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Introduction to process safety for undergraduates and engineers 1st Edition Ccps (Center For Chemical Process Safety)
Process safety: leadership from the boardroom to the frontline Third Edition American Institute Of Chemical Engineers. Center For Chemical Process Safety
In Chemistry, Process Design, and Safety for the Nitration Industry; Guggenheim, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
ACS SYMPOSIUM SERIES 1 155
Chemistry , ocess Design, and Safety for the Nitration Industry
Thomas Guggenheim , Editor
SABIC Innovative Plastics
Indiana
Library Congr ess Cataloging - - Publication Data
Chemistry , process design, and safety for the nitration industry / Thomas Guggenheim, editor , SABIC Innovative V Indiana ; sponsored the ACS Division
Includes bibliographical references and ISBN 978 - 0 - 8412 - 2886 - 3 paper)
Nitrates - - Safety Nitration - - Chemical processes -Safety measures - - Chemical plants - - Design and construction -Chemical process control -Congresses. Guggenheim, Thomas II. American Chemical Society Division Industrial and Engineering Chemistry 2013 549′.732 - - dc23
The paper used this publication meets the minimum requirements American National Standard for Information Paper for Printed Library ANSI Z39.48n1984.
Reprographic copying beyond that permitted Sections 107 108 the U.S. Copyright Act allowed for internal use only , provided that a per - chapter fee plus per page paid the Copyright Clearance Center , 222 Rosewood Republication reproduction for sale pages this book permitted only under license from ACS. Direct these and other permission requests ACS Copyright Publications 1 155 16th W
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In Chemistry, Process Design, and Safety for the Nitration Industry; Guggenheim, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
For eword
The ACS Symposium Series was first published 1974 provide a mechanism for publishing symposia quickly book The purpose the series publish timely , comprehensive books developed from the ACS sponsored symposia based current scientific Occasionally , books are developed from symposia sponsored other ganizations when the topic keen interest the chemistry audience.
Before agreeing publish a the proposed table contents reviewed for appropriate and comprehensive coverage and for interest the audience. Some papers may excluded better focus the book; others may added provide comprehensiveness. When appropriate, overview introductory chapters are added. Drafts chapters are peer - reviewed prior final acceptance rejection, and manuscripts are prepared camera - ready
a rule, only original research papers and original review papers are included the V erbatim reproductions previous published papers are not accepted.
ACS Books Department
eface
This the third ACS Symposium Series book dealing with the first two having been published 1976 and 1996. The nature this 2013 publication reflects the changes worldwide process safety and geographies research and manufacturing. The contributions this book were first presented the 243 r d ACS National Meeting San California March the Industrial and Chemical Engineering Division.
Several the chapters deal with the bur geoning capacity increases the polyurethane industry , requiring improved methods nitrate benzene and ultimately produce MDI and TDI. Methods manage waste streams from these nitrations plants are also There are several chapters process safety that discuss accident investigation, process redesign, and sensitivity testing ener getic Hazards laboratory and pilot plant nitration studies are addressed. Several the papers describe considerations which must taken into account when analyzing nitration reaction These chapters represent practical application known principles and Some the chapters read more like a tutorial than a scientific paper Those new nitration will benefit the most from reading this but will serve remind the experienced factors consider when operating a nitration facility . By means are all hazards nitration covered this T
Festschrifts are included this publication, one for James Dodgen and one for Chet Both these individuals were highly deeply experienced technologists who studied the processing and nature ener getic They remind the need include minds such theirs when designing and operating nitration facilities.
The Editor wishes thank those who made this book Mary Moore Eastman Chemical Company assisted ganizing the nitration symposium the 243 r d ACS National The expert staf f ACS Books streamlined the publishing Thanks all the authors and reviewers who labored produce each chapter the book. Finally , thanks Jacob Oberholtzer and Roy both working for for encouragement and technical and SABIC for financial support.
Thomas L. Guggenheim
SABIC Innovative Plastics V ernon, Indiana 47620
James Dodgen 1921–2010
Jim Dodgen, born Anniston, Alabama, graduated from Geor gia Institute T echnology with a Chemical Engineering whereupon entered the U.S. Navy . Lieutenant Dodgen was assigned the Air Force, Pacific managing ordnance from 1943 until March 1945 the Marshall Jim married Charlene W ard 1945 and they have two sons, James . and From 1945 until had assignments pertaining bomb - and torpedo - handling equipment for the Bureau Ordnance, and then distributing aviation armaments with the Bureau Aeronautics. From 1946 Jim worked a senior engineer for where designed chemical plants, while staying the military a reservist. 1951, was called back military From 1955 Jim was head the propellants, explosives, chemicals, and pyrotechnic section the Bureau then worked the Naval Propellant plant Indian Head Maryland, serving director from 1959 1962. During this time worked propellant units for multiple systems including T Sidewinder , Sparrow , and Hawk. 1962 served the representative the Bureau Naval W eapons Hercules Utah, where was responsible for engineering and inspection the second stage 1965 was transferred the Naval T orpedo Station W ashington, working Mark torpedoes. retired from the Navy with the rank Commander 1968 and worked briefly Aerojet Solid Propulsion Co., and Cordova Chemical Co.
Charlene died remarried V ginia Britten 1972 and became a wonderful father her three daughters. 1974, Jim started Dodgen Engineering Company , a one - man then consulted with many companies involved the manufacture propellants, explosives, and chemicals until his death
the editor , working General Electric the got work with Jim when started a lar - scale mixed acid nitration plant. Jim was one several consultants hired oversee the engineering and safety aspects the possessed the essential elements required when designing and operating a plant that handles ener getic material namely , deep practical experience and technical The plant started and ran without incident; and his insight and ability teach others lent confidence those who ran the
When a condenser failed another nitration plant (one can read about this one the chapters this Jim was had data his files trinitromethane (the suspected culprit the failure) that was not the public This data proved very useful, resulting the safe redesign the failed Commander James Dodgen was a model technologist and wonderful coworker .
Chester elecki 1927–2007
Chester (Chet) was born Polish immigrants Newton T Pennsylvania 1927, learning English when went school. 1945, left high school and joined the Navy . was dischar ged 1946 and his older sister pushed him finish high school, after which obtained a B.S. chemistry from Kings College biochemistry from Duquesne University , and his Ph.D. physical chemistry from F .O. Rice the Catholic University America W whereupon started working for Thiokol Chem. Corp. the Reaction Motors division. became a manager directing work propellant technology , specifically mixed hydrazine fuel systems. This phase s career concluded with the successful landing Surveyor 1 the moon 1966, which employed the hydrazine Since the Surveyor briefly bounced the surface during the landing, Chet liked claim that the fuel was also responsible for the first successful launch a vehicle from the s
While Thiokol, Chet began testing propellants, commercial explosives, and industrial chemicals determine their thermal stability , detonation velocity , critical diameter , ignition mechanisms, and shock sensitivity . 1963, founded the Fire and Explosion Hazards Evaluation a service the chemical process industries directed the reduction processing accidents. 1968, Chet was appointed Manager Research Operation Reaction directing work propellant and explosives combustion and pilot plant process studies.
with W illiam - founded Hazards Research Corporation (HRC) continue safety studies for the chemical industry . From that date until his Chet directed several thousand studies access the safety chemicals and chemical processes a multitude industries. W ork
was performed for the Army , Navy , Air Atomic Ener Department T ransportation, the OSHA, and the chemical industry lar ge. HRC determined the root cause countless failures chemical facilities, leading safe redesign several cases, opposing parties hired Chet evaluate the circumstances the failure question, and based his findings settled the speaking the high regard others placed Chet married the chemical nature materials with the engineering used handle When interacting with him for the first was not possible discern whether was a chemical engineer a chemist, a physicist for that matter . the early 1970s Chet developed a course Fire and Explosion Hazards Evaluation for the American Institute Chemical Engineers. This proved fective course, and was given hundreds times professional meetings and companies around the Chet was a masterful educator , and special person and tutor authors Odle and Guggenheim. One can only ponder how many industrial incidents and personnel injuries were averted because the forts Chet and all his associates HRC. expertise and experience like s that required when designing and operating complex chemical Chet was a warm individual. was once contracted investigate a pump explosion and interviewed the people the plant the time the asked how their ears were feeling. The question was part compassion and part science: knowing the distance and orientation the witness from the whether the ear drum was intact not, the metallur , and whether the pump impellor housing failed a brittle ductile manner , quickly gave Chet estimate the amount material that had led the explosion and the event was a detonation a deflagration.
T o see s photograph color the printed please see the color insert.
Editor ’ s Biography
Thomas Guggenheim
Thomas Guggenheim earned a B.S. degree Chemistry from St. Olaf College 1978 and a Physical ganic Chemistry from the University Minnesota .G. Gassman) 1983. began his career the Corporate Research Center , working the area engineering before moving Plastics Mt. V ernon, Indiana 1989 (SABIC purchased Plastics
Since that has worked process chemistry new process development, process safety analysis, wastewater management, analytical method patent and expert nitration chemistry and processes manufacture
In Chemistry, Process Design, and Safety for the Nitration Industry; Guggenheim, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
The Adiabatic Mononitr obenzene ocess the Bench Scale 1974
a T otal W orld Capacity Appr oaching
Million MTPY 2012
Alfr Guenkel *
NORAM Engineering and Constructors Ltd., 200 Granville Str eet, Suite 1800, V ancouver , BC, Canada V6C 1S4 * E - mail: aguenkel@norameng.com
The age adiabatic mononitrobenzene (MNB) production began with a meeting held July 1974 the Canadian Industries Ltd. (CIL) Explosives Research Laboratory Quebec, T senior scientists the American Cyanamid Company disclosed the adiabatic MNB and invited CIL contribute its sulfuric acid concentration technology , and lead the piloting the adiabatic Three simple questions had answered that time: What the rate - products formation? Can the spent acid recycled indefinitely? What scale - rules should applied size industrial - scale stirred tank nitrators? The first adiabatic MNB plant was brought line 1979, Louisiana, that the s MNB production was less than 1 million metric tonnes per year (MTPY), all coming from plants based the incumbent isothermal technology The world capacity 2012 for MNB now approaching million MTPY , predominantly from adiabatic This paper a review challenges which had overcome bring the now dominant adiabatic MNB process its current state high reliability , high yield and ener ficiency , and excellent safety record. MNB capacity estimates quoted this paper should viewed only . Producers keep production records confidential.
Backgr ound
The development the adiabatic MNB process started with a meeting held July 1974 CIL ’ s Explosives Research Laboratory . T senior scientists the American Cyanamid Company disclosed, a half - page document, the adiabatic MNB process concept and invited CIL participate a joint development project, where CIL would contribute its sulfuric acid concentration technology . The process concept was simple: Nitrate benzene a lar excess mixed suf ficient absorb all the heat nitration, decant the crude MNB phase, then flash the spent acid under vacuum boil f water generated chemically , char ging the reconcentrated sulfuric acid with additional nitric acid, and finally sending the resulting mixed acid the nitration The potential benefits were immediately evident; the heat nitration was about the same the heat required boil f the water from the spent acid. This would result substantial ener savings relative the isothermal where the heat nitration dissipated cooling the nitrators and thus wasted. Capital savings would come from the elimination almost all the heat - transfer surface areas the isothermal nitrators and the associated sulfuric acid concentrator . During the meeting was agreed that three questions would have answered through a pilot What the rate - products formation? Can the sulfuric acid recycled indefinitely? What scale - rules should applied size the proposed stirred - tank nitrators? These nitrators had achieve essentially complete conversion nitric acid MNB for process economics and environmental reasons.
The MNB Market
American Cyanamid disclosed the 1974 meeting that they were contemplating building MNB plant with a capacity 350,000 MTPY , which seemed surprising the The total MNB production 1974 was only 230,000 MTPY ( 1 ) . What t recognized the CIL party , which included the author this paper , was that a new class polymers, namely polyurethanes, had become a commercial reality the 1960’ and was a rapid growth trajectory , which has continued this day .
The first step the synthesis MDI - based urethanes requires 1978 the total world production MDI was 400,000 MTPY , which steadily increased 2 million MTPY 1998 ( 2 ) This corresponded average growth rate per annum. T o support this growth has been necessary build a world - scale MNB plant almost every year , not counting capacity required the replacement inef ficient isothermal plants. Some lar isothermal plants were, fact, built the 1970’ only scrapped the 1980’
Extrapolation production capacity through 2012 and beyond, accounting for projects known planning stages, suggests that current MDI capacity may over 6 million MTPY , and could exceed million MTPY
Much the growth will take place China, where currently least seven major projects are various stages 2010 the share MNB production worldwide was about 25% for the USA, 30% for Europe, 25% for China and 20%
for the rest the world ( 3 ) s share will likely exceed 50% within the next three years.
MNB has become a commodity chemical, and safe assume that least one world - scale plant will built every year for the foreseeable The other trend has been build plants with lar capacities, half a million MTPY .
First - Generation Adiabatic MNB T echnology
Based the outcome the CIL / American Cyanamid pilot development work, two adiabatic MNB plants came stream 1979, with individual capacities and MTPY ( 4 ) These two plants immediately accounted for about a third capacity ( 1 ) and caused the subsequent shut - down a number isothermal
The pilot work did show that the rate formation nitrophenol - products was somewhat higher than that the isothermal but that was not overly problematic the first two plant sites given the infrastructure the small pilot scale was dif ficult recycle the sulfuric acid more than 100 times, but negative fects could
The problem the acid recycle tests was that the acid inventory had small order maximize the number times the sulfuric acid was and the same time have enough material accommodate the sampling and analysis the process. a full - scale MNB the acid cycle time typically about 5 that 100 pilot plant cycles corresponded only a single plant operating shift.
Surprisingly , meaningful data the kinetics heterogeneous benzene nitration could found the literature the time. the isothermal MNB process, kinetics had never been much interest since the nitrator was always enough”, provided that the required heat - transfer area could accommodated within the nitrator volume, provided that the acid concentration was such that nitronium ions were and provided that the benzene was well dispersed the acid.
the pilot plant the kinetics were studied through adiabatic batch nitration experiments, where the extent nitric acid conversion was established recording the rise nitrator temperature a function T ime zero was when the total batch change benzene was injected into the nitrator a selected initial nitrator mixed acid and agitation intensity All three variables could examined separately through this The outcome the kinetics study – mostly a 100 beaker scale, but also a nitrator vessel diameter , and even a single run a 200 liter reactor – was scale the nitrators the basis maintaining a constant power input per unit T o the surprise the research engineers and and the first commercial users this technology , the nitration rates the full - scale plants were about two times faster than None the common stirred - tank scaling rules could explain the high nitration rates. Evidently something else was having a significant fect the nitration
Sometime after the completion the adiabatic pilot plant work, a few studies the kinetics nitration reactions were presented a number researchers the 169 t h Meeting the American Chemical Society 1975 ( 5 ) . The findings
these studies were useful for comparing relative nitration rates dif ferent aromatic compounds, but they could not used size the adiabatic nitrators. Following the successful commissioning the first two adiabatic plants, and benefiting from the experience obtained during the startups, five more adiabatic plants were built using the stirred nitrators described reference ( 4 ) . Patents were granted the American Cyanamid Company for the adiabatic process 1977 ( 6 ) and 1978 ( 7 ) . the course a review prior art technology was found that the DuPont Company had actually patented adiabatic batch process 1941 ( 8 ) .
The DuPont Company also recognized the potential MDI growth the 1970’ and developed alternative adiabatic process, called the azeotropic where the heat nitration was removed through the boiling benzene and water . Patents were granted for this process 1975 ( 9 ) and 1976 ( ) . W ith a number adiabatic MNB plants having come stream, and view the rapid capacity the Stanford Research Institute published a report the economics the isothermal and adiabatic technologies 1986 ( 1 1 ) . The isothermal MNB technology was still widely used that 1990 a chapter and was published John s Encyclopedia Chemical Processing and Design ( ) , where the technical merits the isothermal and adiabatic processes were compared.
Second - Generation Adiabatic MNB T echnology
the late 1980’ s some the engineers who played lead roles the development the first - generation adiabatic MNB plants came together again see anything could done improve the A motivating factor was answer the nagging question why , the first - generation the plant - scale nitrators gave twice the nitration rates compared those obtained the pilot was then postulated that the benzene was not optimally dispersed the pilot nitrator , had tacitly been assumed. Could that the data generated the kinetic studies were nothing more than the results a transient dispersion phenomenon? T o test this hypothesis, some beaker - scale experiments were carried out where benzene was pre - dispersed sulfuric acid for some time, and where the nitration reaction was initiated the stoichiometric amount nitric This addition sequence dif fered from that used the earlier kinetic where benzene was injected into mixed acid. speculated, dif ferent nitration rates were observed, depending the length time benzene pre - was also noted when stopping the agitator part - way through a run, the reaction would stop within seconds and that the ensuing phase separation was very even though the benzene and nitrobenzene droplets were very small. became apparent that the initial dispersion benzene and the degree benzene - sulfuric acid coalescence have significant fects the nitration rate. These fects are very dif ficult quantify when scaling stirred - tank From these observations a concept for a new type nitration reactor was developed. Benzene would uniformly added through a special inlet manifold, which would disperse the benzene over the cross section the mixed acid
inlet The dispersion would then pass through jet - impingement plates that were spaced and sized meet specific mixing requirements the reacting mixture passed through the plug - flow nitration was soon recognized that the nitration rate - controlling mechanisms changed the reacting mixture passed through the nitration train. A timely opportunity then fered itself demonstrate the jet impingement nitrator a commercial first - generation and subsequently retrofit and expand this plant. the early 1990’ s the first grass - roots second - generation plant was commissioned, and since that time plants have been built, are the process being using this technology , with a combined capacity about 5 million MTPY . Details the technology were publicized the author this paper a presentation given the 209 t h National Meeting the American Chemical Society 1995 ( ) .
The second - generation adiabatic process, which forms the basis the modern MNB incorporates a number important features which distinguish from the first - generation process. uses lower nitric acid concentrations the mixed which lowers the temperature rise through the nitration allowing the MNB / Acid decanter operate under a nitrogen blanket atmospheric This enhances the safety the process that the chance developing secondary exotherms, which are known occur through a reaction between MNB and sulfuric acid temperatures above 180 a pressurized nitrator , greatly reduced. the first - generation process, the MNB / Acid decanter had pressurized prevent benzene flashing, and emer gency quench tank had The second generation process also uses a type plug - flow nitrator rather than the first - generation back - mixed nitrators series (i.e., series This together with the lower operating results a 50% reduction the nitrophenol generation rate. Several specific aspects the new process were patented ( , )
Operational Issues
addition ener ficiency and capital savings the nitration train and acid concentrators, there are many other important aspects which play a role MNB production including plant reliability , safety , MNB purity , waste treatment and disposal, and the impact the environment.
Reliability
W ith reference plant reliability , has recognized that the MNB plant represents just one step the multi - step synthesis The total investment for a world - scale MDI complex the order several hundred million which the MNB plant accounts for less than a quarter Since not desirable hold lar inventories intermediates, the MNB plant reliability and the - stream factor are great economic
Current second - generation adiabatic MNB plants achieve - stream factors over 99%.
The oldest first - generation MNB plant has now been operation for and has similarly achieved very high - stream factors.
Safety
A number key safety aspects always have kept mind during design MNB but also the course its long - term These aspects can classified under the following headings:
Exotherms the Nitration T rain
has been found that significant exotherms occur the nitration train the sulfuric acid / MNB mix reaches temperatures about 180 a pressurized nitrator ( ) . The reactions between acid and MNB result the formation tar and unknown gaseous - which can cause overpressure the nitration train.
Exotherms MNB Distillation
Several incidents have been reported where explosions occurred the sump MNB distillation The culprits have been leaky steam valves the reboiler during shut - downs leading the slow concentration unstable impurities the sump the the accumulation unstable sodium salts nitrophenols the heat transfer area the reboiler ( ) .
Nitric Acid / MNB
explosion caused a reaction between nitric acid and MNB leveled MNB plant 1960 with a number fatalities ( ) . has been shown that nitric acid / MNB mixtures can detonate ( ) .
Ammonium Nitrite
some plants ammonia used MNB washing remove nitrophenols from the crude MNB. More commonly , a caustic solution used for this purpose. Introducing ammonia a plant where X produced a - product always has viewed with concern. Unstable solid ammonium nitrite can form through gas - phase reactions and settle unexpected places (for example vent can deposit the casing benzene pumps handling the benzene recycle stream. V iolent decompositions are known the author have occurred a number
Benzene Handling
The major imported feedstock MNB plant benzene, which classified a Nitric acid often produced While methods for bulk shipment and handling benzene from refinery sources are well developed, the disposal the small benzene waste which can contaminated with trace amounts aliphatic compounds that were initially present the benzene This pur stream commonly sent f - site for disposal. Due consideration has given handling this waste stream environmentally safe manner aliphatics pur process which greatly reduces benzene pur losses has been recently developed NORAM.
Crude MNB Purification
Crude MNB from a nitration train contains nitrophenols (NPh’ s), dissolved entrained sulfuric dinitrobenzene dissolved nitric oxide and excess benzene. The NPh’ s and acid are commonly neutralized aqueous washing system form water - soluble The adiabatic process operates with a stoichiometric excess benzene ensure that essentially complete nitric acid conversion obtained the nitration train. Excess benzene removed steam stripping vacuum and then recycled back the Aliphatic impurities coming with the benzene partially oxidize carboxylic acids, but also accumulate the benzene recycle X stripped the benzene recovery process and the sulfuric acid concentrator , and further treated the X abatement area the MNB Some gas phase aniline processes require very low concentrations DNB (dinitrobenzene, <10ppm) the feed MNB minimize catalyst MNB purification via distillation may required some cases.
W aste T r eatment
A number liquid waste streams are generated MNB plant, including wash water containing nitrophenolic aliphatics - containing benzene pur stream, a possible sulfuric acid pur ge, and a dinitrobenzene containing pur
The following a brief review the status current waste treatment technologies.
T r eatment Nitr ophenols
Nitrophenolic waste treatment was simple the first two adiabatic plants; one plant was permitted use existing injection and the other had available very lar site - wide activated carbon beds. Nitrophenols are toxic the micro - ganisms biological treatment even low concentrations. T reating nitrophenols biological water treatment plants would require massive dilution water volumes for a world - scale MNB plant, which usually not Even there doubt that some the nitrophenolic
isomers are actually A hydrothermal process ( ) has been developed whereby nitrophenol waste water thermally degraded high temperature and pressure under slightly subcritical The fluent from this thermal degradation process can handled biological treatment NORAM has built a dedicated biological treatment plant for nitrogen and BOD removal the fluent from adiabatic MNB using the thermal degradation process for the pre - treatment the nitrophenol - containing wash - water . alternative approach dealing with nitrophenol wash - water incineration.
Aliphatics Pur
V arious aliphatic compounds occur trace quantities nitration grade benzene and are partially degraded through oxidation the but some the aliphatic species can also build the benzene recycle loop a point where they may have pur the pur contains both aliphatics and a stoichiometric excess benzene, well some MNB, this pur results benzene good quality benzene a pur usually not required. However , benzene from certain supplies can contain stable species that can build recycle even they are present very low
Sulfuric Acid Pur
a typical world - scale the sulphuric acid inventory the nitration train corresponds approximately the hourly intake nitric acid. Contaminants present the nitric acid will build the sulfuric acid typically a factor several hundred, until the contaminants reach a steady state concentration the T ypically , this steady state reached through pur from acid entrained the crude MNB, and acid spray entrainment the vapor stream leaving the sulfuric acid concentrator Additional sulfuric acid pur for process reasons normally not required unless the feed nitric acid contains unusually high concentrations non - volatiles such iron, calcium and lead. Sulfuric acid - containing washwater could possibly recycled the nitration train order reduce sulfate concentrations the aqueous plant fluent.
X Recovery
A patent ( ) has been issued for a process operating elevated pressure capture X generated the nitration train for recycle nitric acid. The benefit a slight improvement the nitric acid yield, but more importantly , this process substantially reduces the concentration nitrites and nitrates the fluent water , and thus reduces water treatment costs.
Dinitr obenzene Pur
plants where MNB distilled remove heavy fractions and DNB, the residue has pur ged from the still This pur typically incinerated fsite.
Envir onmental
The total residual X and benzene vent rates from MNB plant can kept below 1 / even a world - scale through conventional scrubbing systems. This is, however , longer suf ficient. new MNB plants the vent from the plant normally sent a plant - wide thermal oxidizer .
Patents and T echnology Advancement
inevitable that a chemical having a long, steady and rapid growth profile, such MDI and its precursor MNB, will increasing commercial significance and become the focus dedicated R&D the case MNB this reflected numerous patent applications ( , ) which have been filed over the past
Nowadays MNB technology advanced small steps, through the know - how accumulated over the past years plant designers and through the day - - day experience the plant Something new learned from every project, and each new plant incorporates incremental
Summary
• The s MNB plant capacity has grown almost - fold between 1974 and from less than one million MTPY a capacity approaching million MTPY , representing a growth rate about per year .
• V irtually all new MNB capacity has come from two generations adiabatic MNB processes. The first process, having been developed uses stirred nitrators series under while the second - generation technology , developed 1988, uses plug flow nitrators operating against atmospheric back - Most the old isothermal plants have been shut down and scrapped.
• The driver for MNB growth has been the growth MDI - based urethanes, which were first commercialized the 1960’
• W ithin the next few years China will account for about 50% world MNB
• The enormous size world - scale MNB plants, some with capacities excess 500 thousand MTPY (1600 has necessitated the refinement and optimization MNB purification technologies, and development technologies deal with - products environmentally sound manner .
• Benzene yields the adiabatic process exceed and nitric acid yields exceed 99.7%.
• Economic technologies exist degrade biotoxic nitrophenols such that the aqueous fluents from MNB plant can treated biological treatment
• Nitrite and sulfate concentrations the fluent can controlled meet site - specific regulations.
• most plants there typically only one aqueous fluent stream dealt with, and a single plant vent, which normally routed a site - wide thermal oxidizer
Refer ences
Dickson, E.; W ahlen, J.; Kitai, Aniline and Nitrobenzene. Chemical Economics Handbook ; Stanford Research Institute (SRI International): Menlo
TDI / MDI ; PERP / - S8; Nexant ChemSystems: San Francisco, October This report not the public domain but can purchased www .chemsystems.com / reports.
L R P Nitr Methylenedianiline
Diisocyanate ; PERP 201 1 - Nexant ChemSystems: San Francisco, May This report not the public domain but can purchased www .chemsystems.com / reports.
Guenkel , ; Prime , ; Rae , Nitrobenzene via adiabatic Chem. 1981 , (16) , .
Albright, F Hanson, Industrial and Laboratory Nitrations ; Gould, F ACS Symposium Series 22; American Chemical Society: W ashington, DC, 1976.
V T V Adiabatic Process for Nitration Nitratable Aromatic Compounds. U.S. Patent 4,021,498, 1977. V T V Continuous Adiabatic Process for the Mononitration Benzene. U.S. Patent 4,091,042, 1978. Castner , Nitration ganic Patent Dassel, W . Azeotropic Nitration Benzene. U.S. Patent 3,928,475, 1974. McCall, Azeotropic Nitration Patent 3,981,935, 1 Y Y . C.; F . omatic Amines ; Process Economics Program Report 76B; Stanford Research Institute: Menlo Park, CA, 1986. J.; W . Nitrobenzene and Encyclopedia Chemical ocessing and Design ; Marcel Dekker , Inc.: New Y 1990; V p
13. Guenkel, A.; Maloney , T . W . Recent Advances T echnology Mononitrobenzene Nitration: Recent Laboratory and Industrial Developments ; Albright, F Carr , V . C., Schmitt, J., Eds.; ACS Symposium Series 623; American Chemical Society: W
14. Guenkel, A.; Rae, M.; Hauptmann, Nitration Process. U.S. Patent
In Chemistry, Process Design, and Safety for the Nitration Industry; Guggenheim, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
Jet
Impingement Reactor Patent 4,994,242, 1991.
Silverstein , ; W ood , ; Leshaw , Case Study reactor design for hazards Loss . 1981 , , .
17. Badeen , C. ; T urcotte , ; Hobenshield , ; Berretta , Thermal hazard assessment nitrobenzene / dinitrobenzene Hazar Mater 201 1 , 188 , .
Lodal , P Distant replay: What can reinvestigation a - year - old incident tell you? A look Eastman s 1960 aniline plant ocess 2004 , , 221
19. Mason , C. ; V Dolah , W . ; Ribovich , Detonability the System Nitric and W ater Data 1965 , , 173 .
20. Larbig, W . Process for W orking fluents Containing Nitro - HydroxyAromatic U.S. Patent
21. Brereton, C. H.; Guenkel, Nitration Process. U.S. Patent 5,963,878,
22. Hermann, H.; Gebauer , Process for the Nitration Aromatic Compounds. Patent
23. Gillis, P . A.; Braun, H.; Schmidt, J.; V erwijs, W V elten, H.; Platkowski, Process for Ring Nitrating Aromatic Compounds a T ubular Reactor Having Static Mixing Elements Separated Coalescing Zones. U.S. Patent 6,506,949, 2003.
Effect Reaction Conditions the Formation Bypr oducts the Adiabatic Mononitration
Benzene into Mononitr obenzene (MNB)
Sergio Berr etta * , 1 and Brian Louie 2
1 NORAM Engineering and Constructors, Ltd., 200 Granville Str eet, Suite 1800, V ancouver , B.C., V6C 1S4 Canada 2 Resear ch, Inc., 200 Granville Str eet, Suite 1800, V ancouver , B.C., V6C 1S4 Canada * E - mail: sberr etta@norameng.com
T main impurities are made the industrial production These impurities are nitrophenols and dinitrobenzene The formation rates these impurities are significantly fected the initial reaction conditions. Understanding these fects important first step the continuous - going research aimed towards reducing the formation these However , very limited work has been published this subject. This paper presents the findings a study done the conducted a laboratory examining the fect relevant industrial operating conditions the formation rates nitrophenols and The selected operating which can usually manipulated most industrial production MNB facilities, are: initial sulfuric acid average reaction and nitric acid concentration the mixed acid feed.
Intr oduction
Mononitrobenzene produced industrially using a number adiabatic nitration technologies. The concept adiabatic nitration was first introduced Castner ( 1 ) the 1940s. However , was not until the 1970’ s when Alexanderson ( 2 , 3 ) proposed a new set process conditions for the adiabatic technology that Castner ’ s adiabatic nitration ideas finally led a new commercial process.
T oday , a few small industrial mononitrobenzene production facilities are still built using the conditions proposed Alexanderson. However , the majority new industrial mononitrobenzene adiabatic plants are now built based the process conditions proposed Guenkel ( 4 , 5 ) the 1990’ The main advantage s nitration process a substantial reduction the formation oxidationproducts, specifically nitrophenols, the case the nitration
Since this last significant development, researchers NORAM Engineering have been working further reducing the formation theseproducts. part this challenge, and within the umbrella a very lar research the authors ran a short test program with the aim further understanding how the process conditions described the Guenkel process ( 4 ) fect - product The findings from that work are the focus this paper .
ocess Overview
Current commercial processes for the manufacture MNB typically consist a continuous addition benzene a mixture sulfuric acid and nitric acid, commonly called acid”. The sulfuric acid acts a catalyst disassociating the nitric acid into the reacting nitronium also acts a heat sink for the significant heat released the formation nitrobenzene. absorbs the water produced the Following separation the ganic and acid phases, the heat reaction, which mainly contained the lar volume sulfuric used aid the - concentration the sulfuric acid a flash evaporator .
Commercially , the nitration reaction benzene follows s s proposed operating conditions. Alexanderson proposed that MNB should commercially made most ficiently when the nitric acid concentration the mixed acid 3 7.5 wt%, sulfuric acid
wt% with the balance water . also specifies that the temperature the initial mixed acid must the range 120 ( 3 ) . Compared the technologies the day (i.e., prior art the time), s conditions led a significant reduction the formation the - product within less than 500 ppm. However , these conditions still lead significant nitrophenol - product the other Guenkel proposed a set operating conditions using a nitric acid / sulfuric acid / water tertiary diagram with the following limits: wt% sulfuric acid and wt% nitric wt% sulfuric acid and wt% water , and 100 wt% sulfuric acid, and with the additional constraint that the initial mixed acid temperature must the range 120 ( 4 ) . s which led a significant
reduction nitrophenol believed characterized a mixed acid composition which nitric acid more fully dissociated nitronium ion leading increase the reaction shown Guenkel ( 4 ) , the formation - product for the conditions the range 1700
Description the T est ogram
Based the referenced works ( 3 , 4 ) and the objectives the broader research was decided focus the test program the fect the following three process variables the formation nitrophenols and DNB - products the production MNB:
The aim this work was manipulate these process variables through a set experiments and measuring their fects the formationproducts. T o minimize the number the study was done based a factorial style analysis.
A typical factorial designed experiment includes experimental runs for all combinations both high and low , the variables The minimum number experiments complete a study then defined 2 N where N the number variables Since there were three variables interest included the test program, then the minimum number required experiments was
Based objectives the broader research program, was decided that changes the process variables interest would limited the following ranges:
• Sulfuric Acid
Concentration: wt%
• Nitric Acid Sulfuric Acid Ratio (mass basis): 0.022 0.033
• Reaction A verage T emperature: 100
The selected experimental conditions are graphically shown Figure 1 Overall, eight experiments were required cover the cube”. However , was arbitrarily decided add additional two experiments better define trends, taking the total number experiments ten. The experiments were repeated twice check the reproducibility the for a total twenty experiments. All reactions were performed using molar excess benzene, relative the nitric T able I summarizes the tar geted operating conditions for each experiment.
Figur e 1 Experimental (Courtesy Ser gio Berr
T able I . (Continued). oposed
Experiment No.
Experimental Conditions for Each Run
Experimental Set
All experiments were performed the pressurized glass reactor (PGR) shown Figure 2 .
Figur e 2 . Experimental Apparatus. (Courtesy Ser gio Berr etta).
In Chemistry, Process Design, and Safety for the Nitration Industry; Guggenheim, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
The PGR consists a 450 hemispherical bottomed glass reactor clamped underneath a thick stainless steel plate. A gasket ensures a tight seal between the reactor and the metal Reactor contents are mixed using a 4bladed T eflon® impeller that connected with a shaft seal overhead variable speed mixer . T antalum baf fles attached the top plate improve mixing while a T eflon® covered T ype J thermocouple was used measure the temperature the solution. Nitrogen gas was used pressurize the reactor and prevent benzene boiling and also inject liquids into the reactor from the overhead The initial heat input was via a manually - controlled heating band.
Experimental ocedur e
a typical nitration experiment the sulfuric acid and the nitric acid were char ged the The reactor was then attached the top overhead feed reservoir was then filled with benzene. The acid mixture was pressurized then mixed and heated the required initial The mixer was then started. Benzene was injected a predetermined rate from the feed reservoir through a T eflon® dip tube into the high intensity mixing zone the reactor
Once the reaction was deemed complete, assessed the temperature rise the the reactor was depressurized and the contents poured into a Pyrex® bottle. A portion the ganic layer , which quickly forms a layer top the acid, was removed with a pipette into a separate vial for analysis. Then a sample the acid was also removed with a pipette into a separate vial and also sent out for analysis. The samples were maintained a refrigerator 4 until their time T o avoid possible the experimental apparatus was rinsed thoroughly and dried before the next experiment.
Each the two samples per experiment MNB and acid samples) was analyzed for:
• Picric acid concentration
• 2,4 dinitrophenol concentration
• dinitrophenol concentration
• 2 - mononitrophenol concentration
• 4 - mononitrophenol concentration
• dinitrobenzene (all isomers)
Each sample was analyzed twice check the reproducibility the results.
Results and Discussion
The actual observed reaction conditions for each experiment varied somewhat from the conditions ( T able I Specifically , the average variable proved hard control. T able presents the actual observed experimental reaction conditions for each
The test results are summarized Figures 3 and 4 The figures show the average analytical result for each combination operating conditions. Let first analyze the experimental results with respect nitrophenol formation. The data Figure 3 was introduced into Microsoft Excel and its multivariable regression analysis tool was used develop a correlation between nitrophenol formation and the process variables: reaction average sulfuric acid concentration, and nitric acid sulfuric acid ratio. Equation 1 the output from the For convenience the following equations 1 and 2 , the units for nitric acid sulfuric acid ratio were changed concentration nitric acid the sulfuric acid
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of them cannot yet have learned to use wisely That however you have done, and as you hold that it cannot now be undone, your task must now be to teach them, if you can, to understand your institutions, to think about the vote they have to give, and to realize the responsibilities which the suffrage implies as these were realized by your New England forefathers when they planted free commonwealths in the wilderness nearly three centuries ago.
Valuable as instruction may be in fitting the citizen to comprehend and judge upon the issues which his vote determines, there must also be the will to apply his knowledge for the public good. What appeal shall be made to him?
We—I say “we” because this is our task in Europe no less than it is yours here—we may appeal to his enlightened self-interest, making self-interest so enlightened that it loses its selfish quality. We can remind him of all the useful work which governments may accomplish when they are conducted by the right men in the right spirit. Take, for instance, the work to be performed in those cities wherein so large and increasing a part of the population now dwell. How much remains to be done to make cities healthier, to secure better dwellings for the poor, to root out nests of crime, to remove the temptations to intemperance and gambling, to bring within the reach of the poorest all possible facilities both for intellectual progress and for enjoying the pleasures of art and music! How much may we do so to adorn the city with parks and public buildings as to make its external aspect instil the sense of beauty into its inhabitants and give them a fine pride in it! These are some of the tasks which cannot safely be intrusted to a municipality unless its government is above suspicion, unless men of probity and capacity are placed in power, unless the whole community extends its sympathy to the work and keeps a vigilant eye upon all the officials. Municipal governments cannot be encouraged to own public utilities so long as there is a risk that somebody may own municipal governments. Have we not here a strong motive for securing purity and efficiency in city administration? Is it not the personal interest of every one of us that the city we dwell in should be such as I have sought to describe? Nothing makes more for happiness than to see others around one
happy The rich residents need not grudge—nor indeed would your rich residents grudge, for there is less grumbling among the rich tax payers here than in Europe—taxation which they could see was being honestly spent for the benefit of the city. The interest each one of us has as a member of a city or a nation in seeing our fellowcitizens healthy, peaceful, and happy is a greater interest, if it be measured in terms of our own real enjoyment of life, than is that interest, of which we so constantly are reminded, which we have in making the State either wealthy by the development of trade, or formidable to foreign countries by its armaments.
We may also appeal to every citizen’s sense of dignity and selfrespect. We may bid him recollect that he is the heir of rights and privileges which you and our ancestors fought for, and which place him, whatever his birth or fortune, among the rulers of his country. He is unworthy of himself, unmindful of what he owes to the Constitution that has given him these functions, if he does not try to discharge them worthily. These considerations are no doubt familiar to us Englishmen and Americans, though we may not always feel their force as deeply as we ought. To the new immigrants of whom I have already spoken they are unfamiliar; yet to the best among these also they have sometimes powerfully appealed. You had, in the last generation, no more high-minded and patriotic citizen than the German exile of 1849, the late Mr. Carl Schurz.
When every motive has been invoked, and every expedient applied that can stimulate the sense of civic duty, one never can feel sure that the desired result will follow. The moral reformer and the preacher of religion have the same experience. The ebbs and flows of ethical life are beyond the reach of scientific prediction. There are times of awakening, “times of refreshing from the presence of the Lord,” as your Puritan ancestors said, but we do not know when they will come nor can we explain why they come just when they do. Every man can recall moments in his own life when the sky seemed to open above him, and when his vision was so quickened that all things stood transfigured in a purer and brighter radiance, when duty, and even toil done for the sake of duty, seemed beautiful and full of joy.
You remember Wordsworth’s lines—
“Hence, in a season of fair weather, Though inland far we be, Our souls have sight of that celestial sea That brought us hither.”
If we survey the wide field of European history, we shall find that something like this happens with nations also. They, too, have moments of exaltation, moments of depression. Their ideals rise and fall. They are for a time filled with a spirit which seeks truth, which loves honour, which is ready for self-sacrifice; and after a time the light begins to fade from the hills and this spirit lingers only among the best souls.
Such a spirit is sometimes evoked by a great national crisis which thrills all hearts. This happened to England or at least to a large part of the people of England, in the seventeenth century. It happened to Germany in the days of the War of Liberation, and to Italy when she was striving to expel the Austrians and the petty princes who ruled by Austria’s help. You here felt it during the War of Secession. Sometimes, and usually at one of these crises, a great man stands out who helps to raise the feeling of his people and inspire them with his own lofty thoughts and aims. Such a man was Mazzini, seventy years ago in Italy. Such were Washington and Lincoln, the former more by his example than by his words, the latter by both, yet most by the quiet patience, dignity, and hopefulness which he showed in the darkest hours. Nations respond to the appeal which such a man makes to their best instincts. He typifies for the moment whatever is highest in them.
Unhappily, with nations as with individuals, there is apt to be a relapse from these loftier moods into the old common ways when selfish interest and trivial pleasures resume their sway. There comes a sort of reaction from the stress of virtue and strenuous highsoaring effort. Everything looks gray and dull. The divine light has died out of the sky. This, too, is an oft-repeated lesson of European
history Yet the reaction and decline are not inevitable. When an individual man has been raised above himself by some spiritual impulse, he is sometimes able to hold the ground he has won. His will may have been strengthened. He has learnt to control the meaner desires. The impulse that stirred him is not wholly spent, because the nobler thoughts and acts which it prompted have become a habit with him. So, too, with a nation. What habits are to the individual man, that, to a nation, are its Traditions. They are the memories of the Past turned into the standards of the Present. High traditions go to form a code of honour, which speaks with authority to the sense of honour. Whoever transgresses that code is felt to be unworthy of the nation, unfit to hold that place in its respect and confidence which the great ones of the days of old have held. Pride in the glorious foretime of the race and in its heroes sustains in the individual man who is called to public duty, the personal pride which makes him feel that all his affections and all his emotions stand rooted in the sense of honour, which is, for the man and for the nation, the foundation of all virtue.
We have seen in our own time, in the people of Japan, a striking example of what the passionate attachment to a national ideal can do in war to intensify the sense of duty and self-sacrifice. A similar example is held up to us by those who have recorded the earlier annals of Rome. The deepest moral they teach is the splendid power which the love of Rome and the idea of what her children owed to her exercised over her great citizens, enabling them to set shining examples of devotion to the city which the world has admired ever since. Each example evoked later examples in later generations, till at last in a changed community, its upper class demoralized by wealth and power even more than it was torn by discord, its lower classes corrupted by the upper and looking on their suffrage as a means of gain, the ancient traditions died out. Whoever, studying the conditions of modern European democracies, sees the infinite fatalities which popular government in large countries full of rich men and of opportunities for acquiring riches, offers for the perversion of government to private selfish ends, will often feel that those European States which have maintained the highest standard of
civic purity have done it in respect of their Traditions. Were these to be weakened, the fabric might crumble into dust.
Every new generation as it comes up can make the traditions which it finds better or worse. If its imagination is touched and its emotions stirred by all that is finest in the history of its country, it learns to live up to the ideals set before it, and thus it strengthens the best standards of conduct it has inherited and prolongs the reverence felt for them.
The responsibility for forming ideals and fixing standards does not belong to statesmen alone. It belongs, and now perhaps more largely than ever before, to the intellectual leaders of the nation, and especially to those who address the people in the universities and through the press. Teachers, writers, journalists, are forming the mind of modern nations to an extent previously unknown. Here they have opportunities such as have existed never before, nor in any other country, for trying to inspire the nation with a love of truth and honour, with a sense of the high obligations of citizenship, and especially of those who hold public office.
Of the power which the daily press exerts upon the thought and the tastes of the people through the matter it scatters among them, and of the grave import of the choice it has always and everywhere to make between the serious treatment of public issues and that cheap cynicism which so many readers find amusing, there is no need to speak here. You know better than I do how far those who direct the press realize and try to discharge the responsibilities which attach to their power.
The observer who seeks to discern and estimate the forces working for good or evil that mark the spirit and tendencies of an age, finds it easiest to do this by noting the changes which have occurred within his own memory. To-day everyone seems to dwell upon the growth not only of luxury, but of the passion for amusement, and most of those who can look back thirty or forty years find in this growth grounds for discouragement. I deny neither the fact nor the significance of the auguries that it suggests. But let us also note a hopeful sign manifest during the last twenty years
both here and in England. It is the diffusion among the educated and richer classes of a warmer feeling of sympathy and a stronger feeling of responsibility for the less fortunate sections of the community. There is more of a sense of brotherhood, more of a desire to help, more of a discontent with those arrangements of society which press hardly on the common man than there was forty years ago. This altruistic spirit which is now everywhere visible in the field of private philanthropic work, seems likely to spread into the field of civic action also, and may there become a new motive power. It has already become a more efficient force in legislation than it ever was before. We may well hope that it will draw more and more of those who love and seek to help their fellow-men into that legislative and administrative work whose opportunities for grappling with economic and social problems become every day greater.
Here in America I am told in nearly every city I visit that the young men are more and more caring for and bestirring themselves to discharge their civic duties. That is the best news one can hear. Surely no country makes so clear a call upon her citizens to work for her as yours does. Think of the wide-spreading results which good solid work produces on so vast a community, where everything achieved for good in one place is quickly known and may be quickly imitated in another. Think of the advantages for the development of the highest civilization which the boundless resources of your territory provide. Think of that principle of the Sovereignty of the People which you have carried further than it was ever carried before and which requires and inspires and, indeed, compels you to endeavour to make the whole people fit to bear a weight and discharge a task such as no other multitude of men ever yet undertook. Think of the sense of fraternity, also without precedent in any other great nation, which binds all Americans together and makes it easier here than elsewhere for each citizen to meet every other citizen as an equal upon a common ground. One who, coming from the Old World, remembers the greater difficulties the Old World has to face, rejoices to think how much, with all these advantages, the youth of America, such youth as I see here to-night in this venerable university, may accomplish for the future of your country. Nature has done her best to provide a foundation whereon the fabric
of an enlightened and steadily advancing civilization may be reared. It is for you to build upon that foundation. Free from many of the dangers that surround the States of Europe, you have unequalled opportunities for showing what a high spirit of citizenship—zealous, intelligent, disinterested—may do for the happiness and dignity of a mighty nation, enabling it to become what its founders hoped it might be—a model for other peoples more lately emerged into the sunlight of freedom.
Transcriber’s Note
Page 48: “Americans” was printed as “Ameritans”, and changed here, presuming it was a typographical error.
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