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Clean Technologies
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Sulfuric Acid
Covering Best PraCtiCes for the industry
Sulfuric Acid T
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Covering Best Practices for the Industry
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IN THIS ISSUE > > > > Changes in the sulfuric acid market over the past 25 years
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speeding up tower replacement
FROM THE PUBLISHER
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Preventing high-temperature superheater casing failures
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On the Cover … 7 Sulfuric Acid Today celebrates 25th Anniversary with a look back at how the industry has evolved from 1994. Departments 4 Industry Insights– News items about the sulfuric acid and related industries 16 Lessons Learned– Case histories from the sulfuric acid industry 29
People on the Move– Who’s who in the industry
34 Product News– News items about sulfuric acid products and services 36 Faces & Places– Covering sulfuric acid industry events 38
Calendar of Events
25 years: A vision realized
When I sat down to write this letter, I was overwhelmed by the feeling that 25 years have gone by so quickly. Yes, it is obvious that time does not stand still—especially when it comes to publishing and deadlines—but I still remember 1994 like it was yesterday. At that time, I was working as an associate for the Baton Rouge, La.-based industrial magazine, Business and Industry Connection (BIC), when the idea of starting a sulfuric acid magazine was tossed around by an advertiser, VIP International Inc. I was both intrigued and unsure at the same time. I went to visit VIP’s office and was introduced to Jack and Becky Harris, Hoss Maddry, Stan Miller, and Darwin Passman—and I immediately felt comfortable. That’s where it all began. With VIP’s vast knowledge and experience in the industry, they encouraged me to compile the first issue. I began networking with veteran industry professionals to learn about sulfuric acid production, maintenance, and operations. I attended the MECS Sulfuric Acid Technology Seminar in Tucson, Ariz., where I met with John Horne of MECS, Ed Knoll of Acid Piping Technology, Howard Tenney of H.A. Tenney, and the late Lou Doerr of Lewis Pumps; and they happily shared their knowledge with me. I traveled to other conferences and roundtables to learn the latest developments in technology and was introduced to George Wang, now retired from Eco Services. George assists me with the magazine’s technical content and is my sulfuric acid industry mentor. I’m eternally grateful for our friendship. From there, the magazine grew into what is it today with the help of many loyal readers, contributors, industry friends, and advertisers.
PUBLISHER Kathy Hayward
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SNC-Lavalin Chile delivers outstanding HSE performance
EDITOR April Kabbash
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Trends in sulfuric acid: 25 years ago vs today
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Changes in the sulfuric acid market over the past 25 years
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Sulfur gun advancements
Marketing ASSISTANT Tim Bowers DESIGN & LAYOUT 281-545-8053 Mailing Address: P.O. Box 3502 Covington, LA 70434 Phone: (985) 807-3868 E-Mail: kathy@h2so4today.com www.h2so4today.com SUBSCRIPTIONS U.S. Plant Personnel —‑Complimentary U.S. Subscription —‑ $39 per year (2 issues) Internat’l Subscription —‑$59 per year (2 issues) Subscribe Online: www.h2so4today.com
I would like to acknowledge the companies that have consistently advertised over the past 20+ years, including: Acid Piping Technology, BASF, Beltran, Central Maintenance & Welding, Chemetics, DuPont MECS, Haldor Topsoe A/S, Koch Knight LLC, NORAM Engineering & Constructors, VIP International, and Weir Mineral Lewis Pumps. I am honored by the trust and support you have shown me over the past quarter of a century. I would like to also thank our new and returning Sulfuric Acid Today advertisers for our 25th Anniversary issue, including: Acid Piping Technology Inc., Beltran Technologies, Breen Energy Solutions, Central Maintenance & Welding, Chemetics Inc., Clark Solutions, DuPont MECS, Haldor Topsoe A/S, Koch Knight LLC, Mercad Equipment Inc., NORAM Engineering & Constructors, Optimus, Southwest Refractory of Texas, Spraying Systems Co., VIP International, and Weir Minerals Lewis Pumps. Over the years, we’ve been very fortunate to have a talented team producing the magazine—our dedicated editors, April Kabbash and April Smith, work diligently on the content of each issue, and designer Carl Accardo, whose creativity is second to none. Thank you all for the long hours and hard work that you put into every publication. Finally, what would a silver anniversary be without a party? We will be celebrating our accomplishment at our upcoming Sulfuric Acid Roundtable in Orlando, Fla., with 170 of the industry’s top sulfuric acid professionals. This year’s event is packed with informative presentations, lively panel discussions, and fun hospitality and networking functions… I’m looking forward to celebrating with all of the event’s Co-Sponsors and plant personnel in attendance. Thank you again—each and every one of you—for your 25 years of support. It truly is appreciated! Kathy Hayward Publisher
FEATURES & GUEST COLUMNS
PUBLISHED BY Keystone Publishing L.L.C.
EDITOR April Smith
A heart of gratitude
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18 Lewis® looks back on 25 years specializing in the sulfuric acid industry 20 Preventing high-temperature superheater casing failures 22 At last, a new mesh pad for the sulfuric acid industry 24
Sulfur recovery gas cleaning
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Further reflections of an acid cooler technical representative
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Checking in: Koch Knight drying tower in 18th year at Veolia
30 Peripherals of process gas and acid systems 32 Acid dew point measurement in sulfuric acid production
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Department
Industry Insights India court clears way for Vedanta Smelter restart
TAMIL NADU, India—India’s Supreme Court has cleared the way for diversified copper producer Vedanta to reopen its Sterlite Copper smelter in Tamil Nadu, after it refused to stay an order for its closure by the provincial government. The interim ruling “paves the way for the Sterlite Copper plant to reopen” and the company will now file an application to environmental regulators to operate the smelter, a Vedanta spokesman said. The plant has a production capacity of 1.1 million tons/year of sulfuric acid. India’s environmental court, the National Green Tribunal (NGT), ordered the restart of the smelter in mid-December, subject to certain environmental protection measures. The Tamil Nadu government appealed this ruling. Indian sulfuric acid buyers are upbeat on the restart of the smelter. Some market participants now anticipate that an April start-up could be realistic. The impact of the Sterlite Copper smelter’s shutdown on the domestic sulfuric acid market has been significant because of limited supply options in the region. The operator declared a force majeure on sulfuric acid deliveries following the closure, which pushed consumers into the international spot market for not only sulfuric acid but also sulfur and finished fertilizer products. Indian sulfuric acid BREEN Ad importsSulfuricAcidToday reached 1.4 millionAd:Breen t in 2018,
according to Argus analysis, up by 59 percent from 2017. For more information, please visit www. sterlitecopper.com.
ITT announces agreement to acquire Rheinhütte Pumpen Group
WIESBADEN, Germany—ITT Inc. announced today that it has signed an agreement to acquire Rheinhütte Pumpen Group, a market-leading designer and manufacturer of centrifugal and axial flow pumps, from Aliaxis Group S.A. The acquisition aligns with ITT’s focused growth initiatives in target markets and will enhance the industrial process (IP) segment’s strategy with a complementary portfolio of centrifugal pump technologies suited to corrosive, abrasive, and high-temperature industrial process environments. The acquisition will bolster IP’s presence in Europe with an expanded product range as well as enhanced pump engineering, manufacturing, testing, and channel-to-market capabilities. Rheinhütte has a 160-year heritage and is regarded as a leading provider of highly engineered pumps suited for the handling of aggressive media. Rheinhütte solutions serve specialty applications for the chemical, mining, renewable energy, and refinery processes and include solutions for sulfuric acid, molten sulfur, fertilizer, and chlorinealkali electrolysis production, among others. 3/6/19 PM Page 1 “The3:17 proposed agreement will bring
together two companies with long legacies of application expertise across a range of harsh conditions in the industrial process space,” said ITT CEO and President Luca Savi. “We look forward to leveraging Rheinhütte’s deep engineering capabilities to deliver better solutions for our customers and unlock additional growth in key global markets.” “This agreement reflects our commitment to delivering a comprehensive value proposition to our customers,” said ITT IP President David Malinas. “The addition of the Rheinhütte Pumpen brand to our current portfolio will broaden our worldwide pump presence. We are excited to join these two teams, leveraging their shared skills and commitment to delivering excellent products for our customers and partners.” Rheinhütte, which is headquartered in Wiesbaden, achieved full-year 2018 revenues of approximately $66 million. Rheinhütte has approximately 430 employees and operates in three main manufacturing locations. The proposed transaction is expected to be accretive to ITT earnings in the first full year after closing. The cash consideration of approximately $91.5 million will be funded from the company’s cash and revolving credit facility and the final purchase price is subject to customary net working capital adjustments. The proposed transaction is expected to close in the second quarter of 2019 and is subject to customary closing conditions, including appropriate regulatory approvals. For more information, please visit www.itt.com.
Electrozinc to be mothballed by mid-2019
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VLADIKAVKAZ, Russia—The Electrozinc plant at Vladikavkaz in southern Russia will be mothballed by mid-2019 and is moving all its raw material and unfinished product inventories to Chelyabinsk Zinc Plant (CZP) and other Urals Mining Metallurgical (UMMC) production sites. The move follows December’s decison by UMMC and Electrozinc to put the plant under care and maintenance indefinitely, after a fire in late October destroyed the electrolytic workshop, a key link in the production chain. The company previously said rebuilding the workshop could take at least 6-8 months. UMMC said it will carry out a feasibility study before making a decision on the plant’s long-term future. Since the beginning of December, Electrozinc has shipped 16,200 t of zinc concentrate, 10,500 t of saleable zinc clinker, and 1,500t of unfinished product from the Vladikavkaz site to UMMC’s plants in the Urals. It had to temporarily restart the secondary roaster— used to separate zinc tailings into zinc and cadmium-bearing oxides and clinker—and the hydro-metallurgical workshop to bring the material-in-process to the intermediate products stage, at which point it could be transported to another plant. The remaining stock will be shipped out before the end of the first quarter, Electrozinc said. During the second quarter, all the plant’s facilities will be put under care and maintenance. Sister company CZP, Russia’s largest
zinc producer, which is receiving the leftover feedstock, has more than double Electrozinc’s capacity for producing zinc and cadmium, but only has limited scope to offset the loss of Electrozinc production, without expansion. CZP said it has made no decision to expand output at this stage. CZP produced 191,000 t of zinc in 2018 and expects to produce 200,000 t this year. The shutdown of Electrozinc means the group will lose a substantial volume of zinc output, but there has so far been no impact on the zinc spot market premium. Some market participants have voiced concern about potential supply tightness in Russia, given that Electrozinc is one of the country’s main producers. If CZP has to supply more of its by-product cadmium to the domestic market to make up for the loss of Electrozinc production, it could have less available this year to export through tenders. For more information, please visit www. ugmk.com/en/.
ACS Group to build two of world’s largest sulfuric acid plants in Morocco
RABAT, Morocco—Morocco’s OCP Group and Spain’s ACS Group announced recently that they have signed contracts to build two factories in Jorf Lasfar, 120 kilometers south of Casablanca, which will cost €255 million, approximately MAD 2.8 billion. The contracts to build the factories “have been awarded by the OCP (Office Chériffien de Phosphates), following a tender process where several international engineering companies have taken part,” said ACS, an international civil and engineering construction company. Construction on the projects has already begun and will take another two to three years for each before they are ready to operate. The projects will be two of the largest sulfuric acid plants in the world. ACS will build the facilities and implement the processing of sulfuric acid per day, in addition to implementing basic engineering, detailed engineering, and equipment and material supply works. The sulfuric acid will be mainly used in the manufacture of granulated phosphate fertilizers. The energy the two plants generate will be used in Jorf Lasfar, “almost eliminating the necessity of resorting to external electrical power.” The plants will also optimize the production of phosphate fertilizers to support the agricultural industry in African mainland countries. Founded in 1997, the Madridbased ACS Group is a leading construction company worldwide with projects in many countries, operating in key services and sectors, including telecommunications. Meanwhile, Morocco’s OCP Group, which holds 75 percent of the world’s phosphate reserves, is one of the leading exporters and producers of raw phosphate, phosphate-based fertilizers, and phosphoric acid in the world. For more information, please visit www. ocpgroup.ma. q Sulfuric Acid Today • Spring/Summer 2019
WASTE HEAT RECOVERY BOILERS SUPERHEATERS ECONOMIZERS
Safety is a top priority at Codelco’s sulfuric acid plant project in Calama, Chile.
SNC-Lavalin Chile delivers outstanding HSE performance While working on the sulfuric acid plants of Corporación Nacional del Cobre de Chile (Codelco) in Calama, Chile, SNCLavalin’s Mining & Metallurgy team has recently achieved 600 Perfect Days on the jobsite without any work-related injuries, security incidents, or environmental releases, according to SNC-Lavalin’s global health, safety, and environmental management system (Bluebook). Over 4 million man-hours have been worked without a lost-time incident, as classified by OSHAS (Occupational Health and Assessment Series), since the start of the project. All of this was achieved in a challenging natural environment where the high altitude and desert climate were made even more difficult by the acidic environment and gas emissions generated by ongoing operations at the existing facility located immediately adjacent to the project. This engineering, procurement, and construction project will replace three existing single-absorption sulfuric acid plants with two new double contact, double absorption plants that are integrated into a large open-pit copper mine and smelter complex. The outstanding safety performance
is attributed to very engaged and committed project team members who, in spite of harsh conditions, have managed to follow HSE best practices and procedures in order to protect themselves and meet SNC-Lavalin’s and the client’s highest safety standards. “This is an outstanding result and I would like to congratulate the team for maintaining its focus on health, safety, and environment matters, preventing incidents at the work site and office,” said Andrew Curtis, general manager of the Mining & Metallurgy sector in Chile. “The challenge now is to safely and efficiently complete the construction of the project on behalf of our valued client.” Furthermore, the Perfect Days have been reached thanks to the above-target reporting on leading safety indicators such as the behavior interaction program (BIP), imminent dangers, HSE campaigns, crew meetings, and safety trainings, which are some of the preventive measures in place at the work site. This result demonstrates SNC-Lavalin’s continued dedication to prioritize safety. For more information, please visit www.snclavalin.com. q
“
This is an outstanding result and I would like to congratulate the team for maintaining its focus on Health, Safety, and Environment (HSE) matters, preventing incidents at the work site and office. The challenge now is to safely and efficiently complete the construction of the project on behalf of our valued client. Andrew Curtis, SNC-Lavalin General Manager of the Mining & Metallurgy sector in Chile
Op�mus delivered its rst sulfuric acid plant waste heat recovery system in 1996. Across the power and process industries, we’ve produced more heat recovery boilers, HRSGs, superheaters, and economizers than any ac�ve company in the USA. Op�mus and its Chanute Manufacturing plant have a long‐standing rep‐ uta�on for high‐quality workmanship and on‐�me performance. Cus‐ tomers trust our unique manufacturing exper�se and have condence in our quality control and comprehensive project execu�on.
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Sulfuric Acid Today • Spring/Summer 2019
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Department
Industry Insights
Acid Piping Technology — The world leader in reliable and cost effective products for the sulfuric acid industry since 1991
MONDI™ PIPINg SySTeMS APT HIgH PerfOrMANCe CerAMICS
MONDI™ Piping Systems – Special ductile iron alloy for 93-99% sulfuric acid at temperatures up to 300 degrees F (149 degrees C) and oleum. Unique alloy and heavy wall construction provide 30-plus years of reliable service. APT step ring gaskets provide leak-free seal in hot acid. • Proven performance in acid plants since 1983 for recirculation and transfer systems • Tough sulfate film formed results in low corrosion rates • Good tolerance to weaker acid excursions due to process upset or shutdown conditions • Industry standard used in over 800 acid systems worldwide including World Class 4500+ ton per day plants • APT maintains large inventory of pipe and fittings for routine and emergency requirements Valves & Instrumentation – Valves are gate, globe, check, plug, ball and butterfly in iron, steel, bronze, stainless steels, alloy or lined with PTFE, PFA, and FEP. Valves are supplied in class 125 psi through 2500 psi. APT has a complete automation facility for valve actuation to supply complete automated package. Instrumentation products include thermocouples, RTD, thermowells, orifice plates, pressure and temperature gauges.
APT High Performance Ceramics – High quality products which meet ASTM C-279 chemical porcelain. Products have excellent chemical resistance, high mechanical strength and low porosity. • Tower packing saddle sizes in 3”, 2”, 1 1/2”, 1”, 3/4”, 1/2” and #1, #2. #3, Super Saddles • Cross Partition Rings, Grid Blocks and Ceramic Balls • APT maintains large inventory of saddles and supports for routine and emergency requirements ASC Acid Plant Valves --- Have been supplied to acid plants for gas duct applications since 1993. These valves are used for many applications within the plant. There valves can have manual gear operators or actuators. • Butterfly valves (BV – metal step 1 percent leakage) for flow control around towers, equipment and heat exchangers • Powercam® BV valves (ANSI Class IV – 0.01 percent leakage) for preheater isolation • Flex-Wedge valves for blower isolation • Refractory BV and Jug valve used on boiler by-pass for flow control
Acid PiPing Technology Acid Piping Technology • 2890 Arnold Tenbrook Road • Arnold, Missouri 63010 USA Telephone: (636) 296-4668 • Fax: (636) 296-1824 • Email: info@acidpiping.com • Website: www.acidpiping.com
Cover Story
Trends in sulfuric acid: 25 years ago vs today
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By: April Smith, Editor, Sulfuric Acid Today
eviewing the past is useful for planning the future, so for Sulfuric Acid Today’s 25-year anniversary, we wanted to take stock of the major changes in the industry over the last quarter century. We turned to the experts, those with the greatest experience in this business, many over 35 years. We surveyed consultants, product and service suppliers, and acid manufacturers about what they see as the predominant shifts from 25 years ago to today. Here are their answers.
Challenges for producers
Leaks The most commonly cited challenge over the years has been leaky systems stemming from poor materials of construction, often cast iron, and the piecemeal manner of construction. The many cast iron sections bolted together resulted in lots of leaky seams, SO2 emissions, and safety hazards. “There were acid coolers leaking at the seams and bio-foulants growing in the joints. Operators frequently had to go out with chipping hammers to remove the algae and scale from the coolers. And this was often done while the plant ran,” (Feryl Masters, Consultant, Feryl Inc.). Knowledge deficit One of the most common issues in the industry today is the shrinking workforce, in numbers and experience. “Twenty-five years ago, most established companies had seasoned staff operating and managing the acid plants. Today, it is not unusual to have inexperienced staff operating the plants, including the supervisory and management positions,” (George Wang, Consultant, GW Consulting Inc.). Headcount reductions have caused “a knowledge vacuum,” with the most senior people reaching retirement age, and too few replacements coming up the ranks. The push from investors wishing to boost financial performance has driven companies to reduce staff. “Deferring reinvestment in human resources causes some to leave the industry and also lowers the morale of those who remain,” (Rick Davis, Consultant, Rick Davis and Associates). Years ago industry suppliers would encounter well-versed owners. “We had clients with 20 or more years of experience Sulfuric Acid Today • Spring/Summer 2019
not only showing us what to do but why to do it. They operated plants before the age of computers and truly understood how an acid plant worked including cause and effect. Those individuals are few and far between today,” (Jack Harris, President, VIP International). In addition, the growing population of inexperienced plant owners are choosing design and build contractors who are also inexperienced. “New producers expect that all bidding contractors have the necessary expertise to specify, design, and build plants, and so they just choose the lowest bid rather than have a thorough bid comparison.” But many of the engineering and construction companies lack the hands-on acid plant experience to complete the job correctly, so these new producers suffer the consequences for years to come, (Wang). Safety Keeping people safe was a challenge 25 years ago that still persists today, but the industry’s commitment to safety has evolved. “In the old days, the attitude at some facilities was ‘we have a job to do. Be as safe as you can.’ Today the attitude is ‘if we are going to do this job, we are going to do it safely or we not going to do it,’” (Harris). Though commitment to workforce safety has improved, today’s experience gap has posed challenges to safety efforts. Companies today are performing more thorough safety reviews than in the past, but their quality depends on the available talent. “The resources and qualification of the review team is critical. If the team members lack hands-on acid plant experience and thorough understanding of the process, then the review may not be as effective,” (Wang). A bright light in the safety realm that respondents cited is the collaborative efforts by a cross-sectional group of industry experts who have been documenting and sharing hydrogen safety information. Stricter standards Another significant challenge facing the industry today is the preponderance of ever stricter standards and goals that producers must meet. Plants today are striving for substantially more stringent environmental, governmental, and finan-
cial goals. Achieving these goals, in turn, involves greater measurement, reporting, and oversight activities.
Most impactful technological advancement
Materials materials materials By far the consensus advancement over the past quarter century is the increased acid resistance of construction materials. “High alloy steels and a variety of corrosion resistant plastics are the main improvements,” (Gavin Floyd, Engineering Manager, Eco Services). Twenty-five years ago most plants used lead, cast iron, and red shale bricks. “The philosophy was to design with a large amount of corrosion allowance. But this meant heavy weights, low flexibility and, in the case of lead in wet gas cleaning systems, materials that were too soft and toxic,” (Mike Fenton, Senior Business Development Manager, Chemetics, Inc.) The variety of better materials enabled equipment designers to select the most suitable material for the specific application. For example: • Stainless steel for converters, towers, heat exchangers • Anodically protected stainless steel for acid coolers • Nickel-based alloys for piping and acid tower replacement projects • Ductile iron alloy (Mondi) for piping • Composite materials and advanced alloys for WESPs • High silicon alloys for piping, ducting, vessels, heat exchangers • Fiber reinforced polymer (FRP) for gas cleaning ducting, piping, dampers, etc. The longevity and efficiencies of today’s materials is irrefutable. “Advancements in materials have allowed plants to run at lower risk, higher temperatures, for longer times between outages, and at greater capacity,” (Charlie Fast, Reliability Lead, Mosaic Co.).
drop was the primary reason for acid plant turnarounds, when plants had to shut down to screen catalyst to remove dust and debris. Better catalyst combined with improved handling techniques have significantly extended turnaround cycles, which has had profound industry effects. While greatly improving plant performance, better catalyst and handling presents a new set of challenges. Comprehensive maintenance planning and inspections are now required to ensure all equipment is reliable for the longer two- or three-year run without any unscheduled outage (Harris). Catalyst also impacts SO2 conversion and so was subject to the pressures of environmental regulation. Developments in cesium-promoted catalyst have greatly improved SO2 to SO3 conversion and reduced SO2 emissions,” (Guy Cooper, Director, NORAM Engineering and Constructors Ltd.). New software technology also came into play to better understand catalyst chemistry, which helped advance design. “New formulations and shape, such as Haldor Topsoe’s LEAP5™ and MECS’ GEAR®, further reduced catalyst pressure drop and improved conversion efficiency. Today’s double absorption plant can achieve 99.9 percent SO2 conversion or higher,” (Wang).
Catalyst Another major advancement during this period is the change in catalyst shape, from pellet to an optimized multi-surface design, which reduces pressure drop and extends plant run time. Catalyst pressure
Heat recovery Today’s heat recovery technologies have increased the benefits of cogeneration. Before 1980 nearly all of the heat generated in the acid system was lost to the cooling water system. With current heat
The many contours of Haldor Topsoe’s LEAP5™ catalyst is a major design advancement over the simple pellet shape of the past. LEAP5™ is specifically designed for oxidizing SO3strong gases.
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Cover Story
recovery systems, more of this heat energy is captured, significantly increasing the plant economics. “Today’s HRS technology can achieve 900 psig and 900 degree steam systems, whereas before 1970, most plants had less than 600 psig and temperatures below 600 degrees,” (Davis). “For plants to be able to boost and then harness their own energy, for example by using MECS® Heat Recovery System (HRS) technology, producers can both increase plant efficiency and materially reduce their carbon footprint,” (Brian K. Blair, Global Licensing Manager, DuPont Clean Technologies). Modeling and measurement With the advancement of the digital age, tools that simulate and measure the acid environment have become part of the process. Respondents identified a few they felt were particularly notable: Emission analyzers: Testing how much SO2 a plant emits can now be accomplished with in-stack analyzers, which provide immediate, precise measurements. This contrasts with the complicated, time consuming, and imprecise Reich test of the old days, (Masters).
Computational Fluid Dynamics (CFD) modeling software allows suppliers to truly understand the physics and chemistry inside the burners/furnaces so they can develop solutions to increase plant performance.
Simulators that most authentically mimic actual plant dynamics are especially valuable, particularly as more plants experience higher retirement levels and knowledge deficits. Brian Lamb of MECS monitors an operator simulator challenge at a MECS SAR Technology Workshop.
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Modeling tools: Computational Fluid Dynamics (CFD) modeling software allows suppliers to truly understand the physics and chemistry inside the burners/ furnaces so they can develop solutions to increase plant performance. CBA WhirlJet and Injector is such an example, (Christy Hofherr, Director, Spraying Systems, Co.). Operator process simulator training: Simulators that most authentically mimic actual plant dynamics are especially valuable, particularly as more plants experience higher retirement levels and knowledge deficits, (Thomas L. Muller, Engineering Fellow, Veolia North America).
Environment: trends, challenges
It’s part of business The last two and half decades have crystalized the notion that environmental stewardship is an indelible aspect of a viable operation. “For a plant to maintain its License to Operate, it must meet its emissions, all other environmental targets, plus safety obligations or it’s only a matter of time before the community or the government will call for it to be shut down,” (Herbert Lee, Sulfuric Acid Sales Manager, Chemetics). S02 Whether it’s 25 years ago or today, producers have been wrangling with this pollutant, the difference being the acceptable limits. The challenge has been making sufficient and economically feasible plant modifications to reduce the formerly allowable 4 lbs/ton emission level to the current 1-2 lbs/ton. “Government regulations, as well as financing institutions such as the World Bank, continue to push producers to reduce stack as well as fugitive emissions every day, all day.” Though compliant plants have been built in the chemical and smelter industries since the 1980s, more and more producers in the fertilizer space are being held to the same standard. Additionally, the need is expanding abroad, becoming necessary in India, China, North Africa, and South America, (Fenton). Over the last two and a half decades the most impactful technologies to mitigate SO2 have been double absorption, low ignition catalyst, and SO2 alkali scrubbers, (Leonard Friedman, Consultant, Acid Engineering & Consulting Inc.). “As a result, single absorption acid plants without scrubbing have virtually disappeared
in the United States,” (Cooper). Industry suppliers have developed a variety of abatement products and services to address SO2 emissions throughout the production process. Some of their solutions are as follows: Acid Piping Technology offers improved stem packing of damper valves used throughout gas ducting. “The stuffing box design impedes internal gas from flowing into high pressure areas and ultimately escaping into the atmosphere,” (Ed Knoll, President, Acid Piping Technology). Chemetics offers full-process acid plant designs using proprietary equipment to achieve required stack emissions in any weather condition and at varying operational rates, (Lee). DuPont Clean Technologies offers MECS® DynaWave® Wet Scrubbing Technology as a Claus tail gas treatment unit supplement or as a stand-alone unit for small-capacity plants. Also DuPont’s catalyst & Brink® mist products help meet stringent compliance thresholds (Blair). NORAM offers a process strategy for reducing start-up emissions for clients having more than one acid plant in which tail gas from the start-up plant is fed to the front end of the operating acid plant, (Cooper). Outotec’s Peracidox tail gas scrubbing system processes post acid plant SO2 before
More focused attention on NOx mitigation in recent years has had a significant impact on sulfuric acid production. VIP International’s “no-NOx” scrubber neutralizes an economizer at Eco Services’ Hammond, Ind., facility.
Chemetics offers a unique NOx abatement technology, Selective Catalytic Conversion (SCR), to reduce emissions in traditional dry gas sulfuric acid plants. The method can reduce incoming NOx emissions by 95 percent.
Beltran’s WESPs remove particulates and acid mist with collection efficiencies of submicron particulate matter at 99.9 percent or greater.
With stricter environmental regulations Outotec offers a gas cleaning plant solution that takes into account the complete process chain.
the stack, for start-up and upset conditions (Hannes Storch, VP Metals and Chemical Processing Business Line, Outotec). NOx, etc. Twenty-five years ago NOx was not on the radar as a toxic substance in the sulfuric acid industry and the only way to measure it, using pumps with colorimetric tubes, was not very accurate. “As awareness of NOx increased, manufacturers developed atmospheric monitors with electrochemical sensors that accurately measure the components of NOx,” (Darwin Passman, Safety Director, VIP International). More recently, attention to NOx, acid mist, and other contaminants have increased and their mitigation has had a significant impact on sulfuric acid production. Industry suppliers have responded by developing a number of viable solutions. A few of the more prominent technologies are as follows: Chemetics offers a unique NOx abatement technology, Selective Catalytic Conversion (SCR), to reduce emissions in traditional dry gas sulfuric acid plants. The method can reduce incoming NOx emissions by 95 percent, (Fenton). Sulfuric Acid Today • Spring/Summer 2019
Cover Story
Beltran’s WESPs remove particulates and acid mist with collection efficiencies of submicron particulate matter at 99.9 percent or greater. The technology can also be customized to reduce heavy metal contaminants in sulfuric acid. “For example, recently a number of metallurgical acid plant WESPs have been sized based on the outlet arsenic requirements instead of the acid mist outlet loadings,” (Michael Beltran, President, Beltran Technologies). Outotec can offer NOx solutions throughout much of its technology portfolio, once legislation demands it. The company also has a wide technology portfolio for removing heavy metal contaminants from the off-gas stream. These products include WESPs, the industry benchmark process for mercury removal, as well as other niche solutions, (Storch).
Operations
Knowledge deficit As mentioned earlier, expertise retiring without equivalent knowledge in a younger workforce has negatively impacted plant operations in recent years. “In the past, after we designed and built a plant, an experienced producer took it over. He knew what he was doing. This certainly is not the case today and is particularly problematic in remote areas with limited skills available in the local community,” (Storch). Remote monitoring, control The digital age and the advancement of instrumentation, most notably distributive control systems (DCS), represent the most prominent operational innovation respondents cited over the last 25 years. DCS enables producers to see how a plant is running in real time as well as view an operational history to understand failures so that they can be avoided in the future. “DCS allows operators and engineers to look at trends with an ease that would have been considered magic in ‘the good ole days,’” (Muller). “Just the ability to share information electronically has been impactful to the industry because large groups of people, whether on- or off-site, can easily look at a problem and come up with better solutions and designs,” (Floyd).
Maintenance issues, advancements
Leaks, corrosion Unsurprisingly, the predominant maintenance concern historically for the Sulfuric Acid Today • Spring/Summer 2019
industry was excessive localized corrosion and the leaks that resulted. “Twenty-five years ago it was common to have staff regularly walking around the plant fixing leaks.” These days, as mentioned previously, corrosion is better managed with better equipment design and improved materials of construction, (Fenton). Pressure drop Pressure drop was also much more common 25 years ago and particularly damaging to an operation if it required a plant shutdown to address. “Today, improved catalyst and mist eliminators have made great progress managing this issue and extending turnaround time,” (Blair). Sulfur gun plugging Plugged nozzles and resulting poor atomization and furnace/burner performance have persisted for 25 years or longer. Although the industry has gained traction here, “these issues still represent a primary concern for producers,” (Chuck Munro, Refinery Application Specialist, Spraying Systems Co.).
and proactive maintenance strategies to maximize equipment efficiency. It also fosters teamwork throughout the organization, emphasizing empowering operators to help maintain their equipment. RCM uses the most effective maintenance approach, employing preventive, predictive, proactive, and reactive techniques in an integrated manner to increase the operational efficiency of equipment within its design life cycle with minimal maintenance. Materials Predictably, the most impactful advancement to the industry overall plays a large role in easing the burdens of maintenance. Though stainless steel, alloys, and the like were available 25 years ago, their use has broadened as their benefits become better realized. In the past, the industry evaluated these better materials only by their higher cost. “Today, there is the environmental ethic that says leaks are unacceptable and that improved performance with better materials, though more expensive, is ultimately good for business,” (Muller).
Maintenance planning programs Twenty-five years ago, maintenance planning was much more rudimentary. “It largely entailed keeping the right spare parts on hand,” (Blair). And “equipment records were kept in someone’s filing cabinet,” (Davis). Today, records are digital and the emphasis is on predictive maintenance so that unexpected shutdowns do not occur. Planning today is much more formalized. “Acid plants in the forefront of maintenance planning today practice Total Productive Maintenance (TPM), Reliability Centered Maintenance (RCM), or both,” (Wang): TPM uses preventive, predictive,
Better equipment and designs Innovations in equipment design have contributed significantly to managing common maintenance issues of corrosion and pressure drop, and others. Some exam-
Acid Piping Technology’s Mondi ™ piping’s corrosion allowance withstands weak acid excursions, thus reducing the potential for hydrogen events.
Koch Knight’s FLEXERAMIC® ceramic structured packing lowers pressure drop, is subject to less settling and sulfur buildup, lasts longer, and lowers power consumption.
Mercad’s larger diameter main cathodes for use in anodically protected acid coolers save producers maintenance time because they can be cleaned easily and their longer life means fewer replacements.
Customized configurations of Lewis® pumps, like this one made from specialty Lewis® alloys, is a solution Weir Minerals offers producers with persistent weak acid corrosion in pump tanks. Lewis® proprietary alloy materials are designed to handle hot concentrated acid and oleum, and provide a long service life.
ples of equipment advancements industry suppliers have developed include: Acid cooler cathodes: Mercad’s larger diameter main cathode for use in anodically protected acid coolers save producers maintenance time because they can be cleaned easily and their longer life means fewer replacements, (Barry Krentz, President, Mercad Equipment, Inc.). Acid distributors: The design of Chemetics ISO-FLOW™ Acid Distributor with SWIFTLOCK™ uses so few nuts and bolts hardware that plant personnel can quickly assemble/dissemble the unit in the tower as needed,” (Lee). Acid pumps: For persistent weak acid corrosion in pump tanks, Weir Minerals offers customized configurations of Lewis® pumps made from alternative alloy materials, (Mick Cooke, Director of Sales and Marketing, Weir Minerals Lewis Pumps). Acid tower packing: Koch Knight’s FLEXERAMIC® ceramic structured packing lowers pressure drop, is subject to less settling and sulfur buildup, lasts longer, and lowers power consumption, (Douglas Popek, Sales Manager-Carolinas, Koch Knight). Catalyst: Pressure drop issues have been reduced through catalysts with improved hardness and shape, (Blair). Cold exchangers: NORAM’s cold exchanger with a hot sweep helps prevent condensation/fouling at the cold end of the exchanger. Design and fabrication techniques for ducting and expansion joints promote longer life, (Cooper). Mist eliminators: A wide variety PAGE 9
Cover Story
of corrosion-related issues have been addressed by reducing the amount of mist carry-over through improved performance of MECS® Brink® mist eliminators, (Blair). Mondi piping: Distribution systems and thick-wall construction withstands rapid corrosion from weak acid excursions, (Knoll). Sulfur guns: The improved design of Spraying System’s CBA WhirlJet and Gun minimizes plugging, translating to easier maintenance for producers, (Bandish Patel, Project Engineer, Spraying Systems Co.). Expert contractors Survey respondents cited contractors who specialize in servicing sulfuric acid equipment as a growing segment of the acid industry in the last 25 years, and one that producers have come to rely on. “One of the most significant changes is the business relationship between the sulfuric acid producer and the service contractor. 25 years ago the contractor was seen as an outside entity and many times merely an expendable labor force, a necessary evil required to execute tasks the producer was unwilling or unable to complete with plant personnel. As one old, crusty maintenance manager told me, ‘Son, you have to realize you have two strikes against you when you come through the gate because you’re a contractor. If you were worth your salt you would be working at a plant like we are.’ Today this attitude is replaced with one of cooperation and partnership, which has transformed an adversarial role into one of mutual success. Long-term relationships are fostered by building on experiences from the past and vision for the future,” (Harris). “Employing sulfuric acid maintenance contractors, such as VIP International, to work in acid towers, mist eliminators, converters, and heat exchangers, has had the biggest impact on maintenance for us. They have the know-how to get the job done correctly and safely, often in a very dangerous and nasty environment,” (Carl Yamada, Consultant, Eco Services). The lack of sufficiently knowledgeable maintenance staff on site in recent years had prompted industry suppliers to become experts in their customers’ processes, and to develop services to keep customer plants up and running. “We have expanded our service business to support the industry challenges and the new breed of customers/producers. Over the past ten years we have therefore gained significantly more intimate knowlPAGE 10
MECS® sulfuric acid plant equipment made with the ZeCor® alloy delivers superior corrosion resistance in a wide range of sulfuric acid concentrations, temperatures, and applications.
edge of how our plants are operating. This shift in our business even enables us to offer guarantees on plant availability,” (Storch).
Turnarounds
Extension of TA cycle, shorter durations A significant trend in recent years, and one that has become critical to site profitability, is the push to increase the duration between turnarounds (Fenton). Many producers are running two- to threeyear cycles, or longer. Producers also look to minimize their TA schedules so they can resume production more quickly. Achieving these ends requires more complex planning and monitoring of equipment maintenance trends to avoid unplanned surprises that can extend the outage and increase costs, (Davis). Better materials, designs Utilizing stronger, lighter materials and more efficient equipment designs have played a large role in reducing turnaround durations and extending cycles. These are some of the products industry suppliers have developed to help meet those goals: Acid towers: Non-bricked high silicon alloy NORAM SX™ acid towers can be assembled offsite and easily placed in the final location using a standard crane, (Cooper). Converters: NORAM converters with enhanced ducting design allow simultaneous warming of two to four beds for quicker start-up, (Cooper). Drying and absorption vessels: Acid Piping Technology’s open spiral shaped tower packing design for drying and absorption vessels prevents fouling and plugging, which reduce pressure drop and repacking frequency. Long-term pressure drop performance exceeds conventional packing, (Knoll).
Drying towers: MECS’ drying tower made of lightweight ZeCor® alloy can be assembled offsite and easily placed in its final location with a standard crane, (Blair). Modular designs: Chemetics’ modular equipment minimizes site work to accommodate abbreviated TA schedules. The designs also enable simple retrofit of large capital equipment like converters, acid towers, and gas-gas heat exchangers onto existing or new foundations to minimize shutdown timing, (Lee). WESPs: Beltran’s modern WESPs use advanced materials and electronics, making them more compact and easily installed without the whole system having to be shut down, (Beltran). TA contractors The same workforce reduction trends affecting plant maintenance have impacted turnaround work. Downsizing of plant maintenance personnel has increased the need for outside maintenance contractors; and contractors are becoming increasingly versed in site and acid industry specifics. Some examples include: Chemetics optimizes turnaround plans to suit the client’s site, taking into account the available space, local contractor skill set, site safety rules, and shutdown duration, (Lee). DuPont Clean Technologies can respond quickly to unforeseen turnaround needs, including stocking catalyst at key locations, offering emergency Brink® mist cartridge repacking services, and supplying other process-critical equipment. Technical experts are also available to respond to urgent requests. Other service offerings include catalyst performance analysis via PeGASyS, fiber analysis for mist eliminators, and the Brink® stick test app, (Blair). DuPont Clean Technologies, in coordination with Koch Knight, can quickly service MECS acid towers with Koch Knight’s Type 88 FLEXERAMIC ceramic structured packing. “Koch Knight’s inventory levels allow companies, such as DuPont Clean Technologies, to service customers more rapidly for critical equipment changeouts,” (John Horne, DuPont Clean Technologies, MECS® Sulfuric Acid & Environmental Technologies). Outotec begins its support of customers twelve months before a major shutdown to plan and schedule the turnaround, (Storch).
Better records, planning The use of digital record keeping and planning tools has seen major growth over the last 25 years. Good scheduling tools have enabled shorter outages while maintaining safety and cost goals. For example, computerized maintenance management systems (CMMS) allow accurate sorting and planning for the long term issues that have to be addressed during TA periods (Fast). Even commonplace tools like MS Project help sites optimize resources more effectively (Floyd) and digital photographs captured during inspections simplify equipment histories, (Wang).
Safety
Twenty-five years ago, safety and health centered around workers compensation insurance and accident reports. “Then industry leaders began to see the toll taken on the workforce and the bottom line, and sought to reverse the negative trends,” (Passman). Today safety is seen as an integral part of doing business, even from an economical perspective. “A plant makes money only when it runs safely, reliably, and within emissions requirements. Every safety event, just like every leak or emissions issue, causes a plant shutdown. It is more cost efficient to spend a few extra dollars, about 5 percent more, to build a safe and reliable plant versus a minimum-cost plant. One unplanned three-day shutdown comes to roughly the same cost as the difference between the quality and low-cost plant,” (Fenton). “The difference between then and now is that instead of viewing safety as an expense, management now believes a safe plant can also be an efficient plant,” (Davis). “We have zero tolerance for incidents. Being just good was not where we wanted to be. People still were getting hurt. Now with the goal of zero, we actively work to find all the potential hazards and work them out of our processes,” (Fast). Knowledge deficit As with other areas of sulfuric acid production, workplace safety has been affected by dwindling numbers of experienced staff. “Today there is a real safety impact to gaps in workforce knowledge, skill, and experience,” (Wang). Many companies recognize this knowledge gap and are looking to enhance their safety systems through training and coaching. “Studies into critical facets Sulfuric Acid Today • Spring/Summer 2019
Cover Story
the participation of seasoned operators and maintenance personnel to ensure the knowledge transfer to younger staff,” (Yamada).
of workplace safety have gathered large amounts of data that have been used to bring about new strategies in company initiatives. Stringent regulations by governments and a new thought process regarding the safety of workers have initiated changes in the area of safety that are continuing to evolve today,” (Passman). Safety programs More facilities are voluntarily incorporating safety management programs into the workplace, and formal management tools like PSM (process safety management) and RMP (risk management plan) have had a significant impact. These tools enable teams to understand the effects each facet of an operation has on safety and organize efforts in a way that brings focus to each facet and shares safety responsibility across the entire organization, (Ron Cloud, Consultant, RDC Enterprises LLC). “Companies implementing these programs properly have been realizing significant benefits in productivity, safety performance, and reduced costs for maintenance, operation, capital expense, and insurance,” (Wang). Prior to implementing the safety program at Eco Services, “we experienced explosions of electrostatic precipitators, tank fires, major SOx excursions, major boiler failures, etc,” (Yamada). Working in a potential NOx environment has its own protocol involving a precise sequence. This requires training, experience, and the equipment to safely enter and work in an Immediately Dangerous to Life and Health (IDLH) atmosphere, (Passman). Safer equipment In response to the call for safer working conditions in acid plants, industry suppliers have incorporated various features in their equipment designs. For example: Chemetics designs its equipment and plants to provide feedback on plant operating conditions and prevent a runaway weak acid corrosion event. Anodically protected acid coolers automatically warn clients of an acid cooler leak, (Lee). DuPont Clean Technologies plant and equipment designs enable maintenance activities to be accomplished in both a less invasive and more ergonomically correct manner, (Blair). Mondi piping’s corrosion allowance withstands weak acid excursions, thus Sulfuric Acid Today • Spring/Summer 2019
Future
Respondents had these thoughts on what the future of the sulfuric acid industry might look like. NORAM’s Smart™ acid distributor has clean-out ports at the ends of each acid distribution arm so any collected chips can be removed from outside the tower, thus avoiding tower entry.
reducing the potential for hydrogen events, (Knoll). NORAM’s acid tower designs place the exit duct on the top head to prevent potential accumulation of hydrogen that could occur with a side exit. NORAM’s Smart™ acid distributor has clean-out ports at the ends of each acid distribution arm so any collected chips can be removed from outside the tower, thus avoiding tower entry (Cooper). Some safety devices/instrumentation have experienced failures, causing unanticipated mishaps. “This topic is seldom addressed but it happens all the time,” (Wang). Wang cites these examples: Failures of combustion safeguard/ management system causing a spent acid precipitator fire or explosion around the preheater/converter area. Failures of O 2 / SO 2 analyzer measuring high stack SO2. Failures of acid concentration analyzer measuring high stack opacity. Information sharing Respondents noted greater levels of collaboration within the industry around safety issues over the last 25 years. Safety training in Confined Space Entry procedures, Hazards Materials Handling, the proper use of PPE, and eliminating the use of asbestos materials are more common (Egan Godfredsen, Plant Superintendent, Border Chemical Co.). Situations regarding hazardous incidents are being openly and more commonly discussed at industry forums. Some examples are: A hydrogen safety workgroup comprised of industry designers, operators, and process consultants has been collaborating in recent years to study
Sulfuric acid workshops offer producers and suppliers from around the world the opportunity to share technology, experiences, and mishaps in the acid industry. George Wang, center, shares his experience with participants of the 2010 Australasia Sulfuric Acid Workshop in Sydney, Australia.
the causes and prevention of hydrogen incidents. The group has shared its findings industry-wide in an effort to improve plant safety (Storch). Sulfuric acid workshops offer producers and suppliers the opportunity to share technology, experiences, and mishaps in the acid industry around the world. Safety topics have been increasingly brought out in these workshops, (Wang). “Conferences around the world allow a free exchange of information, ideas, and best practices to be shared throughout the industry. Sulfuric Acid Today has without a doubt had the largest effect on this exchange of information and ideas. Congratulations to Kathy Hayward on an excellent job and I wish her another 25 years of success,” (Harris).
Training
Plant simulation training is the predominant training advancement respondents cited. Operators can experience mock plant failure events and practice responding to them. “Simulators that most authentically model the actual plant are most useful, as well as those that interface with the DCS the operators will ultimately use,” (Muller). “I’ve used a simulator for training brand new operators for two new acid plants. I would not want to start a new plant without one. While still relatively expensive and not in widespread use, I’ll be surprised if they do not become a standard training tool in the near future,” (Muller). “It is also valuable to configure sulfuric acid training classes that cover both theory and practice, and that include
Predictions Plants getting larger and SO 2 emissions limits below 10 PPMV, (Leonard Friedman, Consultant, Acid Engineering & Consulting Inc.). Materials improvements to minimize leaks in acid and gas, (Friedman). Computerized control of electric power/efficiency, (Davis). Artificial intelligence taking a greater role in process control and safety systems, (Davis). Emphasis on mitigating greenhouse gases and pollution levels globally, which will level the playing field and drive further innovations, (Cloud). Hopes An industry-wide database of incidents, created by and for the industry, that includes equipment and instrument failures. This could be located on the Sulfuric Acid Today website, (Wang). Corporate reinvestment into human and plant resources to address decades of little investment, the growing knowledge gap, and aging plant infrastructure, (Davis). Compulsory and continuous training at all levels of the organization should be a core principle to have a sustainable operation. Technology is good, but in-house staff with detailed working knowledge of the operation, equipment, and failure modes of each component is critical, (Cloud). A recognition among the next generation of acid plant engineers and maintenance workers that a career in the industry is challenging yet rewarding, (Floyd). We hope this retrospective has helped illustrate how far the industry has come and helps you consider where to take it over the next 25 years. In the words of one survey respondent: “There are many opportunities for improvement and technological advances waiting to be conquered,” (Floyd). q PAGE 11
Feature
market outlook
Changes in the sulfuric acid market over the past 25 years By: Fiona Boyd and Freda Gordon, Directors of Acuity Commodities
It has been 25 years since the first issue of Sulfuric Acid Today was published and while much has changed in the acid market, the number one rule remains: keep the product moving. This is because the majority of acid that is traded in the global market is a by-product of base metals smelting. The inelastic nature of smelter-based sulfuric acid means that no change in demand, either in a positive or negative direction, can alter the production volumes outside of voluntary production curtailments. Since around mid-2017, the price of acid globally has been stable due to the inelasticity of smelter acid at a time of firm demand. This has incentivized those with ability to supply the merchant market with sulfur-based sulfuric acid, typically consumed on site, to fill the void and change market dynamics in the process. Before we discuss where the market is today, we will review the most notable developments in the sulfuric acid market over the last 25 years.
Early 1990s
The main supply sources of globally traded sulfuric acid in the 1990s were the same as today due to the concentration of base metals smelters in Asia and Europe. The Americas were prevalent importers then, as they are today. The difference in the early 1990s compared to today was the traders involved. Interacid was among the top three traders and held a strong European position due to its ownership roots. While the company is not as active in Europe today, it remains a key player in Chile. It played a pivotal role in developing trade between Japan (home to acid produced by its now parent company, Sumitomo Corporation) and offshore countries. Boliden Chemtrade (BCT) was also one of the top three traders, and it was eventually renamed Aglobis when acquired by Mitsui in 2017. Rounding out the top three was Metallgesellschaft (MG), also with a strong connection to Europe, but no longer operating. The phosphate fertilizer market in North America then was very different, with over 10 companies producing in Florida compared with just two today. The theme of consolidation in phosphate fertilizers continues today and could result in further changes to trade flows as we have seen over the last two years, as discussed later in this article. Due to the demand back in the early 1990s, there were notable import needs into Tampa. Import demand into Tampa was at its peak at around 1 million t/yr, compared with 3,000-81,000 t/yr between 2012-17. Tank capacity was developed by SATCO, the same company that is building the first import tank capacity on the west coast of North America, scheduled to enter service later in 2019.
Mid 1990s to mid 2000s
Changes in ownership of assets were notable during this period, which one could argue is an element of the industry that has not been repressed. In the base metals sector, some of these changes in turn impacted sulfuric acid trading partnerships. Smelter closures also contributed to a changing market environment, with several in the U.S. between 19992002. Consolidation in the phosphate sector continued, which saw sulfuric acid import demand in Florida decline notably, shifting the hub of U.S. activity to the Gulf Coast. This included the 1999 opening of the import terminal at Beaumont, Texas, now owned by Saconix. During this time, consumption in Chile to support copper leaching surged. By 2007, import demand in Chile rose to 1.4 million t, although notably lower than the close to 2.9 million t imported in 2018. PAGE 12
The increase in activity in Chile paved the way for trader Transammonia (now Trammo) to increase its market share in the acid market. With the exit of MG by this time, the top three traders were BCT (now Aglobis), Interacid, and Trammo.
2007-09: The commodities boom and bust
In the second half of 2007, commodity demand and pricing firmed significantly, mainly driven by demand in China. That country’s appetite for products such as phosphate fertilizers and supporting raw materials such as sulfur caused prices to increase sharply. This was followed by the 2009 global economic collapse. As an indication of the boom and bust seen in 2007-09, the quarterly molten sulfur price in Tampa, a North American price benchmark, was $600/long ton, delivered (lt DEL) in the third quarter of 2008 before dropping to $0/lt DEL in early 2009. Meanwhile, U.S. spot sulfuric acid import prices peaked at $400s/t cost and freight (CFR) in 2008, compared with $125-135/t CFR in early February 2019.
These unprecedented market conditions created new trade patterns. In the boom cycle, this included sulfur-based exports from China, the same product that is filling the void today. In the bust cycle, product from unusual sources was seen in order to keep product moving, often at negative pricing. This included the exports from west coast India, for example. The crisis in 2007-09 opened up opportunities for new traders to enter the market, which remains a prevailing theme in the current market. Some of the traders were from the fertilizer side, such as Ameropa, who remains active in the market today.
2010-19 and beyond
In 2010, demand for commodities began to improve and a significant boom/bust cycle like that seen in 2007-09 has not been repeated since. We continued to see organizational changes in the base metals sector that impacted sulfuric acid. One example was the closure of the Kidd Creek smelter in Canada (then owned by Xstrata, itself acquired by Glencore in 2013), resulting in a loss of around 500,000 t/yr. This has been the most significant change in Canadian production in recent years, surpassing the 2017 loss of at least 350,000t from the Vale smelter in Sudbury on its transition to a single furnace. The consolidation in the North American phosphate market also continued. This included the late 2014 closure of the Mississippi Phosphates plant and Mosaic’s acquisition of CF Industries’ phosphate operations in 2013. CF’s lone phosphate operation was in Plant City, Fla., which Mosaic idled indefinitely in December 2017. Part of the reason to
Fiona Boyd, Acuity Commodities
Freda Gordon, Acuity Commodities
cease phosphate production at Plant City was growing production from other producing countries that export, including Morocco. The growth in Morocco in phosphate fertilizer production resulted in an equal surge in sulfur and sulfuric acid import demand. This along with a rebound in demand in Chile in 2017-18, based on improved copper pricing, has contributed to the current firm market conditions.
*Morocco as of end Nov
Since 2017, a slew of unplanned operational issues as well as maintenance in key producing regions have squeezed acid availability. Non-traditional supply has been a regular feature in the traded sulfuric acid market since around mid-2017. This includes opportunistic sulfur-based exports from China, Italy, South Korea, and Spain. Of note is China exporting close to 1 million t in 2018, up from its previous record of 700,000 t in 2017. One of the most notable unforeseen issues on the production side was the March 2018 idling of a 1 million t/ yr smelter in Tuticorin, India, operated by Sterlite Copper. At the time of writing, the smelter was poised to restart sometime in 2019, which is seen as a market restraint for the second half of the year. Another bear factor is the potential for stalled economic growth, in part driven by the ongoing trade war between China and the U.S. At the time of writing, an early March deadline for a deal to be reached was looming with sentiment over a resolution slightly improved in early 2019. Turning to recent developments in the trading arena, lower acid prices in 2015-16 encouraged producers to develop direct relationships with consumers, thereby reducing some trader volumes. Conversely, in 2018-19 when prices have firmed, some consumers have been proactive in consuming volume directly from smelters amid the tight supply, such as between Chile and Asia. The global tight availability intensified competition among traders to secure long-term contracts. Agreements for 2019 contract supply reflected higher than anticipated prices. With firm demand, traders were able to pass costs on to buyers. We also continue to see changes in active trading companies, with no expectation this long-term trend will dissipate. One of the newest entrants has been Tricon Energy and next year we are expecting a newly-founded trading company to become more active in the sulfuric acid market. Acuity Commodities provides insight into the sulfur and sulfuric acid markets through price assessments, data, and supporting analysis. Offerings include weekly reports on the global sulfur and sulfuric acid markets and a biweekly report focusing on North America as well as bespoke consulting work. Please visit www.acuitycommodities.com for detailed information. q Sulfuric Acid Today • Spring/Summer 2019
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Feature
Sulfur gun advancements In production of sulfuric acid from molten sulfur, it is critical that the sulfur is atomized into droplets so that combustion occurs efficiently. The spray nozzle converts bulk sulfur into a predictable droplet size distribution, spray angle, and coverage. The most widely used nozzle in sulfuric acid production today is the BA WhirlJet® nozzle. These nozzles provide superior performance during normal operation, but when flow is decreased or turned off, the nozzles may plug. This happens because the nozzles protrude beyond the steam jacket of the sulfur gun. Without the cooling provided by the steam jacket, the sulfur flowing inside the nozzle heats up beyond the normal working temperature. This causes the sulfur viscosity to increase and plugging may occur. Operators have been compensating for this by purging the nozzles or removing the guns at the end of operation. However, if one of these actions doesn’t occur quite quickly, pluggage is likely. Flexibility in production rates is required to optimize sulfuric acid production. Sulfur guns are either turned on and off, or flow rate is increased or decreased. To meet this requirement and minimize pluggage, a new sulfur nozzle and gun have been introduced. The CBA SulfurJet™ nozzle has the same superior performance as the BA WhirlJet nozzle. The CBA SulfurJet gun features a steam jacket that fully protects the nozzle to minimize or eliminate plugging. As sulfur passes through the CBA SulfurJet nozzle, sulfur temperature is maintained in the optimal range as production rates change.
Fig. 1
PAGE 14
Fig. 3
In production of sulfuric acid from molten sulfur, it is critical that the sulfur is atomized into droplets so that combustion occurs efficiently. (3,847 lbs/hr) sulfur at 5 psig ΔP (0.35 bar). The feed sulfur temperature was set at 284°F (140°C) and steam in the steam jacket pipe was at 293°F (145°C) and 60 psig (4.1 bar). At full flow conditions for both spray nozzles, the sulfur temperature was maintained until it exited the spray nozzles. The temperature change in the BA WhirlJet nozzle was validated
CBA SulfurJet nozzle and CBA SulfurJet gun validation research
Computational Fluid Dynamics (CFD) was used to model heat transfer in a sulfur gun with BA WhirlJet nozzles and a gun equipped with CBA SulfurJet nozzles. A full flow rate condition of 9,410 kg/hr (20,745 lbs/hr) sulfur at 150 psig ΔP (10 bar) was compared to a reduced flow condition of 1,745 kg/hr
By: Chuck Munro, Refinery Application Specialist, Spraying Systems Co.
Fig. 2
when the reduced flow conditions were used. Fig. 1 shows the BA WhirlJet nozzle at the reduced flow conditions. The sulfur polymerizes inside the nozzle as the temperature rises above 305.6°F (152°C) and starts to form a skin. Over time, the skin grows thicker and reaches the point where the sulfur can no longer pass through the nozzle. The CBA SulfurJet nozzle
is shown in Fig. 2. At the same reduced flow condition, the sulfur temperature remains at 289.4°F (143°C) as it passes through the nozzle. Polymerization does not occur. Due to the hydraulic atomization design, the pressure to the gun is decreased as the flow rate is reduced. As a result, velocity through the internal cavity is decreased. Velocity for the BA
WhirlJet nozzle at the exit is reduced from approximately 32 m/s (105 ft/sec) at full flow rate to approximately 8 m/s (26.2 ft/ sec) at reduced flow rate as shown in Fig. 3. Since the fluid moves more slowly through the gun, the temperature near the walls of the sulfur cavity increases to 635°F (335°C). This causes the sulfur to polymerize at 318.2°F (159°C) and eventually build a skin inside the nozzle. The velocity decrease in the CBA SulfurJet has a smaller impact temperature of 442.4°F (228°C) and pluggage is avoided.
Summary
The new CBA SulfurJet nozzle and CBA SulfurJet gun deliver the flexible performance required by producers. The new nozzle provides superior atomization of bulk sulfur so producers can achieve the same or better performance than the BA WhirlJet spray nozzles currently in use. In addition, the new gun design allows production rates to be adjusted with reduced risk of pluggage. Producers will be able to maximize production time, reduce maintenance time, and extend gun life. Chuck Munro has more than 20 years of experience in spray technology with Spraying Systems Co. He is a specialist in the petrochemical and chemical industries and is active in several industry committees. For more information, visit www.spray.com. q
Sulfuric Acid Today • Spring/Summer 2019
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sulfuric acid products & services
Department
lessons learned: Case histories from the sulfuric acid industry
Speeding up tower replacement By: Nicolas Lepeu, Key Account Manager EMEA, DuPont Clean Technologies
When acid producers come to replace sulfuric acid towers, time is often of the essence. They want to avoid lengthy shutdowns and losing valuable production time. With good planning and collaboration between the plant operator and the engineering/design supplier, it is possible to keep installation time for the new tower to a minimum. Sulfuric acid plant operators can speed the project along by managing on-site work themselves. DuPont Clean Technologies has recently worked on a project where the plant operator hired local contractors to dismantle the old tower and install the new drying tower internals under close supervision by DuPont. Preparations for the installation of the new tower were greatly assisted by the production of a 3D model by the plant operator based on DuPont drawings and existing assets. This model was extremely helpful to ensure the correct positioning of the new tower structure and acid piping, as well as the connections and gas ducts between old and new equipment.
Good planning—the key to a safe and timely execution Planning is a crucial element to safeguard against any incidents in the runup to commissioning. It is important to take time to calculate the weight of the old tower to determine the correct crane size and to structure each step of the dismantling process. Here also, the 3D model was very helpful for accurate positioning of piping and platforms.
Lifting preassembled MECS® ZeCor® tower into position on site, ready for connection and start up.
A section of a MECS® ZeCor® tower complete with inspection platforms and MECS® Brink® mist eliminators.
Lifting into place MECS® ZeCor® tower, fully assembled offsite and ready for “plug in and play” at a sulfuric acid plant.
critical phases of the manufacturing process while at the same time allowing for increased logistics agility to ensure reactive and on-time delivery and installation of the new tower. All tower internals can also be pre-assembled near the plant operator site and installed by a local contractor under supervision. In this way, final installation can be limited to the removal of the old tower and the “plug in and play” of the new one. With all connections also prefabricated, final adjustments can be made during installation, so that a tower can be substituted in a normal turnaround window without losing extra production time for the replacement.
Safety considerations
as any damage during these activities can not only delay start-up, but also seriously impact future plant operation. Crane size and positioning are therefore extremely important: to be able to lift the old tower at actual weight, the right size crane needs to be hired. For example, for a 50-ton tower including packing and bricks, a 500-ton crane provides a capacity of 100 tons at actual distance. Given these planning, collaboration and design parameters, it is possible to achieve replacement of a sulfuric acid tower within the space of just a few days.
During the dismantling of the old tower and installation of the new tower, it is critical that all contractors, subcontractors, and suppliers receive the necessary training to work safely in an environment affected by the different hazards that an acid plant presents. All projects should have their own risk assessment prior to execution and planning should carefully assess all crane lifting activities. Because old equipment and new replacement engineering often has to be lifted over and across other critical plant equipment, assessing risk is essential
Achieving fast installation
Designing a new tower that is light and fits into the same plot size as the old tower significantly contributes to minimizing or avoiding modifications to existing civil works. MECS® ZeCor® is an extremely light, highly corrosionresistant alloy that has proved its worth in a variety of sulfuric acid concentrations, temperatures, and application. Its low weight means MECS® ZeCor® towers can simply be lifted by standard cranes and placed in the exact same location as an old tower. A MECS® ZeCor® drying tower with advanced DuPont Clean Technologies design standards allows for maximum drying efficiency and low pressure drop by including eight feet of ceramic packing, a MECS® UniFlo® acid distributor, and MECS® Brink® mist eliminators. In order to keep shut-down to a minimum, fabrication of the replacement tower can take place off-site. This also ensures good quality control during all PAGE 16
3D Model: 3D plant models help plan installations.
About DuPont Clean Technologies and DowDuPont Specialty Products Division
The Clean Technologies division of DuPont is a global leader in process technology licensing & engineering, offering critical process equipment, products and services that enable industries to minimize their environmental impact. We provide extensive global expertise across our portfolio of offerings in key applications – MECS® sulfuric acid production, STRATCO® alkylation, BELCO® wet scrubbing, and IsoTherming® hydroprocessing. For more information, visit www.cleantechnologies.dupont.com. DowDuPont Specialty Products, a division of DowDuPont (NYSE: DWDP), is a global innovation leader with technologybased materials, ingredients and solutions that help transform industries and everyday life. For more information, visit www.dowdupont.com. q Sulfuric Acid Today • Spring/Summer 2019
Feature
Lewis® looks back on 25 years specializing in the sulfuric acid industry By: Martha Villaseñor, Sales and Marketing Manager, Lewis®
Weir Minerals recently celebrated the 127th anniversary of Lewis® pumps and valves. In the last 25 years, Weir Minerals has maintained its international reputation in the design and manufacture of pumps and valves in the sulfuric acid, phosphoric acid, and sulfur industries. There have been many challenges and Weir Minerals continues to advance to meet the demands of the sulfuric acid industry, as this is a niche market where Lewis® provides the most reliable products for this harsh chemical. Safety is a core value of Weir Minerals, and Lewis® has embraced this commitment based on its performance in the sulfuric acid industry. End users enjoy the high reliability of Lewis® pumps and valves because they perform from turnaround to turnaround without premature failures, unscheduled downtime, or compromising safety. The reliable design supports producers in complying with the fume containment requirements from environmental control entities worldwide. One clear example is the new legislation taking effect in Chile to convert all the sulfuric acid plants from single absorption to double absorption, and Lewis® is the pump of choice countrywide. One particular smelter is located at a high elevation and needed a tailored impeller design with lower NPSH requirements. These custom pumps were provided for the two new, larger capacity plants in the Atacama desert. Lewis® provides custom solutions like this to end users in over 100 countries worldwide.
Lewis® milestones in the last 25 years
Lewis® has specialized in sulfuric acid equipment since manufacturing its first sulfuric acid valve in 1975. From then on, Lewis® continued to focus on the development of proprietary alloys and product features for environments with high-concentration, hot sulfuric acid. Weir Minerals has added gate, globe, and butterfly valves with the proprietary Lewmet® alloy, proven to be highly effective in sulfuric acid plants. As processes in sulfuric acid PAGE 18
customers’ requirements, some initiatives such as collection of usage data are in place to plan production and provide high quality, reliable products to meet customers’ expectations during emergency situations. To ensure successful implementation, Weir adopted a LEAN manufacturing strategy to access and share global best practices and training between all Weir factories.
Investment An assembly technician installing the impeller on a Lewis pump.
plants evolved and producers required hotter acid and faster velocities, Lewis® valves became standard for acid service and heat recovery service. Lewis® became part of the Weir Group in 1994. Weir’s well-established manufacturing excellence programs were implemented at Lewis, resulting in an even greater level of quality and performance. In 1995 Weir Minerals shipped the first 30” gate valve to a Zambian copper smelter. And by 1996 the valve product line expanded to include metric faceto-face dimensions. “Due to sulfuric acid market needs we have increased pump sizes to 10, 12, 14, and 18 throughout the years,” said Randy Stanfill, senior sales engineer. In 2000, the size 18 acid pump of 3,000 m3/hr capacity was designed and tested. “The industry keeps evolving and demanding greater capacities so a new larger size pump is under consideration,” explained Mick Cooke, sales director. In 2012, the 36” (900mm) Axial Flow pump was shipped for phosphoric acid plant evaporator service. In the same year, the first Lewis® molten salt pump was manufactured. These highly engineered centrifugal pumps are integral to molten salt system circulation in the solar power industry. A full range of pumps engineered for the unique requirements of molten salt was developed. With over 100 years of experience focused on high density and high temperature,
Weir Minerals engineers were able to develop a Lewis® pump that has a superior feature set to provide high reliability and low operating costs. In just a few years, sensitive to the needs of extremely harsh HRS applications, Weir Minerals engineers developed an upgraded submerged-bearing design for severe HRS service intended to extend the submerged bearing life in the most difficult operating conditions. This upgrade consists of a modification to the volute bearing (bearing, journal, and bearing housing were enlarged). Today, Weir Minerals still manufactures a wide range of Lewis® pumps and valves and has made significant investments to develop and enhance its product line to better serve sulfuric acid plants. One pressing concern in the sulfuric acid industry is avoiding weak acid formation. Regardless of constant efforts, there are times when weak acid corrosion incidents persist and Lewis® provides support in troubleshooting and helping minimize the effects of this corrosion.
Weir Minerals Lewis Pumps recently invested in the modification of its test stand area for axial flow pump testing. This enables engineers to test all pumps extensively, under real-life working conditions, before they leave the facility. In the last 3 years there have been additions, such as the opening of a new Distribution Center with 42,000 square feet of manu-
facturing and office space, allowing them to manufacture, assemble, and ship Weir Minerals Lewis Pumps’ products to customers around the world with ease. The process has been streamlined to allow all departments to review the orders on a daily basis. This allows all departments to ask questions at the time the orders are processed, improving the flow throughout the system. Weir Minerals has remained dedicated to the market and their customers as demonstrated by the evolution of Lewis® pumps and valves. The product innovations and dedicated group of employees will not only provide better service to our valued customers but will enable Weir Minerals to continue to deliver solutions for sulfuric acid industry customers for years to come. For more information, please visit www.global.weir. q
Strong customer focus
With an international market of over 100 countries where Lewis® products are sold, Weir Minerals continues to focus on careful planning, identifying the most requested spare parts, and ensuring stock is constantly replenished for the needed items. As part of the continuous improvement in understanding
A Lewis pump in the vertical position ready for a freedom of rotation test. Sulfuric Acid Today • Spring/Summer 2019
Hello, future Sustaining our world for generations to come through technological and environmental innovation, we deliver Comprimo® sulfur and Chemetics® sulfuric acid solutions around the globe with a focus on site reliability, plant economics and workforce development.
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Feature
Preventing high-temperature superheater casing failures By: Matthew Hauth, P.E., Design Engineer, and Mike McGuire, Product Manager, Optimus
Eliminating unnecessary downtime for critical process equipment is always at the forefront of any plant operator’s mind. While plant components such as converters, burners, pressure vessels, piping, and valves obviously require monitoring and regular inspections, other aspects of the plant can be easily overlooked. High temperature superheaters, boilers, and economizers, as well as their external insulation, are key items that easily go unchecked. In recent years, we have seen problems arise with casing and stiffener cracks or warping, all due to either improper insulation blanket installation or inadequate rain/water protection. Over the past five years or so, Optimus has visited several sulfuric acid plants during their maintenance outages to investigate instances of casing cracks in the inlet transition ducts of high-temperature superheaters. These are superheaters downstream of the sulfur burner that receive flue gas exiting the first converter pass at about 1155°F. Some of the installations were more than 15 years old, but a few were less than five years old and, as such, the casing cracks were unusually premature. Experienced plant maintenance personnel have provided useful insight as to what environmental factors can cause such failures, and our own 20+ years of experience with such equipment helped us identify some root causes. Fig. 1 depicts a typical superheater inlet transition duct which, due to the design conditions, features 304H stainless steel casing and external stiffeners that are six to seven inches tall.
Proper casing insulation
Failures in the superheater inlet duct can often be attributed to improper external insulation techniques. To prop-
Fig. 1: Typical superheater inlet transition duct. PAGE 20
erly insulate a stiffened, hot casing, even layering of the insulation blanket is critical. If the field insulation contractor is inexperienced and not following well established technical specifications, they may be tempted to pack insulation into the areas between stiffeners leaving the tops of the stiffeners uncovered, or insufficiently covered, as in Fig. 2. Left uncovered, the stiffeners act as heat-wicking fins with a potentially enormous thermal gradient through the height of the stiffener. Where the stiffener is attached to the casing plate and well insulated, the metal temperature will be near the hot flue gas temperature and will experience the most thermal expansion. At the outer tip, the stiffener will be much cooler with much less thermal expansion. The result is wavy and distorted stiffeners, sometimes generating stresses high enough to break the stiffener-to-casing welds. Fig. 3 is a recent picture of an inlet duct where the tips of the stiffeners were not adequately insulated. Notice the waviness and distortion featured in some of the stiffeners. The advisable method is to contour the rolls of insulation blanket continuously over both the casing plate and the stiffeners, creating even layers across the entire vessel. Fig. 4 shows the proper insulating technique. The technique minimizes the temperature differential across the height of the stiffeners, thereby keeping stresses relatively low.
To achieve maximum protection from water exposure, some plants have installed rain shields to cover the top and sides of the superheater. Even if there is only enough room to shield the inlet transition duct and front portion of the superheater, benefits can be well worth the expense.
If you operate or maintain a hightemperature superheater in your sulfuric acid plant, it may be beneficial to ensure the casing stiffeners are properly insulated, and the unit is adequately protected from environmental water For more information, please visit www.optimus-tulsa.com. q
Fig. 2: Improper insulation of external casing stiffeners.
Protection from rain water
Another key to preventing high stress events in hot casing is to keep water outside the external lagging. Water and moisture coming in contact with hot casing thermally shocks the casing metal which can cause numerous cracks to form quickly. The unit shown in Fig. 3 suffered from rain water exposure in addition to inadequate insulation. Superheaters are often lagged with light weight corrugated sheet metal. At a minimum, the lagging should be installed so the over-lapping seams are orientated in a way that prevents driving rain from penetrating under the lagging. This may be difficult to achieve on the flat “roof” of the inlet duct where water can pool and seep through the seams. Switching to a heavier lagging with taller corrugations that provide a “standing seam” configuration can help protect against roof water.
Fig. 3: Inadequately insulated stiffeners of three-year-old superheater inlet transition duct.
Fig. 4: Proper insulation of external casing stiffeners. Sulfuric Acid Today • Spring/Summer 2019
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Feature
At last, a new mesh pad for the sulfuric acid industry By: Rana Van Tuyl, Jacobs
For more than 40 years, mesh pads have been used successfully in sulfuric acid drying towers with one exception—sustainability. When acid is met with high temperatures, the lifespan of a mesh pad decreases, and replacement is required. Frequent replacement of mesh pads increases operational costs for plant owners and operators due to expenses incurred for product purchase, installation, and associated downtime to perform the maintenance.
The making of a new mesh pad
Through its R&D lab and custombuilt fabrication facility in Canada, global transportation and logistics management capabilities, specialized project teams, and worldwide network of trusted suppliers, Chemetics set out to design a new alloy mesh pad using SARAMET® 35, Chemetics’ proprietary alloy. By creating a mesh pad using SARAMET, a sulfuric acid resistant, austenitic stainless-steel alloy, Chemetics offers producers an innovative way to improve operational reliability and plant economics. Field results of the new SARAMET 35 Mist Eliminator shows no indication of mechanical vibration damage or corrosion after two years of operation. “Chemetics’ technical service staff has been supporting our clients in turnarounds and emergencies for over 50 years. During this time, we have commonly seen catastrophic mechanical failure of mesh pads leading to the residual metals of the mesh pad collapsing into the acid distributor troughs and tower
Common mechanical failure seen on historical mesh pad designs.
packing. To correct the problem, plant staff need to dig the mesh pad residuals out of the acid contaminated tower and reinstall a new mesh pad,” said Chemetics Technical Manager and Chief Metallurgist Grant Harding. “This is time consuming, difficult, and dangerous work that can be nearly eliminated with a mesh pad that is made of materials highly resistant to sulfuric acid and that is structurally strong enough to resist mechanical damage from flow pulses and negative pressure. The SARAMET 35 mesh pad by Chemetics has been designed to achieve these goals.”
Technical features of the SARAMET 35 mesh pad
A sustainable design for the future, the Chemetics SARAMET 35 mesh pad reduces tower down time by decreasing the need for frequent replacements, enables higher
Chemetics SARAMET 35® Mist Eliminator Mesh Pad assembly. PAGE 22
Installation suitable for greenfield projects, as well as maintenance and turnarounds.
plant availability, and improves worker safety by minimizing exposure to hazardous conditions. Constructed by combining the SARAMET 35 mesh with two layers of Alloy 20 screens to eliminate mist, the Chemetics mesh pads are made of the heaviest knittable wire gauge to maximize equipment life. Key features include: • Superior acid corrosion resistance, including the filament wire materials. • Greater heat resistance to blow back from the sulfur furnace. • Durable design with Alloy 20 wafers added to withstand handling and washing, preventing disintegration at end of life/related obstruction of acid distributors and other equipment. • Heavy duty, stainless steel frame to eliminate flow-induced vibrations, as
well as any movement between the pad sections that could lead to premature pad failures and mist by-passing. • Structural frame designed specifically for each tower to minimize deflection, eliminating flexing and resultant potential of a mechanical failure. • Custom design to enable easy installation via manways. • Optional tray designs available to allow removal and washing of the mesh pad from outside of acid tower. For every SARAMET 35 mesh pad installed, it is anticipated that three fewer traditional mesh pads are required over the lifespan of a dry tower. For more information, please contact chemetics.equipment@jacobs.com. q
SARAMET® 35 Iso-corrosion curve. Sulfuric Acid Today • Spring/Summer 2019
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Feature
Sulfur recovery gas cleaning By: Gary Siegel, Marketing Director, Beltran Technologies, Inc.
In petrochemical refining processes, hydrogen sulfide “sour gas” is commonly present in oil and gas formations. With respect to product and environmental requirements, it must be removed from petroleum and natural gas products. Hydrogen sulfide at low concentrations smells like rotten eggs. At high concentrations it is dangerous, as it is heavier than air, and impairs detection since it reduces our ability to smell. Exposure above 500 ppm can be fatal. Also, it is combustible when mixed with air, and can cause fires or explosions. Three Beltran wet electrostatic precipitators (WESPs) were purchased by a major petrochemical refinery where off-gases containing sulfur compounds are converted to sulfur in sulfur recovery units (SRU) and thereafter the remaining sulfur compounds and particulate are reduced in tail gas cleanup units (TGCU). The TGCUs utilize the Wellman Lord Process where finally the process gases are treated in the Beltran WESPs to remove sulfuric acid mist and particulate before being exhausted from the tailgas stacks. Due to the installation’s location in the California San Francisco Bay Area, the emissions must meet the PM 10 requirements and other strict DEQ regulations. SRUs are used to recover sulfur by the conversion of hydrogen sulfide (H2S) to elemental sulfur. In this application, refining high-sulfur crude oil produces hydrogen sulfide as a by-product. There are many sulfur recover technologies available for different applications, however, the most common conversion method uses the Claus process, which produces 90-95 percent of recovered sulfur. The Claus Process typically recovers 95-98 percent of the hydrogen sulfide feed-stream. This refinery’s SRU is based on the modified Claus Process, which is a multi-step reaction scheme. A portion of the total H2S is burned in the reaction furnace to form SO2. Then the H2S and SO2 react to form elemental sulfur across the Claus reactor. After each catalytic stage, liquid sulfur is recovered in the Claus condensers. The remaining unreacted H2S and SO2 then proceed to the next stage, where the equilibrium-limited Claus reaction continues in the presence of the Claus catalyst. Oil refineries are required to recover between 95 and 99.99 percent of the total sulfur introduced to the SRU. A conventional three-stage SRU with three Claus reactors is expected to recover 98+ percent. To meet the strict Bay Area DEQ requirements, the SRU must be followed up with a Tail Gas Clean-up Unit (TGCU). The TGCU consists of an SO2 clean-up system followed by a Beltran WESP to remove particulate and sulfuric acid mist. The Beltran WESPs are designed to reduce outlet loading of particulates and sulfuric acid mist below 1 and 5 mg/cubic meter, respectively. The WESPs are built of Beltran conductive graphite composites and C-276 internals, with FRP housings, so they are cost effective and corrosion resistant to the collected sulfuric acid. Industries that generate sulfur oxides and sulfuric acid, including metallurgical and mining, in many cases need a common and cost-effective solution for capturing and utilizing sulfur oxides and corrosive sulfuric acid emissions incorporated in downstream sulfuric acid manufacturing plants. Operators of these facilities can take advantage of the high industrial market value of purified sulfuric acid, a primary industrial chemical.
Sulfuric acid gas cleaning
An efficient sulfuric acid manufacturing process strictly requires the removal of contaminants from the input gas streams, especially fine particulates and acid mists such as those emitted from metal ore roasters and smelters, petroleum refineries, and coal-fired industrial boilers. This is necessary for protecting downstream components such as catalyst beds from corrosion, fouling and plugging, as well PAGE 24
Beltran WESP operating at Hindustan Zinc, Ltd. smelter plants in Udaipur, India.
as for preventing the formation of a “black” or contaminated acid end-product. Proper gas cleaning also results in lower maintenance and operating costs for the plant. For removing fine particulates, acid mists, and other contaminants from the gas stream, the one technology that is almost universally specified for this application is the wet electrostatic precipitator. Primarily targeted at capturing submicron-scale particulate matter, saturated sulfuric or other acid aerosols, and condensable organic chemicals, a well-designed and correctly operated WESP unit is often incorporated after the gas scrubbers, and can achieve collection efficiencies of these materials of greater than 99.9 percent—far superior to other equipment. Although the basic principle and design of the electrostatic precipitator have been around since the early 1900s, recent innovations have produced dramatic advances in efficiency, cost-effectiveness, ease of maintenance, and wider applicability. Beltran WESPs in particular have demonstrated a level of performance that environmental and plant engineers appreciate. However, it is important for engineers to recognize that there are key differences in features and benefits offered by the various precipitator systems. Although they may share the similar operating principles and basic structures, WESPs can vary greatly in design, materials, gas flow rate, durability—as well as collection efficiency. A basic WESP is comprised of an array of ionizing electrodes such that negatively charged discharge rods generate a strong electric field and corona. These are surrounded by or interfaced with positively charged or grounded collection surfaces that attract and hold the charged particles. In operation, the source gas is passed through the electrode array, which induces a negative charge in even the most minute, submicron-size particles, propelling them toward the grounded collection surfaces, where they adhere as the cleaned gas is passed through. The captured particles are cleansed from the plates by recirculating water sprays and residues, including aqueous sulfuric acid, are extracted for further use or disposal. The cleaned gas is ducted to downstream equipment or to the stack, depending on the application. Beltran WESPs can process a wide range of gas streams; they are often used downstream from wet or dry
Hindustan Zinc, Ltd.
flue gas desulfurization units, which cannot capture fine particulates and acid aerosols. They are also superior on high ash content and sticky residues (which may also contain mercury and heavy metals), oily residues/tars, mercury (as condensed oxide), and emissions from municipal solid waste (MSW) in waste-to-energy applications, etc. A traditional problem has been with high-resistivity contaminants, such as low-sulfur coal ash. Beltran WESP system configurations and designs overcome this challenge using multistage ionizing rods, star-shaped discharge points, and space-saving hexagonal tube designs. This unique geometry generates a corona field 4-5 times more intense than other WESPs, achieving superior collection efficiency on resistant materials. This feature also allows higher velocity gas streams, resulting in faster through-put. Beltran WESPs impose a significantly lower pressure drop compared to scrubbers and fabric filters, and thus also contribute to increased production speeds. Furthermore, these gains in efficiency enable the use of smaller-scale, less-expensive equipment for a given set of operating parameters. Beltran WESP systems are designed with advanced electronic controls, which can optimize operating parameters such as gas flow, saturation, temperature, corona intensity, etc., to achieve maximum efficiency. Since the WESP operates at cooler temperatures— usually at the process gas saturation temperature between 100-170° F—the WESP is uniquely adept at capturing condensable organic materials and acid mists, making this technology an invaluable component for sulfuric acid production plants, petrochemical refineries, and spent acid recovery plants. For more information, please visit www.beltrantechnologies.com. q Sulfuric Acid Today • Spring/Summer 2019
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Strong acid Distributors
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Strong acid distributors | MaxiFlowTM
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The MaxiFlowTM strong sulfuric acid distributors are designed and built to provide homogeneous liquid distribution across the entire packed bed area and wall neighborhood. The distribution density can vary from 10 pts/m2 to as much as 100 pts/m2, depending on the process requirements. The distributors can be designed to with stand turndown ratios of as much as 80%, allowing users to set acid flows according to instantaneous capacity. The equipment can be built in Clark Solutions CSXTM high silicon sulfuric acid steel or other metal alloys such as 310S Stainless Steel, Alloy 20 or Hastelloys. Clark Solutions has 30 years experience in sulfuric acid and more then 250 liquid distributors installed and in service.
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The XI Congresso Brasileiro de Ácido Sulfúrico (COBRAS) is the largest sulfuric acid gathering in Latin America. Sulfuric Acid plant operators, vendors, consultants and sulfuric acid professionals actively discuss and share experience in a diverse range of subjects: process and equipment design, materials of construction, operating and maintenance technics, safety and environmental aspects. On its 11th bi-annual edition, COBRAS 2019 will take place from October 14th to 17th at Recanto Cataratas, Foz do Iguaçú, Paraná. Brasil.
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Feature
Further reflections of an acid cooler technical representative
By: R. Barry Krentz, President, Mercad Equipment Inc.
Continuing from the previous (Fall/ Winter 2018) issue of Sulfuric Acid Today, I’d like to share several more interesting “gems” that I’ve witnessed over the years while servicing the anodic protection (AP) of acid coolers, piping, and storage tanks. Story 4: Tube side blockages of acid coolers can be devastating Any complete restriction of cooling water sets up serious corrosion problems for an acid cooler, as in these scenarios: • Heat exchangers using demineralised water for energy recovery suffer immediately from shell side tube corrosion due to the loss of anodic protection (AP); fortunately the chance of blockage with demineralised water loops is small. • In the case of cooling tower circuits, something called “stress corrosion cracking” (SCC) of the tube failure mechanism is likely on blocked tubes, a characteristic intrinsic to many types of ss tubes. Cooling tower water likely has several hundred ppm Cl-, and together with overheated tube walls and stress, the cracking phenomenon often shows up after several months. • In the case of sea water, deterioration can be rapid and more likely due to tube bore pitting failures. I recall a case when a sea water tube failure occurred a week or so after initial start-up. The cause was attributed to several pieces of rubber that blocked off huge tube sheet areas in multiple acid coolers. The tube bores and tube sheets under the rubber were attacked, mainly due to pitting corrosion. Tube failures were numerous and rapid. Of course once the remaining tubes had pits already started, the exchanger continued having failures for many years in those areas where blockage had created high tube wall temperatures. Solution: In all scenarios mentioned previously, flush lines out before start-up, inspect inlet tube sheets/tubes a few weeks after start-up, remove all debris lodged inside tubes during every turnaround, and inspect strainers for damage and verify that the mesh size is smaller than the tube I.D. Story 5: Safety, low corrosion, & high acid quality justifies AP for storage tanks The corrosion of carbon steel tanks results in more Fe- being added to the acid, iron sulphate sludge collecting on the floor, plus hydrogen bubbles streaming up the walls and collecting in the dome space. In the case of stainless steel tanks, the acid may receive some addition of chromium and nickel plus other goodies not usually desired in the acid for resale. By using AP, the owner reduces all these effects by 80-90 percent on average (as confirmed PAGE 26
by independent corrosion studies and users alike). These cases demonstrate the benefits of AP in acid storage tanks: Storage tank failure Back in the early 1970s there was an unfortunate tank failure which luckily did not result in injuries. A new tank was being built beside the old one and the workers went for their morning coffee. Moments later the old tank “unzipped” with a split up the wall spilling a wave of acid. The acid wave pushed the new, empty tank off its foundation toward the acid plant where it knocked over a rail car and a pipe section, stopping just short of the Control Room. Much of the acid that reached the acid plant drained through a water drainage pipe and out into the adjacent river where it collected at the bottom. Although there was no AP on this
tank, it probably could have reduced the corrosion factors. The real cause was the acid inlet line dropping acid in from the top, too close to the tank wall. The acid velocity kept washing away the natural buildup of iron sulphate, which is a natural corrosion layer that reduces the corrosion rate for carbon steel. As a consequence, the wall became thinned down from the top and the pressure of acid broke through the steel plate. Had AP been working, the result would have been an extended life and perhaps the regular tank inspection program would have caught the problem before failure. Clean tank farm It has been reported by tank farm clients that their immediate observation during regular five-year inspections is that the iron sulphate sludge that used to have to be
Storage tanks (CS & SS) are adaptable to the use of anodic protection.
removed during cleanup before inspection was minimal or non-existent. Now isn’t that a nice problem to have! Of course it was also reported during the years prior to inspection that the iron pick up in the acid was generally very low or minimal, even on a static tank using AP. Let’s protect the inside of these tanks so that we can all have a safer area outside! Story 6: Keep water & moisture out of the acid-side of a drained cooler A client was having a turnaround and invited us to inspect the acid coolers. The first day of inspection we opened the side ports (acid side) and the tubes were viewed, photographed, and measured for any corrosion or deposits. There had been some silica/ sulphate deposits and the cooling ability of the cooler was affected, so that night a contractor came in to clean the acid side. The next morning we found huge green puddles on the ground around the coolers. This is evidence of weak acid corrosion that wasn’t there the day before. The cleaners had done their cleaning and aged the coolers by many years! The contractor was called in and questioned. He said they had followed procedure, which we immediately challenged, asking for specifics. The cleaning connection on the acid nozzle was connected to a large hose, fire water was pumped into the cooler, and then drained on the ground. Then a soda ash solution was circulated through the cooler and drained again. This “flushing procedure” was done to avoid the foaming problem when soda ash reacts with acid sulphate. Our assessment and suggestions include: • The green color liquid was chromic acid caused by the weak acid dissolving (corroding) the chrome, etc. from the SS cooler. • The soda ash foaming (CO2 gas being liberated) helps to clean the fouled surfaces. • Water and moist air should NEVER be introduced into a cooler that has acid sulphates/acid residue because weak acid (<90%) can be seriously corrosive. • Cover inspection openings with plastic to keep moist air out. • Blank cooler acid nozzles to keep weak acid or moist air from entering from open acid lines, pump tanks, and towers. Recommendation: Follow the procedures from the OEM. I hope you’ve enjoyed reading some of these stories from my years in this industry. I hope to be able to share more of them in future issues of Sulfuric Acid Today. q Sulfuric Acid Today • Spring/Summer 2019
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Feature
Checking in: Koch Knight drying tower in 18th year at Veolia In the Spring/Summer 2002 issue of Sulfuric Acid Today, we reported on Koch Knight’s drying tower installation at DuPont’s Wurtland, Ky., plant, now owned by Veolia. Back in 2000, during the project’s final planning stages, the client specified a number of goals it wanted in its new tower. We thought we’d check in to see how the unit is measuring up. The Veolia plant in Wurtland, Ky., is a sulfur-burning facility manufacturing sulfuric acid with a 625 ton per day capacity. The customer wanted a technologically advanced drying tower that could meet the plant’s dry air process requirements (-60°F dew point) with minimal maintenance costs. Koch Knight of Canton, OH, designed, built, and installed the tower within tight turnaround conditions, and the unit began operating in October 2001. Now in its 18th year of operation, tower performance “has been excellent,” said George Brown, Engineering Fellow at Veolia, and in some aspects, better than expected. The configuration of the unit’s FLEXERAMIC® ceramic structured packing, with its high surface area and low flow resistance, is designed for minimal sulfate buildup. “And the buildup has actually been less than expected,” Brown said. There has also been no settling in the packed bed and pressure drop has been operating as expected since startup. Other features of the tower have also been tracking well. Brown is very happy with the high efficiency acid distributor, designed to minimize splashing and mist generation. “We were skeptical at first with
The FLEXERAMIC ® ceramic structured packing is installed.
Koch Knight has procured a reputation over the years as a very able contractor in the realm of shipping and delivery. As with the Wurtland job, the company has the capability to construct off site and deliver the goods to a customer fully lined and ready for installation.
Because of the reduced tower size, Koch Knight was able to utilize a novel approach to construction on the Veolia job and line the tower in-house at the company’s Canton, Ohio, facilities.
the clip-on downcomers to the trough, but they have done extremely well with no issues since startup,” he said. Given the tower sits on a wind and earthquake prone area, structural resilience was particularly important. The tower is lined with a combination PYROFLEX® acid resistant sheet lining
and KNIGHTWARE® acid resistant brick outer liner; and multiple inspections have revealed no issues. “No heaving or signs of sulfate behind the brick have been noted,” Brown reports. Similarly, the unit’s dished bottom head and protective lining (designed to reduce maintenance due to buckling of the brick floor) has met expectations, also with no signs of heaving or sulfate behind the brick. One issue that cropped up pertained to the particular distributor mesh pad that was used initially. “In the first couple of years of operation, we had multiple repairs due to holes and gaps in the Style 221 mesh pad. It was replaced in 2009 with an alloy
66 Style 713 mesh pad, and no issues have been noted since,” Brown said. The only other repair, completed in 2013, was to a hole caused by a liner failure in the ETFElined air inlet elbow. In continuous operation since startup with no fouling, Veolia has experienced excellent service from this installation overall. With Veolia continuing to invest in the Wurtland plant, the company has expressed interest in additional brick lined towers and FLEXERAMIC® ceramic structured packing from Koch Knight in the future. For more information, please visit www.kochknight.com. q
The finished product is placed into position at the Wurtland, Ky, facility with the assistance of Koch Knight’s subcontractor ENERFAB Inc. of Cincinnati.
PAGE 28
Sulfuric Acid Today • Spring/Summer 2019
Teck announces new Vice President appointments
Vancouver, B.C.—Teck Resources Limited recently announced the appointment of Greg Brouwer to Vice President, Technology and Innovation; Amparo Cornejo to Vice President, Chile Sustainability and Corporate Affairs; Chris Dechert to Vice President, South America; Sepanta Dorri to Vice President, Corporate Development; Karla Mills to Vice President, Project Development; Crystal Prystai to Vice President and Corporate Controller; and Keith Stein to Vice President, Major Projects. As Vice President, Technology and Innovation, Greg Brouwer is responsible for advancing technology activities and strategy at Teck. Brouwer joined Teck in 1998 and was previously General Manager, Technology and Innovation. As Vice President, Chile Sustainability and Corporate Affairs, Amparo Cornejo is responsible for corporate and government affairs, employee communications, health, safety, environment and community systems, and environmental permitting activities for operations and development projects in Chile. Cornejo joined Teck in 2014 and was previously Director, Social Responsibility and Corporate Affairs. She holds a degree in Journalism and a Bachelor in Social Communications, both from Pontificia Univerisidad Católica de Chile. As Vice President, South America, Chris Dechert is responsible for directing Teck’s operations in Chile to achieve overall site objectives for safety, sustainability, production, and financial performance. Dechert also supports Teck’s various interests in Peru. He joined Teck in 2009 and was previously Vice President, Copper Operations, Chile. As Vice President, Corporate Development, Sepanta Dorri will be responsible for the identification and pursuit of external growth opportunities while also providing corporate support to each business unit’s internal growth initiatives. Dorri joins Teck from Teranga Gold Corporation, where she
was Vice President, Corporate and Stakeholder Development, Canada. In earlier roles, Ms. Dorri was General Manager, Corporate Development Canada at Xstrata Nickel, and Vice President, Investment Banking, Metals and Mining Group Canada at Merrill Lynch Canada. As Vice President, Project Development, Karla Mills is responsible for the successful delivery of capital projects across Teck’s base metals and steelmaking coal business units. Mills joined Teck in 2013 and was previously Acting Vice President, Project Development. As Vice President and Corporate Controller, Crystal Prystai will be responsible for all of Teck’s corporate controller functions. Prystai joined Teck in 2008 and is currently Director, Finance, Reporting and Compliance. As Vice President, Major Projects, Keith Stein will focus on the successful delivery of projects across Teck. Stein joined Teck in 2012 as Vice President, Project Development, and was most recently Acting Project Director for Quebrada Blanca Phase 2 in Chile. For more information, please visit www.teck.com.
Sauereisen promotes Michael J. Briglia to Associate Material Scientist
PITTSBURGH—Sauereisen, Inc., a global leader in corrosion protection materials, announced recently that Michael J. Briglia has been promoted to the position of Associate Materials Scientist. Working from the company’s corporate headquarters, his responsibilities include new product development, contractor training, technical assistance, inspections on job sites throughout the United States, and in-house quality control testing. Briglia began his career at Sauereisen as an internal laboratory technician in 2015 after graduating from the University of Pittsburgh with a B.S. degree in chemistry and biology. “We are very proud to have Michael as part of our team,” said company
president J. Eric Sauereisen. “What drives this promotion is attitude, ability, and motivation in moving forward.” During his time at Sauereisen, Briglia has advanced his knowledge of coating and lining systems by completing the nationally recognized NACE Coating Inspector Programs, CIP Level 1, and CIP Level 2. He has led laboratory experiments to explore the processes behind geopolymerization, helping to create a new family of cements, based on an emerging technology, for construction and wastewater environments. Briglia also is heavily involved in Sauereisen’s inorganic cement technologies and is responsible for the development of new ceramic and structural cements. For more information, please visit www.sauereisen.com.
J.R. Simplot Company names Darron Page new Global Solutions Leader
LATHROP, Calif.—The J.R. Simplot Company has named Darron Page Senior Vice President of Global Solutions. Page will be responsible for the vision, strategy, and functional model for the Global Solutions organization, which includes four critical areas: Sustainability, Procurement, Enterprise Services, and Facilities/Wheels/Aviation. He will report to President and CEO Garrett Lofto and represent Global Solutions across the company as a member of the Simplot Leadership Team. Page will take over for former Global Solutions Vice President Sue Richardson who is tasked with enabling a digital transformation strategy as Senior Vice President of Global Business Transformation. Page has worked as Vice President of Business Development and Optimization in the Company’s AgriBusiness Group for the past two years. In that role he led the Group’s strategic business development process in collaboration with commercial and operational partners. For more information, please visit www.simplot.com. q
416.444.4880 admin@mercad.com ● www.mercad.com
Sulfuric Acid Today • Spring/Summer 2019
PAGE 29
Department
people on the move
Feature
Peripherals of process gas and acid systems
By: Andrés Mahecha-Botero, Hongtao Lu, Guy Cooper, John Orlando, Kim Nikolaisen, Andrew Pedersen, JP Sandhu, NORAM Engineering and Constructors Ltd.
Introduction
Plant peripherals interconnect the fluid systems of the major process vessels, and are an essential part for the operation of any acid plant. The category of peripherals generally includes gas nozzles, ducting, dampers, expansion joints, acid piping, and valves. Most leaks of gas and acid take place as fluids are transferred between process vessels, so while peripherals may not get as much attention as more costly capital equipment, they are a major contributor to the overall health and safety of a plant. Thoughtful design and implementation of peripherals can prevent leaks and help avoid damage to process equipment. The design and implementation of these items is a specialized skill and there are many examples of peripheral failures with significant consequences. The process performance, on-stream time, reliability, maintenance costs, and most importantly the safety of industrial systems are often determined by the design and implementation of the plant peripherals. This article presents some of the preferred choices for the sulfuric acid industry.
Gas side peripherals
Process safety and environmental considerations It is important to use reliable designs and materials of construction to protect operators and to prevent environmental issues. Gas leaks are most often caused by either differential thermal expansion in the hightemperature areas or by corrosion due to acid condensation in the lower temperature areas. Process gas containing SO2, SO3 and H2SO4 vapors can be dangerous to operators and can cause environmental compliance issues. Fig. 1 shows some example leaks. Gas ducting Process gas ducting must handle very high volumetric flows at high temperatures but relatively low pressures. Ducting must tolerate these conditions as well as corrosive environments and significant thermal expansion.
Catalytic converters expand considerably as they heat up, typically over six inches vertically and four inches in diameter. Ducts into and out of the converter are commonly made from different materials and are exposed to different service temperatures, and thus will expand differently. Mechanical designs should allow for movement of equipment due to heating and cooling. Table 1 shows the preferred materials of construction for ducting. Fig. 2 shows implementation of NORAM ducting. Gas dampers Gas dampers are important to maintain proper gas temperatures to the converter beds. Dampers that become seized limit acid plant operation. The swingthrough butterfly damper with a single disc for flow control is one of the most common styles. To prevent process gas leaking to the atmosphere through the shaft seal, a proper stuffing box is required. (The stuffing box can optionally include an instrument air purge.) Also, do not go cheap on the actuator as a little extra torque may be required for a sticky valve. Expansion joints Large sulfuric acid plant equipment experiences considerable thermal growth, especially due to temperature changes from shutdown to operation. The interconnecting ducting needs to be designed to handle a wide range of growth and angular movement; and this is done through expansion joints. Thin-walled, multiple-convolution expansion joints can handle a wide range of angular and lateral movement, but tend to be the weak link in the ducting system. Often the thinness of the convolutions make repair welding difficult. Where shutdowns are expensive, such as with smelters, the owner often will enshroud the leaking expansion joint and run temporary ducting to an appropriate disposal location until replaced at a scheduled shutdown. Single-convolution, or donut, expansion joints are larger in diameter and made with a thicker plate than multi-convolution expansion joints. To accommodate a large
Fig. 1: Ducting failures, from left: SO3 gas leaking from ducting, SO3 gas leaking from an expansion joint, and failed ducting segment.
PAGE 30
Process condition affecting gas equipment
Minimum Temperature
Maximum Temperature
Preferred Materials of Construction
Relative Capital Cost
Relative Lifetime Cost
Very high temperature
Acid dew point temperature
650°C to 1800°C (1200°F to 3270°F)
Refractory-lined carbon steel (various grades)
High
Medium
426°C to 650°C (800°F to 1200°F)
Stainless steels (various grades, including 304H SS)
Medium
Low
426°C (800° F)
Carbon steel
Low
High
650°C (1200° F)
Stainless steel (typically 316L)
Medium
Lower
High temperature
Medium temperature Medium temperature with potential for condensation
Depending on the process, typically below 150°C (300°F)
Table 1: Materials of construction for gas equipment peripherals.
range of duct movement, singles can be paired. The key advantage to the single convolution is they can be repaired by welding in the field because of the thicker metal. Acid entrainment mitigation devices NORAM introduced the acid Entrainment Mitigation Device (EMD) to address the issue of acid mist carryover typically found downstream of acid towers. This acid mist causes corrosion and fouling in downstream equipment and results in increased pressure drop and reduced equipment life. Acid mist carryover is most commonly caused at the tower by poor acid distribution or demister failures, but can also be caused upstream in gas cleaning or downstream of towers by excessive gas cooling. NORAM’s EMD is installed in-line with ducting and is designed to remove a significant portion of acid mist carryover by catching and draining sulfuric acid entrained with the process gas. The EMD also removes sulfuric acid that flows along
the surface of the ducting, is simple to install and maintain, and has minimal pressure drop (1-2” WC).
Acid side peripherals
Process safety and environmental considerations Acid leaks are typically a consequence
Fig. 3: NORAM actuated gas damper, top, and manual damper, bottom.
Fig. 2: 3-D Model of NORAM ducting, top, and spool ready to ship.
Fig 4: NORAM expansion joint.
Sulfuric Acid Today • Spring/Summer 2019
Acid piping Acid piping is one of the most important peripherals in an acid plant, and failures or leaks can be an extreme safety concern as well as a source of downtime and equipment damage. Many plants are mitigating these risks by replacing their remaining cast iron piping with piping made from a high silicon alloy like NORAM SX™. High silicon alloy piping has practically no corrosion in the normal operating range of acid systems, and is considerably less susceptible to erosion even in areas of high turbulence. This erosion resistance allows for acid velocities 2-3 times higher than what is possible in a cast iron system, which is typically limited to 1m/s. A signif-
Feature
of corrosion and/or erosion of acid piping, installation issues, or flange issues. Acid leaks can have devastating consequences to plant personnel, especially if complete rupture of piping takes place in the circulation loops potentially releasing concentrated sulfuric acid at up to 110°C (230°F) at flows exceeding 1,000 m3/h (589 cfm).
icant drawback to cast iron piping is that, unlike alloy, it cannot be welded. Cast iron systems consequently require numerous flanges, which are a source of leaks and also require complete spare spool pieces to correct failures. Acid strainers A well-designed acid strainer can catch small solids (approximately 6mm, depending on requirements), that can damage acid pumps or plug acid coolers or tower distributors. A well-designed acid strainer removes solids from the circulating acid efficiently, reliably, and with low pressure drop. Some of the features of NORAM’s acid strainer are: • Made out of high silicon alloy NORAM SX™. • Low pressure drop to prevent hydraulic issues and pump NPSH issues. • In-line with piping. Can be located at ground level and upstream/downstream of the acid pumps, which simplifies cleaning and protects as many pieces of equipment as possible.
Fig. 7: NORAM ChipGuard CGTM acid strainers. Shop fabrication (left and center) and three strainers in parallel.
• •
Options for draining, isolation, and cleaning. Robust mechanical design to tolerate the service conditions, including pressures up to 8bar, temperatures up to 120°C, and acid concentrations of 90 to 100 wt% H2SO4.
Acid valves Acid valves control acid temperature by controlling the bypass of coolers. Acid
temperature affects both the corrosiveness of the acid and its efficiency as an absorbing liquid in towers. The NORAM-SOMAS valves made out of NORAM SX™ alloy offer a triple offset design with tight shut-off, and can be used for control or isolation purposes. As all the metal in contact with acid is NORAM SX™, the valves are not susceptible to liquid erosion and have the same corrosion resistance to acid as other NORAM SX™ products.
Conclusions
Peripherals frequently do not get the same attention as major equipment, but when poorly designed or maintained they can be one of the largest sources of downtime and safety hazards. Taking advantage of opportunities to update and modernize your ducting, dampers, piping, and valves is less capital intensive than major equipment upgrades, and can have a significant effect on the overall reliability of the plant. NORAM Engineering and Constructors Limited performs engineering studies, training and supplies improved equipment at attractive prices for sulfuric acid plants. For more information, email sulfuric@ noram-eng.com, or call (604) 681-2030. q
Fig. 5: NORAM acid entrainment mitigation device (EMD) design schematics, and shop inspection of an all-welded unit.
Fig. 6: NORAM SX piping installations.
Sulfuric Acid Today • Spring/Summer 2019
Fig. 8: NORAM-SOMAS acid valves, from top to bottom: tight shut-off butterfly valve (MTV-type), tight shutoff butterfly valve (VSS-type), and ball segment-type.
Hats off and congratulations to Kathy Hayward on the 25th anniversary edition of Sulfuric Acid Today. Your magazine and conferences bring the sulfuric acid industry together without peer. We are significantly more knowledgeable and aware of safety, equipment, and practices because of your dedicated service. A heartfelt thank you! Your friends at NORAM. PAGE 31
Feature
Instrument to detect, measure process gas dew point/moisture leaks By: Daniel T. Menniti, Senior Director of Marketing and Sales, Breen
Sulfuric acid is manufactured by oxidizing SO2 gas to SO3 in a converter through a catalytic oxidation process. The most common sources of SO2 are: • Burning elemental sulfur. • SO2 off-gas from a primary process such as a copper smelter. • Decomposition of H2SO2 in a spent acid regeneration process. The SO2 gas produced from those processes is passed over a catalyst in the presence of oxygen to oxidize it to SO3. The SO3 gas is then absorbed into 97–98 percent H2SO4 to form oleum (H2S2O7), also known as fuming sulfuric acid. The oleum is then diluted with water to form concentrated sulfuric acid.
Acid dew point measurement in sulfuric acid production
In sulfuric acid production, sulfur dioxide (SO2) is oxidized over a solid vanadium catalyst to generate sulfur trioxide. The sulfur trioxide is then absorbed in water contained in 98 percent sulfuric acid to form new sulfuric acid. The SO2 is either produced by burning elemental sulfur or is an off-gas from other processing plants such as a copper smelter or a spent acid regeneration process. The gas laden with SO3 in the process is kept moisture free and the only time moisture gets introduced in the gas is when there is a process upset. This is a highly undesirable condition and can be potentially hazardous. Moisture in the flue gas combines with the SO3 which then condenses on the process equipment surfaces. This is generally indicative of one of the following conditions, among others: • Drying tower malfunction. • Moisture in feed. • Waste heat boiler tube leaks. • Economizer tube leaks. • Cleaning system malfunctions. The presence of moisture and therefore weak acid vapor in the gas stream is detrimental to equipment health and can cause extreme corrosion. A secondary impact of moisture in the flue gas can be the formation of hydrogen gas creating an explosion hazard [1]. • SO3+H20 → H2SO4 • Fe+H2SO4 → FeSO4+H2 The H2 formed as described by the previous equations can create an explosion hazard in the presence of O2 and an ignition source.
•
Fig. 1: Typical moisture ingress points in a sulfuric acid manufacturing process.
• • • •
Drying tower Raw material feed stock Waste heat boiler tubes Economizer tubes
Monitoring each of these individual process points (see Fig. 1) to prevent malfunction and moisture ingress becomes expensive and manpower intensive. Traditionally, operators measure the acid dew point to indicate such moisture leaks, which would, in theory, provide a step change response should moisture enter the upstream process. Up until recently the available technologies have not been able to withstand the harsh conditions presented by the application. Understanding this need, Breen embarked on a product development project to design a system that would withstand the harsh environment, as well as simplify the output to provide the desired response.
Challenges for the measurement of acid dew point in sulfuric acid plants
There are several requirements for an instrument that can survive in a sulfuric acid plant and provide the necessary measurement. Chief among them are: • A completely sealed design to isolate process gases from the system internals. • Must withstand a process positive pressure of up to 20 Psig (typically 6-10 Psig). • Safety features to isolate the system in case of sensor failure/breach.
Material of construction designed to handle high concentrations of sulfuric acid. • Process mounting system designed to seal and allow online system removal for maintenance while the process is running. The Breen Dew Point meter was originally designed for negative pressure, combustion gas processes. These processes allowed for a probe system that only needed to be sealed from the atmosphere once it was inserted into the process. The probe did not have any protection or a process to allow for a hermetically sealed insertion. Subsequently, the system was redesigned to meet the challenge above. The commercial design for the Breen SA Probe can be seen in Fig. 2. After successful factory testing, the probe was taken to a sulfuric acid manufacturing plant and installed at the exit of the economizer on a sulfuric acid production train in Fig. 3. The economizer outlet location presents itself with a process gas temperature of approximately 400 degrees F and a process gas pressure between 6 and 10PSI. The process gas dew point was expected to be at approximately 250 degrees F. After initial installation the dew point probe provided sound dew point results as seen in Fig. 4. Over the next several weeks the system successfully measured the process gas dew point on a continuous basis. Periodically, the system was able to detect an increase in process gas dew point as a result of moisture ingress into the process. This moisture
Fig. 2: Breen SA-Probe for sulfuric acid manufacturing plants.
Fig. 3: Installation of AbSensor-ADM-SA Rev 2.
ingress was simulated by introducing moist plant air through the dew point sensor cleaning air tube, aka “sootblower” tube, as seen in Fig. 5.
“Above dew point” measurement tests
To keep the sensor free of process condensables for the long term and also provide moisture leak detection, it was decided to operate the system at an “above dew point cycle.” The above dew point cycle would allow the probe to operate in the duct at a temperature higher than the
Fig. 4: Preliminary dew point measurements.
Moisture leak detection
As stated earlier, there are several potential sources of moisture ingress into the process gas stream. The more typical sources include: PAGE 32
Fig. 5: Beta system output (right) showing increased dew point due to moisture ingress into process. Sootblower tube (left).
Sulfuric Acid Today • Spring/Summer 2019
As seen above, the system was then left to measure normal dew points for 6 hours (16:00 - 22:00) on November 18, 2016 to verify the normal process dew points. Moisture detection test 09:45 November 18, 2016 Fig. 6: Above dew point operation.
Fig. 8: SA Probe normal cycle and check cycle.
Fig: 9: SA Probe responds to small amounts of moisture.
Sulfuric Acid Today • Spring/Summer 2019
Moisture leak detection commercial design In late September/early
October 2018, Breen installed the commercial design into a sulfuric acid plant in California (Fig. 7). The probe system was allowed to run in “above dew point mode,” with weekly “check cycle” cooling the sensor to the process gas dew point. The probe cycle and check cycles are shown in Fig. 8. On January 23, 2019, the plant performed a test to verify that the system would indeed detect a moisture leak. At approximately 10:45 (Fig. 9) you can see a probe response when a pressure point line was cleared out with instrument air. A compressor was then hooked up to the line to pump ambient air into the duct; no response was seen, and it was assumed that the air pressure was not powerful enough to push sufficient air into the duct. Subsequently, the process engineer put water into the pressure point line and used instrument air to push that water into the duct. The amount of water added was approximately a gallon. At 13:15 you can see the
Feature
Figure above shows the probe sensor operating under dry conditions cycling between 285 degrees F and 350 degrees F. On November 6, 2016 at approximately 09:45 am the system was run to detect normal dew point and verify operation.
process gas dew point, but low enough to detect an increase, or step change, in process gas dew point. There were two objectives that needed to be met during operation in this mode: 1. Detect moisture ingress. 2. Provide a method to verify measurement integrity. The system was operated in this mode with periodic check cycles (i.e. dew point measurements) and moisture detection (via moist air into the sensor sootblower tube). This can be seen graphically in Fig. 6. During this time there were no signs of sensor fouling or system malfunction. The system was allowed to continue to run for several weeks to verify the probe integrity for the application. Subsequently, further design changes were made to eliminate any additional leak points from the probe and bring the beta design to its current commercial design.
Fig. 7: Installation of SA Probe (photos courtesy of J.R. Simplot, Lathrop plant).
probe immediately responded to the event. It was concluded, with a fairly strong certainty, that the probe is very responsive to even small amounts of moisture. There were also other minor responses in the previous weeks, which were believed to have been caused when other pressure point lines were cleaned out.
Summary It has been demonstrated that
the dew point measurement system has the capability to measure continuous process gas dew point temperatures. Understanding that the industry desires long term, ultra-low maintenance, it appears that the “above dew point mode” measurement philosophy has merit as a method to detect moisture leaks, while maintaining a clean and dry sensor in between moisture events. This method also allows for the in situ verification of sensor function using a periodic system “check cycle” outputting a measured dew point on demand. The commercial system has been running over five months with no failures or maintenance. For more information, please visit www.breenes.com. q Acknowledgment: Note [1] Information developed and presented by the Hydrogen Safety Workgroup. PAGE 33
Department
product news Haldor Topsoe launches connected service for optimal plant
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KONGENS LYNGBY, Denmark— Haldor Topsoe, a world leader in high-performance catalysts and proprietary technologies, and the connected plant leader Honeywell announced a technology alliance to expand the benefits of connected services to a broader range of the chemical and refining industries. As a product of this alliance, Topsoe has launched ClearView™–a breakthrough service to maximize plant output, save energy, and improve reliability. Using Honeywell’s cloud-based software platform, the ClearView™ service gathers operating data from the plant, cleanses the data, applies Haldor Topsoe’s tools and experience, and delivers performance-enhancing insights straight to the plant’s process engineers and managers. “As a global market leader in catalysts and technology, we are thrilled to offer our customers a service that puts our decades of experience at their fingertips every hour of every day. Using Honeywell’s proven software platform and tools, ClearView™ applies Topsoe’s unique insights and allows our experts to work more closely with plant engineers to meet critical performance targets and reduce the risk of unplanned shutdowns,” said Bjerne S. Clausen, CEO, Haldor Topsoe. Haldor Topsoe’s proprietary modelling and simulation tools have been constantly updated and refined to design increasingly energy-effi-
cient and reliable plants and help customers optimize existing production and catalyst utilization. Now, the ClearView™ service gives Topsoe customers continuous access to these tools to increase the profitability of their plants. As part of the service, Topsoe engineers follow plant performance and proactively guide the customers’ plant engineers in optimizing performance and quickly addressing operational issues based on output from the ClearView™ service. “In essence, ClearView™ constitutes a completely new way for plant personnel and Topsoe experts to join forces in pursuing optimal utilization of a plant or a unit,” said Michael Fjording, Director, Connected Services, Haldor Topsoe. “The ClearView™ service is a great addition to the Honeywell Connected Plant partner ecosystem, because it meets a growing need in a broader area of the chemicals and refining processes,” said Zak Alzein, vice president and general manager of Honeywell’s Connected Performance Services business. “The technology alliance with Topsoe leverages the power of the connected plant and brings the deep domain expertise of Topsoe into a growing partner network.” Honeywell Connected Plant solutions is already well-proven, as such solutions have been deployed or are in the process of being deployed in more than 60 customers’ process units. The first ClearView™ service has been developed specifically to boost ammonia production. ClearView™ services for other segments in the chemical and refining industries will follow. For more information, please visit www. topsoe.com or www.honeywell.com. q
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PAGE 34
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Sulfuric Acid Today • Spring/Summer 2019
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Faces & Places Sulphur 2018 Conference November 5-8, 2018 • Gothenberg, Sweden James McCullagh, oil products analyst of Energy Aspects presented the paper, “IMO 2020: How is the industry responding as the deadline nears?” to the participants of the Sulphur 2018 conference. Also pictured, from left, are Dr. Moncef Hadhri of CEFIC, Sergei Sushko of World Fertilizer Market, Juan von Gernet of PhosAgro, and Dr. Peter Harrisson of CRU.
Stefan Bräuner of Outotec shares his company’s information with Sulphur 2018 attendees. Graeme Cousland of Begg Cousland explains the benefits of his company’s candle filters to an attendee at the Sulphur 2018 conference.
Discussing the topic of digitization, industry and digital transformation at the Sulphur 2018 conference are, from left, Oliver Lieske of Team PwC, Collin Bartlett of Outotec, Stefan Bräuner of Outotec, Mike Allenspach of nVent, and Frank Scheel of Jacobs Comprimo Sulphur Solutions.
Dirk Hensel of BASF, left, and Marco Kennema of BASF, right, network with Sulphur 2018 attendees in their company’s exhibition booth.
Sulphur 2018 offered several panel discussions. Chairing the panel discussion, “Digitization and Industry 4.0: understanding the opportunities offered by digital transformation,” are, from left, Oliver Lieske of Team PwC, Collin Bartlett of Outotec, Stefan Bräuner of Outotec, Mike Allenspach of nVent, Kent Kalar of AKOS, and Frank Scheel of Jacobs Comprimo Sulphur Solutions.
Celebrating a new name in industrial process solutions IPCO, previously operating as Sandvik Process Systems, invited all Sulphur 2018 attendees to join them for an informal evening of fun during the conference.
Dr. Moncef Hadhri, chief economist with CEFIC, presented the paper, “Challenges and opportunities for the European chemical market,” to the participants of the Sulphur 2018 conference. Also pictured, from left, are James McCullagh of Energy Aspects, Sergei Sushko of World Fertilizer Market, Juan von Gernet of PhosAgro, and Dr. Peter Harrisson of CRU.
A relaxed evening of great food, drink, and fun was had by all at IPCO’s evening function during the Sulphur 2018 conference. Guests were treated with live entertainment provided by the international cover band Johnny JukeBox, and entertaining illusions from a group of talented magicians.
Outotec’s team, Anders Ohlin, left, Stefan Bräuner, center, and Jan Albrecht, facilitated a technology workshop, “Outotec’s life cycle philosophy to boost sulfuric acid plant profitability,” during Sulphur 2018.
35th Oil | Gas | Fertilizers | Metallurgy | Industrial
Sulphur 2019 + Sulphuric Acid 4-7 November, 2019 Hilton Americas, Houston, Texas, USA
CALL FOR PAPERS DEADLINE 24 MAY
CRU Sulphur + Sulphuric Acid 2019 is the global gathering for the sulphur and acid industries to meet, learn, and do business.
CALL FOR PAPERS FAQ Why submit an abstract? The conference is an ideal platform to demonstrate thought-leadership and operational experience, or showcase your product or service to a large global audience of technical experts. How to submit All abstracts must be submitted online at www.sulphurabstracts.com by 24 MAY 2019 to be considered for the technical agenda. Who can submit an abstract? We welcome abstracts from all organisations, but papers authored or co-authored by operating companies will be prioritised.
What subjects are we looking for? We welcome operational case studies, and/or new technology, process, materials or equipment developments, that offer the potential of improved reliability, safety, environmental or production efficiencies. For a full list of subject areas, visit: www.sulphurconference.com What happens next? Abstracts are reviewed by a technical steering committee chaired by CRU. Selection criteria include: Operational experience Novelty Operational challenges, and their solutions Objectivity
Where can I go for more information? Visit the website www.sulphurconference.com or contact amanda.whicher@crugroup.com
INTERESTED IN SPONSORING OR EXHIBITING? Another great way to increase your profile at the conference is to sponsor or exhibit. Each year more than 70 solution providers from around the world exhibit at the CRU Sulphur + Sulphuric Acid conference â&#x20AC;&#x201C; to access a global audience of sulphur and acid professionals. Packages are tailored to ensure high-profile brand exposure, and to maximise face-to-face interaction with delegates. For more information on the exhibition, and sponsorship opportunities available, please contact: michelle.fisk@crugroup.com Sponsors:
+44 (0)20 7903 2159 Official Publications:
For more information and to book you place, please visit: www.sulphurconference.com
SU19 CFP 10 inches x 12 1/4 inches.indd 1
04/03/2019 22:37
Department
calendar of events 43rd AIChE Clearwater Conference planned
The biennial world-class gathering will bring together
companies in Latin America.
The predominantly technological and scientific event
Clark Solutions by email at gabriel@clarksolutions.com.br.
members of the AIChE Central Florida Section and
in the fields of phosphates and its derivatives; technical,
all levels of the phosphates and sulfuric acid industries.
CLEARWATER, Fla.–Each year for the last 42 years,
colleagues from all over the world have gathered at Clearwater Beach to share ideas concerning chemical
process technology, specifically the production of phosphoric acid, phosphate fertilizers, and sulfuric acid.
The Sheraton Sand Key Resort in Clearwater will once again be the site for this anticipated event, scheduled for June 7-8, 2019.
On Friday, June 7, there will be a sulfuric acid
workshop with presentations and a panel discussion. Participants can earn Professional Development Hours for attending.
As always, the convention also provides a relaxing
getaway with friends and family, good food, and a lot of
fun. Social and networking events are planned during the event, with a little something for everyone.
For more information, please visit www.aiche-cf.org.
showcases the progress and research and development
scientific, and technological innovation; new agricultural applications; and sustainable development and renewable energy.
Attendees of the SYMPHOS 2019 will be able to
connect with over 1,200 participants including producers,
consumers, traders, market analysts, engineers, and technical experts.
For more information, please visit www.symphos.com.
Congress Brazilian of Sulfuric Acid slated for October
SÃO PAULO, Brazil–At the XI Congress Brazilian of Sulfuric Acid (COBRAS), top market discussions are held
between top sulfuric acid professionals in the industry. The meeting is scheduled for October 14-17 at the
Recanto Cataratas Resort in Foz do Iguaçu, Brazil. The
Morocco to host SYMPHOS 2019
agenda of the 2019 COBRAS will consist of presentations
BENGUERIR, Morocco–The 5th International Phosphates
and debates with the largest players in the sulfuric acid
(SYMPHOS) will be held at Mohammed VI Polytechnic
operations and maintenance and will discuss the latest
Symposium
industry. COBRAS will address key issues regarding
University-Congress Center in Benguerir October 9-11.
technologies in the industry with some of the largest
Industry
Innovation
and
Technology
For more information, please contact Gabriel Seiji of
Sulphur 2019 + Sulphuric Acid conference planned for Houston
LONDON–CRU’s Sulphur + Sulphuric Acid conference
is the annual global gathering for the sulfur and sulfuric
acid industries and will take place November 4-7 at the Hilton Americas in Houston, Texas. The conference
attracts over 480 delegates, representing sulfur and sulfuric acid operators, producers, buyers, sellers, and solution providers.
For more than 30 years, the conference has been a
premier event for anybody working in sulfur and sulfuric acid production, consumption, and trade to come together
to meet, learn, share experiences, discuss challenges,
and do business. The four-day agenda incorporates key
market insights on supply, demand, and price, with indepth technical content focused on practical applications of technology, equipment, and operations know-how.
Whatever information you need to further develop
your business for the year ahead, you can be sure this four-day event delivers the content and networking opportunities to enable business success.
For more information, please visit www.events.
crugroup.com/sulphur. q
2020
Australasia H SO W O R K S H O P 2
4
S U L F U R I C A C I D T O D AY
Save the Date April 5 - 8, 2020 Hilton Brisbane
2020 Aus trala Worksho sia Sulfuric Acid p will off er: — Keynote
A Acid Ma ddress on the Global rket Sulfuric — Informa tive Co-Spo nsor prese — Insightfu nta l — Mainten producing plant pres tions an c e p an e l entations dis — Safety p anel and in cussions cident revie — Co-Spon ws s — Network or exhibits ing opportu nities
Brisbane, Queensland • Australia Sponsored By:
Sulfuric Acid T
O
D
A
Y
Industry’s Premier Event for Networking & Sharing Best Practices™ Register On-Line Today! www.acidworkshop.com PAGE 38
Sulfuric Acid Today • Spring/Summer 2019
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