other highly successful cooperative gas hydrate research studies in India, northern Alaska, and the Gulf of Mexico. In most cases, the cooperative nature of these efforts directly contributed to their success. It is also not surprising that the most aggressive and well funded gas hydrate research programs are in countries highly dependent on imported energy resources, such as Japan and India.


Boswell, R., Hunter, R., Collett, T.S., Digert, S., Hancock, S., Weeks, M., and Mount Elbert Science Team, 2008, Investigation of gas hydrate bearing sandstone reservoirs at the Mount Elbert stratigraphic test well, Milne Point, Alaska: Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008), July 6-10, 2008, Vancouver, British Columbia, Canada, 10 p. Claypool, G.E., 2006, The Gulf of Mexico Gas Hydrate Joint Industry Project; Covering the cruise of the Drilling Vessel Uncle John;

Mobile, Alabama to Galveston, Texas; Atwater Valley Blocks 13/14 and Keathley Canyon Block 151; 17 April to 22 May, 2005. 196 p. GOMJIPCruise05. pdf Collett, T., Riedel, M., Cochran, J., Boswell, R., Presley, J., Kumar, P., Sathe, A., Sethi, A., Lall, M., Siball, V., and the NGHP Expedition 01 Scientific Party, 2008a, Indian National Gas Hydrate Program Expedition 01 Initial Reports: Prepared by the U.S. Geological Survey and Published by the Directorate General of Hydrocarbons, Ministry of Petroleum & Natural Gas (India), 1 DVD. Collett, T., Riedel, M., Cochran, J., Boswell, R., Presley, J., Kumar, P., Sathe, A., Sethi, A., Lall, M., Siball, V., Guerin, G., Malinerno, A., Mrozewski, S., Cook, A., Sarker, G., Broglia, C., Goldberg, D., and the NGHP Expedition 01 Scientific Party, 2008b, Indian National Gas Hydrate Program Expedition 01 Downhole Log Data Report: Prepared by the U.S. Geological Survey and Published by the Directorate General of Hydrocarbons, Ministry of Petroleum & Natural Gas (India), 2 DVD set. Dallimore, S.R., and Collett, T.S., eds., 2005, Scientific results from the Mallik 2002 gas hydrate production research well program, Mackenzie Delta, Northwest Territories, Canada: Geological Survey of Canada Bulletin 585, two CD-ROM set. Dallimore, S.R., Uchida, T., and Collett, T.S., 1999, Scientific results from JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well, Mackenzie Delta, Northwest Territories, Canada: Geological Survey of Canada Bulletin 544, 403 p. Dallimore, S.R., Wright, J.F., Nixon, F.M., Kurihara, M., Yamamoto, K., Fujii, T., Fujii, K., Numasawa, M., Yasuda, M., and Imasato, Y., 2008, Geologic and porous media factors affecting the 2007 production response characteristics of the JOGMEC/NRCAN/AURORA Mallik Gas Hydrate Production Research Well: Proceedings of the

6th International Conference on Gas Hydrates (ICGH 2008), July 6-10, 2008, Vancouver, British Columbia, Canada, 10 p. Moridis, G.J., Collett, T.S., Boswell, R., Kurihara, M., Reagan, M.T., Sloan, E.D., and Koh, C., 2008, Toward production from gas hydrates: assessment of resources and technology and the role of numerical simulation: Proceedings of the 2008 SPE Unconventional Reservoirs Conference, Keystone, Colorado, February, 10–12, 2008, SPE 114163, 45 p. Park, Kuen-Pil, 2008, Gas hydrate exploration activities in Korea: Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008), July 6-10, 2008, Vancouver, British Columbia, Canada, 10 p. Smith, S., Boswell, R., Collett, T.S., Lee, M.W., and Jones, E., 2006, Alaminos Canyon Block 818: documented example of gas hydrate saturated sand in the Gulf of Mexico: Fire in the ice, Methane hydrate newsletter, US Department of Energy, Office of Fossil Energy, National Energy Technology Laboratory, Fall Issue, p. 12-13. Takahashi, H., and Tsuji, Y., 2005, Multi-Well Exploration Program in 2004 for natural hydrate in the Nankai-Trough Offshore Japan: Proceedings of 2005 Offshore Technology Conference, Houston, Texas, May 2-3, 2005, (OTC17162). Wu, N., Yang, S., Zhang, H., Liang, J., Wang, H., Su, X., and Fu, S., 2008, Preliminary discussion on gas hydrate reservoir system of Shenhu area, North Slope of South China Sea: Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008), July 6-10, 2008, Vancouver, British Columbia, Canada, 10 p. Yamamoto, K., and Dallimore, S., 2008, Aurora-JOGMEC-NRCan Mallik 2006-2008 Gas Hydrate Research Project progress, in DOE-NETL Fire In the Ice Methane Hydrate Newsletter, Summer 2008, p. 1-5. http://www.netl.doe. gov/technologies/oil-gas/publications/Hydrates/Newsletter/HMNewsSummer08.pdf#Page=1

Petrotech Journal December Issue 2009


MoU between Indian Oil and Deakin University on “Collaborative Research” 17 January 2010 Deakin University, one of Australia’s leading University with very strong industry connections in India and Australia, has further strengthened its research partnerships in India with the signing of a Memorandum of Understanding (MoU) with the Indian Oil Corporation Limited (IOCL) on the 17th of January 2010. Dr. R K Malhotra, Executive Director Indian Oil R&D and Prof. Lee Astheimer, Deputy Vice Chancellor (Research) signed the MoU on behalf of Indian Oil and Deakin University respectively. IOCL is amongst the leading energy companies in India and ranked 105 amongst Fortune 500 Global company rankings. The new partnership, an extension of the Deakin India Research Initiative (DIRI), will bring

researchers working with Indian Oil to Deakin under Indian Oil Golden Jubilee Research Fellowships and vice versa. There would be focus on Research Projects with a high scope for commercialisation. IOCL R&D which has so far developed over 3500 lubricant formulations and commercialised 11 in house developed technologies for different refining processes and products, has identified two projects in the area of environmentally friendly lubricants through this partnership. Mr. L N Gupta, Jt. Secy., Ministry of Petroleum and Natural Gas, Director R&D Mr. Anand Kumar and Director Refineries Mr. B N Bankapur attended the signing and welcomed this new initiative.

The Year that was 2009

Petrotech Society celebrated a decade of Excellence on 9th June, 2009

18th Governing Council & 7th Annual General Body Meeting of Petrotech Society held on 20th November 2009

Seminars and Annual Schools

Regional Meets


South India

Inauguration of 5th Proficiency Course on “Modern Practices in Petroleum Exploration” by Dr S J Chopra, Chancellor, UPES at KDMIPE ONGC, Dehradun

Mr K K Acharya delivering the Inaugural address at the Inaugural Session of Seminar on “Advances in Value Chain of Hydrocarbon Sector” at Chennai



Mr J C Agrawal "OTR (HR) IOCL with the participants of the 4th Summer School on “Petroleum Refining & Petrochemicals” held at 11pm Gurgaon

Mr. N M Borah, CMD OIL delivering the inaugural address of National Seminar on Sustainability through Environment Management: Back to Basics Approach held at Bangalore


North East

R&D Conclave III - Mr. Vikram Singh Mehta, Chairman Shell India. Inaugurating the conclave

“Hydrocarbon Industry Growth- Prospects & Challenges in North East” held at Numaligarh Refinery, Assam



Ms Indira Samarasekara, President, University of Alberta, Edmontoh Canada inaugurating the Academiea Industry Interface during Petrotech 2009

Inauguration of Petrotech Chapter at RGIPT Rae Bareilly

PETROVISION 2009 organized by PETROTECH Chapter at MIT Pune

Management Conclave at Pandit Deendayal Petroleum University, Gandhinagar

Industry Awareness

Petrotech Chair Professor, Dr A N Bhaskaran delivering a lecture on Nanotechnology organised by Petrotech IIT Delhi


Lecture in NIT, Jallander “Refinery and Petrochemical”


Events E-Newsletter: Petrascope

Inaugural Session of 2nd tional Tour to University of

Industry Alberta,


Mr R S Sharma, Chairman Petrotech & Mr Naresh Kumar President , Petrotech launched the E-Newsletter & released the Petrotech brochure

Veterans Forum

International fourm on Talent, Training Trend in the context of Globalization at SINOPEC, China

1st Meeting of Petrotech Veterans Forum organised on 20.11.2009

Guest lecture on Invention & Innovation. Some Personal ReďŹ&#x201A;ections by Dr M M Bhasin, Senior Scientist, MATRIC, USA


Mr R S Pandey, Secretary MoP & NG and Mr R S Sharma CMD ONGC & Chairman Steering Committee at the 1st Core Group meeting of Petrotech 2010

Convenor, Petrotech-2009 handing over report to convenor, Petrotech 2010

Signing of MoU between Petrotech- 2010 and ITE (JV), Ltd, UK (Exhibition Partner), Petrotech-2010

Corporate members

The Petrotech Society

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Petrotech Journal December 2009