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On the Cover … 7
The Tenke Fungurume mine in the Democratic Republic of Congo brings its second sulfuric acid plant on line.
Departments
4 Industry Insights News items about the sulfuric acid and related industries 28 In the News 32 Lessons Learned Case histories from the sulfuric acid industry 38 Faces & Places Covering sulfuric acid industry events 40 Calendar of Events
Dear Friends, Welcome to the Spring/Summer 2016 issue of Sulfuric Acid Today magazine. We have dedicated ourselves to covering the latest products and technology for those in the industry, and hope you find this issue both helpful and informative. As we send this issue to press, we’re gearing up for another information sharing event, our 2016 Australasia Sulfuric Acid Workshop, April 4-7 in Townsville, Queensland, Australia. This version of the workshop is packed full of informative presentations from worldwide industry professionals. Some of the key topics for this year’s meeting include converter maintenance, catalyst screening, sulfur handling and filtration, heat exchanger maintenance and materials, mist elimination solutions, acid resistant linings and materials, process gas monitoring, materials of construction for equipment and hydrogen safety and incident reviews. If you would like more information about the event, please visit www.acidworkshop.com. Meanwhile, we hope this issue of Sulfuric Acid Today will provide you with some innovative technologies for your profession. Be sure to read such articles as “Global acid market: changing fundamentals,” (page 10), “Solutions for common problems in sulfur spraying” (page 12), “Dry and wet precipitators–the yin/yang of off-gas acid production” (page 14), “Fiber bed mist eliminator refresher: theoretical fundamentals vs. real world” (page 17), “Aggressive corrosion and demanding conditions need aggressive solutions” (page 20), “Modernization of a
EDITOR April Kabbash EDITOR April Smith Marketing ASSISTANT Connor Chapman DESIGN & LAYOUT 281-545-8053 Mailing Address: P.O. Box 3502 Covington, LA 70434 Phone: (985) 893-8692 Fax: (985) 893-8693 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
Sincerely, Kathy Hayward
FEATURES & GUEST COLUMNS
PUBLISHED BY Keystone Publishing L.L.C. PUBLISHER Kathy Hayward
sulfuric acid plant in three easy steps,” (page 21), “Acid mist elimination in sulfuric acid plants” (page 24), “Weir Minerals Lewis Pumps manufactures API 610 11th edition qualified pumps as standard” (page 26), “Creating reliable, durable seals in glass-lined steel equipment” (page 30), “‘Quick Fit’ pre-assembled acid-proof lined equipment” (page 34) and “Moisture-free surface cleaning technology: NitroLance™” (page 36). I would like to welcome our new and returning Sulfuric Acid Today advertisers, including Acid Piping Technology Inc., Beltran Technologies, Central Maintenance & Welding, Chemetics Inc., Clark Solutions, Conco Services Corp., Corrosion Service, Dresser-Rand, El Dorado Metals Inc., Haldor Topsøe A/S, Koch Knight LLC, KSB AMRI Inc., OPSIS, MECS Inc., NORAM Engineering & Constructors, Optimus, Powell Fabrication & Manufacturing, Saint-Gobain NorPro, Southwest Refractory of Texas, Spraying Systems Co., Southern Environmental Inc., STEULER-KCH GmbH, VIP International, Weir Minerals Lewis Pumps and W.L. Gore & Associates. We are currently compiling information for our Fall/ Winter 2016 issue. If you have any suggestions for articles or other information you would like included, please feel free to contact me via e-mail at kathy@h2so4today.com. I look forward to hearing from you.
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10 Global acid market: changing fundamentals 12
Solutions for common problems in sulfur spraying
14
Dry and wet precipitators–the yin/yang of off-gas acid production
17
Fiber bed mist eliminator refresher: theoretical fundamentals vs. real world
20 Aggressive corrosion and demanding conditions need aggressive solutions 21
Modernization of a sulfuric acid plant in three easy steps
24 Acid mist elimination in sulfuric acid plants 26
21
Weir Minerals Lewis Pumps manufactures API 610 11th edition qualified pumps as standard
30
Creating reliable, durable seals in glass-lined steel equipment
34
“Quick Fit” pre-assembled acid-proof lined equipment
36
Moisture-free surface cleaning technology: NitroLance™
36
Info sharing at CRU’s conference, Sulphur 2015
34
Department
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PAGE 4
Morocco’s King Mohammed VI inaugurates OCP projects
JORF LASFAR, Morocco–Early this year, Morocco’s King Mohammed VI inaugurated a fertilizer plant and the first stage of a seawater desalination plant for an overall budget of $600 million USD. The new plant, Africa Fertilizer Complex, is dedicated to supplying the African market. Initiated by Morocco’s Office Cherifien de Phosphate (OCP), these largescale projects represent the Sovereign’s new commitment to south-south cooperation and the willingness to support OCP innovation and sustainable development initiatives. The move also represents a consolidation of Morocco’s leadership in the global phosphates market. Africa Fertilizer Complex, which was developed upon the instructions of King Mohammed IV, aims to accompany the growth of African markets through continued and regular supply of fertilizers (DAP/MAP/NPK). The new plant consists of a sulfuric acid plant (1.4 million tons per year), a phosphoric acid plant (450,000 tons per year), a fertilizer plant (one million tons of DAP per year), a 62-megawatt solar station and up to 200,000 tons of fertilizer storage infrastructure. This mega project encourages technological and environmental innovation in sulfuric acid production through a 10 MW electric energy gain and an important reduction in seawater consumption. Sulfur dioxide emissions are significantly lower than international norms. The seawater desalination plant, part of OCP’s water strategy, aims to meet the additional needs created by the development of a Khouribga-Jorf Lasfar platform without additional demand for conventional water. The plant, which will be built in three stages, will reach an annual production of 75 million cubic meters. For more information, please visit www.ocpgroup.ma.
Boliden invests in new acid plant at Harjavalta smelter
BOLIDEN, Sweden—Boliden Harjavalta operates two acid plants that produce sulfuric acid and liquid sulfur dioxide from smelter off-gases formed in the copper and nickel smelting processes. Boliden is investing in a new and more efficient acid plant using best available technology. The investment program, that will run from 2016-2019, consists of two parts. The first part will be about 65 million EUR with the total investment estimated to be 90 million EUR.
“The performance of Boliden Harjavalta has developed positively over several years. This investment improves our technical infrastructure, which is fundamental for our long term competitive position. Continuity of the site, together with the improved environmental performance, is important for our local community too,” said Timo Rautalahti, general manager, Boliden Harjavalta. With the new plant in operation, the efficiency and environmental performance of Boliden Harjavalta will improve in several areas. SO2 emissions will be reduced by 20-25 percent and cooling water by 40 percent, as heat is recovered, resulting in higher energy efficiency. In addition, minor bottlenecks will be resolved, especially on the copper line, making future expansion projects possible on both the copper and nickel lines. For more information, see www.boliden.com.
IFFCO’s Paradeep unit receives accolades
ODISHA, India—The Indian Farmers Fertilizer Co Operative (IFFCO), a multi-unit cooperative with 40,000 member cooperatives and over 50 million members, is one of the biggest agricultural cooperatives in the world, generating over $5 billion in turnover. It supplies fertilizer and services to agricultural producers and currently holds five fertilizer manufacturing units in India, including one at Paradeep. IFFCO Paradeep’s achievements have recently been recognized through various awards in the fields of CSR, energy savings, technical innovation, water conservation, and environment management. These awards include: FAI Environment Protection Award 2015, Greentech Environment Award 2015, Kalinga Safety Award 2014, CII 16th National Award of excellence in energy management 2015, Paradip Port Trust for handling the highest tonnage raw materials in 2015 and Krushak Bandhu Award 2012. The Paradeep unit was taken over by IFFCO in October 2005. The unit consists of two sulfuric acid plants with a capacity of 3,500 MTPD per plant, a phosphoric acid plant having a capacity of 2650 MTPD of ‘P2O5’ (the world’s largest single stream) and three DAP/ NPK fertilizer plants with a capacity of 19.20 lakh metric tons per annum. The principal raw materials are rock phosphate, sulfur, sulfuric acid and ammonia which IFFCO Paradeep imports from various countries. The facility also includes a captive jetty located at Paradeep Port as well as unloaders with capacities of 1200 MTPH and 800 MTPH. The raw materials are transported from the jetty to the plant through 5-km long conveyor belts and pipelines. Water required for the plant is supplied from Taladanda Canal 2
Sulfuric Acid Today • Spring/Summer 2016
km away from the plant site. Electricity requirements are met through two dedicated power plants, each having capacity of 55M, as well as two 110-MTPH coal fired boilers used to balance power and steam requirements. IFFCO’s Paradeep unit gives prime importance to the welfare of both its employees and the local population, as well as preserving the environment. For more information, please visit www.iffco.in.
Uganda phosphate project beneficiary of China-Africa partnership KAMPALA, Uganda—The construction of Uganda’s Sukulu phosphate factory in the Tororo District received a boost of $240 million at the China-Africa Investment and Financing Forum held in South Africa last December. The Industrial and Commercial Bank of China (ICBC) in cooperation with the Standard Bank of South Africa will disburse the money in tranches to the project’s developer, Guangzhou DongSong Energy Group Company Ltd. The Sukulu facility will consist of a mine and a beneficiation plant with annual capacity of two million metric tons, a phosphate fertilizer plant with annual production of 300,000 metric tons, a sulfuric acid plant with annual production of 400,000 metric tons, a 12MW waste heatbased power generation plant and a steel mill with annual production of 300,000 metric tons. The company is expected to hire more than 1,200 local people in all of its plants, in addition to investing in schools, hospitals and other public welfare projects. “The project will boost agriculture production through the provision of fertilizers, support infrastructure development through iron and steel production, offer jobs to the region, support other industries and boost our export earnings through value addition of the primary commodities,” the Energy Ministry’s Permanent Secretary, Fred Kabagambe-Kaliisa, said. The Uganda government has granted mining rights to the investor in the form of a 21-year mining lease, and other exploration licenses to finalize additional exploration work. The government has further provided 600 acres of land to facilitate the development of the industrial complex, the construction of staff residences and the administration block.
New acid plant at India’s largest steel producer ORISSA, India—A new sulfuric acid unit with a capacity of 125 metric tons per day was inaugurated at the Rourkela Steel
Department
Industry Insights Plant (RSP) in Orissa in February. The Rourkela plant, owned by Steel Authority of India Ltd. (SAIL), replaced an older, obsolete unit. The acid produced in this unit is used in the company’s Coal Chemical Department, Cold Rolling Mill and Captive Power Plant-I. The surplus production will be marketed externally. RSP has developed 20 new specialized products, including products for the defense sector as part of its drive to slash the country’s import burden and adopt the ‘Make in India’ mission. RSP is the first integrated steel plant in the public sector in India. After implementing a massive modernization and expansion that is in the last leg of completion, RSP has enhanced its capacity to 4.5 million metric tons of hot metal and 4.2 million metric tons of crude steel. SAIL, India’s largest steel producing company, is among the seven Maharatnas of the country’s Central Public Sector Enterprises. SAIL has five integrated steel plants, three special plants, and one subsidiary in different parts of the country. For more information on SAIL, please visit www.sail.co.in.
Jordan and China’s firms to build $1.3 billion fertilizer plant
AMMAN, Jordan—The national Jordanian Phosphate Mines Company and China’s Chongqing Minmetal and Machinery Import and Export Co. (CMMC) signed an agreement in the first quarter of 2016 to build a $1.3 billion industrial fertilizer complex in the southern city of Aqaba. Officials in Amman hope the new project will breathe life into the struggling company and the fertilizers produced will be exported to several markets across the world. Thousands of jobs will also be created from the project, helping to absorb numbers of unemployed among the rapidly growing population. Jordan Phosphate Mines Co., founded in 1949, is a mining and fertilizer producer operating in the Hashemite Kingdom of Jordan, which has the fifth largest phosphate reserve in the world. The company is the second largest exporter, and sixth largest producer of phosphate, with production capacity exceeding 7 million tons of phosphate annually. CMMC, founded in 1983, specializes in contracting overseas projects, exporting labor services, self-supporting and acting as an agent for the import and export of various commodities and technologies, and engaging in domestic trade. For more information on Jordan Phosphate Mines Co., please visit www. jpmc.com.jo. For more information on CMMC, please visit www.cqmmc.com. q
Sulfuric Acid Today • Spring/Summer 2016
PAGE 5
By: April Kabbash, Editor, Sulfuric Acid Today
T
he Democratic Republic of Congo (DRC), deep in the heart of Africa, is home to some of the world’s largest known copper deposits. Tenke Fungurume Mining (TFM), located in the Lualaba Province, is one of the country’s largest copper producers, as well as the world’s premier producer of cobalt. The facility, which includes surface mining, leaching and SX/EW operations, currently produces 205,000 metric tons of copper and 16,000 metric tons of cobalt each year. As capacities increase, so do the demands for sulfuric acid, an important component in processing the ore. After the successful installation of the site’s first sulfuric acid
Sulfuric Acid Today • Spring/Summer 2016
plant in 2009, increasing capacities led to higher demands for acid. Always looking ahead, the company quickly realized the benefits of adding a second, larger acid plant, which came online in the first quarter of 2016. This addition brings the company’s investment in the area to over $3 billion so far, representing one of the largest private investments in the country’s history.
History
The Tenke Fungurume deposits are located within concessions totaling over approximately 600 square miles in the Lualaba Province of the DRC, about 110 miles northwest of Lubumbashi,
the republic’s second-largest city. In the southeastern section of the country, the area was first explored in 1917 by Union Miniere, a Belgian mining company that was later succeeded by La Generale des Carrieres et des Mines (Gecamines), with drilling beginning in 1919. The Mobutu government nationalized the project in 1969. A private/government consortium, Societe Miniere du Tenke Fungurume, then made an investment of $280 million. In 1996, TF Holdings Ltd. (TFH), a subsidiary of Lundin Group, acquired majority interest in the project through a public tender process. Tenke Fungurume Mining was formed for the purpose of
developing the deposits of copper, cobalt and associated minerals. Today, Freeport-McMoRan Inc. owns 56 percent of Tenke Fungurume Mining; Lundin Mining Corp holds 24 percent; and Gecamines, which is wholly owned by the government of the Democratic Republic of Congo, owns 20 percent. The Tenke Fungurume deposits are sediment-hosted copper and cobalt deposits with oxide, mixed oxide-sulfide and sulfide mineralization. The dominant oxide minerals are malachite, pseudo malachite and heterogenite. Important sulfide minerals consist of bornite, carrolite, chalcocite and chalcopyrite. PAGE 7
Cover Story
Tenke Fungurume looks to the future with second acid plant
Cover Story
Aggregate reserves total 99 million metric tons (mt) of ore at 3.19 percent copper and .37 percent cobalt with recoverable metal amounting to 7.2 billion pounds of copper and .9 billion pounds of cobalt.
Adding acid
The next logical step in streamlining production at TFM was the addition of on-site sulfuric acid manufacturing. The facility’s first acid plant, AP1, was brought on-line in 2009 with a capacity of 600 metric tons per day. Before that, TFM was importing all of its acid from other locations. The original acid plant met some, but not all, of the facility’s needs, even after a de-bottlenecking of AP1 in 2012, which increased annual acid production name plate capacity to 825 metric tons per day. While this was an improvement, it still didn’t provide all the acid necessary for the facility. “TFM’s acid requirements are constantly increasing with the mining of ores with higher copper content,” said Daudet Zeka Songesa, acid plant superintendent at Tenke Fungurume. “Producing acid at the site to meet this increased demand is more economical than purchasing and transporting sulfuric acid to the site, with an improvement in acid availability. As an additional benefit of this project, the number of acid trucks on the road will be reduced, improving the safety and environmental impact risks in the region.” So, planning began for a second, larger acid plant. After the successful integration and operation of AP1, there was no need to reinvent the wheel when planning AP2. “We built on our success with the first acid plant, creating the second on a larger scale,” said John Wellington, Tenke Fungurume’s acid plant manager. A formal and systematic “lessons learned” session was conducted during the feasibility study phase of AP2. Key project team members met to review all aspects of the design and generate ideas on what could be done to make AP2 better than AP1. “While AP1 was a very successful project, improvements can always be made,” said Wellington. “Several beneficial changes came out of the sessions, including changes to the plant layout to incorporate recommendations from the operators and an upgrade in the DCS system with an improved interface.”
As with AP1, Saramet alloy acid towers were prefabricated, trucked in and lifted into position.
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This schematic of the AP2 converter shows the inter-reheat exchanger.
In the ISO-FLUX trough distributor, acid flows from the main header to the bottom of the trough. It then flows up via a series of calming plates which also filter out debris. Choking of flow orifices through the downcomers is virtually eliminated.
The Tenke Fungurume facility will produce all the sulfuric acid it needs onsite, with the addition of AP2.
Layout changes included increasing the size of platforms around the front end of the sulfur furnace, in the area where sulfur guns are changed, to allow for better access. The DCS interface upgrade helped simplify things, while still providing all the vital information. “The DCS screens were revamped to enable operators to see the “core” of the acid plant in only two screens,” said Chemetics Sales Manager for Sulfuric
Acid, Herbert Lee. “This means it is easier to keep track of all the critical operating parameters at a quick glance.” One new feature for AP2 is a continuously operating caustic scrubber that increases recovery of SO2, reducing emissions to less than 20 ppm. AP2 will also include a power cogeneration plant, with a nameplate capacity of 20 MW, which is expected to come online in
The prefabrication of the acid towers saved the TFM team time and money.
March. The power produced will be used to reduce the overall power demand from the grid and greatly improve reliability. Chemetics, with their depth of knowledge and cutting edge technology, was brought on board in the early days of the project. As with AP1, Chemetics provided the core detail engineering for the acid plant and supplied key proprietary equipment. “Our project team focused on leveraging proven experience from the first acid plant project and developing new innovations to improve reliability and capital costs for the second plant, which has twice the capacity.” said Songesa. The Chemetics-patented, all-stainless converter featured a modularized design, instead of the conventional “field erection” approach. The converter was shipped to the site in prefabricated modules after being trial fit in the shop, significantly reducing cost and improving the overall quality of the fabrication. “Site assembly was significantly simplified using a small crew compared to the traditional “field erection,” said Lee. “The final quality of the converter is also better as most of the welding is done in a controlled shop environment.” An internal steam superheater and inter-reheat exchanger are located inside the core of the converter to eliminate hot gas ducting between beds 1 and 2 and beds 2 and 3. The acid towers, acid distributors, and strong acid piping incorporated proven Chemetics’ Saramet™ sulfuric acid alloy. To minimize welding on site and avoid the associated quality risk the acid towers were supplied to site completely shop fabricated. The acid distributors feature complete modular bolted assembly and the Saramet acid piping was supplied in prefabricated spools suitable for shipment to site in standard shipping containers, further minimizing installation costs and optimizing schedule. The newest generation of ISO-FLUX™ trough distributors was installed in the acid towers to minimize packing chips fouling while reducing the total number of parts, simplifying installation and maintenance. The sulfur furnace was also completely prefabricated before being shipped to the site. Chemetics’ design features individual combustion air control to each sulfur gun for optimal air-sulfur mixing. This design also requires no internal baffle walls. Chemetics also played vital roles in commissioning and start-up training services throughout the project. TFM currently employs approximately 3,400 people, a number that is not expected to change with the new plant. “We are not planning to hire any additional people to operate the acid plant,” said Wellington, “but rather be more productive at the current manpower level.” Ninety-eight percent of TFM’s employees are DRC Sulfuric Acid Today • Spring/Summer 2016
Cover Story
The Chemetics-designed sulfur furnace was built offsite.
citizens, making the company one of the largest employers in the region.
On the fast track
The quick time frame of the project, along with the location, presented a unique set of obstacles for the team. The fast-paced project, which at $245 million came in below the original budget, took approximately 24 months from feasibility to start up. Commissioning of AP2 was very successful due to a combination of an adaptable and flexible commissioning team made up of FMI, TFM, Chemetics and Hatch employees as well as the robust proven design of AP2 that allowed the TFM operators to easily transition to the new plant. First acid was made in early February and the plant had already exceeded nameplate capacity of 1,400 metric tons per day within less than three weeks. “This was a fast-tracked project that involved coordination of project personnel from several different companies,
The furnace provides optimal air-sulfur mixing with no internal baffle walls.
including Freeport-McMoRan, TFM, Chemetics and Hatch, who were located in very different time zones,” said Songesa. “We had to find ways around that, to avoid slowing down the process.” Several members of the Freeport-McMoRan project team were moved to South Africa to reduce inefficiencies associated with extreme geographical and time zone differences, as well as to ensure purchasing, logistics and shipping issues could be dealt with quickly. Having them closer to the site avoided lag time and helped move the process along. All key project team members also attended frequent design review meetings to ensure all parties were on the same page. Transportation of equipment within the DRC was another challenge. Ground transportation in the DRC has always been tricky. The terrain and climate of the Congo Basin present serious barriers to road and rail construction, making shipping of large, heavy equipment very difficult. These difficulties were overcome by ordering long-
Team members celebrate the first acid production from the new plant.
Sulfuric Acid Today • Spring/Summer 2016
lead equipment quickly and optimizing equipment design to fit within the shipping limitation, taking advantage of modular pieces whenever possible.
Dedicated to environmental, community improvements
At Tenke Fungurume, safe production is the most important factor in the company’s success, and everyone shares responsibility for safety, both in and out of the mine. “TFM is committed to managing the mine in a way that benefits the local community, promotes good governance, respects local culture, minimizes disruption to the ecosystem and supports the evolution of the country toward sound mineral development,” said Songesa. The company has also made significant investments in community development ranging from education and agriculture to healthcare and infrastructure development. Since 2006, TFM has funded a total of $120.4 million in community development projects. Additionally, since the commencement of commercial production, TFM has set aside 0.3 percent of net metal sales revenue to fund the TFM Social Community Fund. Since the commencement of production, contributions committed to the fund have totaled $23.6 million. Both TFM’s direct community
AP2’s stainless steel converter was assembled from prefabricated modules, simplifying installation.
development and TFM Social Community Fund projects are focused on supporting sustainable development of the concession communities by investing primarily in education, healthcare, infrastructure and agriculture. TFM was the proud recipient of two significant awards at the 2015 iPAD DRC Mining & Infrastructure conference in Kinshasa, winning recognition as both Mining Company of the Year and Best Performer in Environmental Management. These just highlight the ongoing commitment the company has made, both to its employees and the region.
Looking to the future
While Tenke is currently producing more copper and cobalt than ever before and serves as a major employer and
support for the entire region, the company refuses to simply rest on its laurels. The addition of the facility’s second sulfuric acid plant should help it reach new heights in the coming years, while also cutting costs. “Production of acid from AP2 allows processing of higher acid-consuming ore, and it is anticipated to provide an improvement to copper and cobalt production due to the certainty of acid supply at an improved operating cost compared to importing acid,” said Wellington. In addition, TFM continues to engage in exploration activities and metallurgical testing to evaluate the potential of the highly prospective minerals district at Tenke Fungurume. According to Songesa, “These analyses are being incorporated in future plans for potential expansions of production capacity, which could exceed 1 billion pounds of copper per year.” q
Tenke Fungurume is one of the largest copper producers in the Democratic Republic of Congo, producing 205,000 metric tons per year.
PAGE 9
Feature
market outlook
Global acid market: changing fundamentals
By: Fiona Boyd, Director, Acuity Commodities
As the first quarter of 2016 commenced, low commodity prices continued to overhang global markets. The most significant impact on the traded sulfuric acid market is lower consumption to support base metals leaching, which has resulted in significant demand destruction in markets such as Chile and the United States. Meanwhile, low crude prices continue to overhang the market, but by-product sulfur production has remained stable because of healthy refinery operating rates. Around 90 percent of sulfur is used to produce sulfuric acid and of the acid produced, around 50 percent is used to support phosphate fertilizer production. It is used as a raw material to process phosphate rock to produce phosphoric acid, a key intermediate in products such as diammonium phosphate (DAP). Last fall, signs of weakness in the phosphate fertilizer sector were beginning to emerge and sulfur prices began to respond accordingly. With limited demand for phosphate fertilizer products in key import markets such as India and Latin America, phosphate producers began to push for lower sulfur prices, particularly in China, the largest consumer of sulfur
on a global basis. In North America, the major domestic benchmark sulfur price, the Tampa quarterly price, settled at a $15/ long ton reduction for the first quarter at $95/long ton delivered. In the first half of February, the outlook turned increasingly bearish and major phosphate producer Mosaic—the largest consumer of sulfur in North America—announced it would curtail phosphate production by up to 400,000 metric tons in the first quarter in response to weaker market conditions. At the time of writing, this and other signals in the global market were leading to speculation of further downward pressure in sulfur prices. A turnaround in the phosphate fertilizer market as the year progresses could see sulfur prices firm, however. If sulfur prices remain under downward pressure, there are implications for the sulfuric acid market. It is already facing challenging market conditions for 2016, mainly because of the aforementioned reduction in demand to support metal leaching. The dip in sulfur prices impacts buyer sentiment and, if prices slide significantly, has the ability to impact levels of sulfurbased production versus purchasing of in-
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1.800.676.4984 acid@corrosionservice.com www.corrosionservice.com
cremental sulfuric acid from the market. This is occurring at a time when production of sulfuric acid traded in the global market is stable, so any further pressure to place volume would be challenging. Production is stable because despite the bearish tone in the base metals market, it has had more of an impact on consumption of sulfuric acid for leaching rather than smelting operations. Smelters are said to be running as close to capacity as possible in order to achieve lower overall unit production costs amid a weak mining sector. This results in stable production of by-product sulfuric acid, which drives global trade and sets prices. In Chile, the world’s largest importer of offshore sulfuric acid, weaker demand for sulfuric acid for copper leaching has resulted in significantly reduced import requirements. As a result, smelter acid producers in Japan and South Korea (historically key suppliers to Chile) have been forced to look for alternative markets to keep product moving. This hasn’t been an easy task, with most smelter acid moving at negative netback prices at the time of writing. Increased demand in markets such as Vietnam and Thailand has provided some relief, but as the year progresses, the PASAR smelter in the Philippines is expected to increase production levels as capacity is expanded, resulting in the need to market additional tonnage. Therefore, demand in southeast Asia will be key in keeping the region balanced. China will play a role in absorbing supply, but this could result in curtailing of sulfur-based acid production if acid prices move low enough, thereby exacerbating conditions in the sulfur market if further demand destruction is realized. Looking ahead, Chile’s import needs could see a rebound if conditions in the copper sector improve, but a retreat to historical levels is not expected given a longstanding forecast for declining import needs. The decline is being driven by lower overall consumption requirements in addition to increased domestic production. Peru is the largest supplier to Chile, supplying around one million metric tons/year to the country, but its excess sulfuric acid levels could contract if leaching projects in the region progress. The two most likely—Tia Maria and Macobre—have the potential to consume up to a combined 800,000 metric tons/year of sulfuric acid, reducing its export availability accordingly. This could help Asian suppliers increase export volumes to Chile in the long-term. Outside of Asia, Europe is another key exporter of offshore sulfuric acid. The majority of acid is delivered to Mo-
rocco, Brazil and the United States. At the time of writing, European suppliers were comfortable but market participants are closely watching to see if major phosphate producer OCP in Morocco curtails its production as Mosaic in the United States announced. If it does, this is likely to result in lower demand for imported sulfuric acid. Planned smelter maintenance could counterbalance any dip in demand from Morocco, however. Looking to 2017, a shift in European trade could be seen if additional sulfurbased sulfuric acid production by Sherritt in Cuba ramps up as planned. Its Moa nickel leach facility is expected to commence operations of additional sulfuric acid production in the third quarter 2016. Once running at optimal utilization, this could back out up to 400,000 metric tons/ year of offshore acid imports. This acid is currently supplied mainly from Europe, so similarly to how suppliers in Asia are currently dealing with lower demand in Chile, European suppliers will be forced to look to alternative markets to place product. Some market players are making strategic moves to deal with a shift in tradeflows. For example, sulfuric acid producer and trader Glencore, which has smelter production capacity globally including in Asia and Europe, is investing in additional import ability in the United States. It is understood new tanks will be operational in Savannah, Ga., by the end of 2016. This will represent Glencore’s second import location in the United States following tanks going into service in Houston, Texas in the fourth quarter 2014. The import ability gives Glencore options for managing its global sulfuric acid portfolio amid shifting market fundamentals. In summary, the key factors to watch for the remainder of 2016 are the performance of the phosphate fertilizer sector and the subsequent impact on the sulfur and sulfuric acid markets. The health of the base metals sector is also important, both in terms of a rebound in demand for leaching and production of smelter acid. Further ahead, changing fundamentals including a shift in tradeflows in Asia, Europe and Chile/Peru will influence the performance of the global sulfuric acid market. Acuity Commodities provides insight into the sulfur and sulfuric acid markets through price assessments, data and supporting analysis. The newly-formed company is currently offering North Americanfocused services, but will be adding global content as the year progresses. Please visit www.acuitycommodities.com for detailed information. q Sulfuric Acid Today • Spring/Summer 2016
Feature
Solutions for common problems in sulfur spraying (8 lpm) to reduce the flow rate. Note the streaky spray pattern, condensed coverage and larger droplets at the lower pressure as compared to the upper picture. When comparing the two photos of the FloMax air atomizing nozzles, the change is more subtle and no visual difference can be detected. The performance is more consistent even at the lower flow rate and pressure.
Problem #1: Achieving proper atomization Solution: Understand drop size The reason atomization is so important in sulfur burning is that it has a direct impact on the rate of heat transfer between the combustion gas and the sulfur. Spray nozzles used on sulfur guns are often selected based on flow rate. A better approach is to select spray nozzles based on drop size and performance. Here’s why: • A single droplet with a diameter of 500 microns has roughly the same volume as 121 droplets with diameters of 100 microns. • However, the surface area coverage of the smaller droplets is approximately 484 percent larger. • This increased surface area increases the rate of heat transfer. • The smaller droplets decrease the likelihood of sulfur impingement on furnace walls and baffles and the chance of sulfur carryover. Optimizing sulfur spraying is dependent on many variables including atomization, drop size, residence time, gun placement and operating conditions in the furnace. Computational Fluid Dynamics (CFD) modeling is a powerful tool that can determine the optimal drop size for full evaporation and complete vaporization prior to installation to minimize production disruptions. In addition to ensuring proper atomization will be achieved, CFD can also determine the best placement for the guns to avoid sulfur wall contact and carryover to downstream equipment.
Problem #2: Maintaining consistent spray performance Solutions: Use nozzles with a high turndown ratio or consider air atomizing nozzles Another common problem challenging sulfur producers is maintaining consistent perforPAGE 12
Problem #3: Plugged nozzles
Fig. 1: CFD model shows the difference in wall impingement when using hydraulic nozzles (top) and air atomizing nozzles (bottom).
Fig. 2: The difference between hydraulic nozzles and air-atomizing nozzles under different levels of pressure is easy to see.
mance over a wide operating range. Spray performance needs to be consistent during start-up, low flow operation and peak flow operation. Pressure is changed to obtain different flow rates. However, when pressure is changed, spray performance changes as well. For example, when using hydraulic nozzles, a decrease in pressure results in an increase in drop size and contraction of the spray pattern and coverage, and leads to incomplete evaporation or vaporization. There are a few options for solving this problem:
• •
•
Use nozzles with a high turndown ratio. Use multiple sulfur guns and control flow rate by turning guns on or off and/ or adjusting the operating pressure of the individual nozzles on the guns. Consider changing from hydraulic to air atomizing nozzles. While pressure adjustments still affect performance, the changes are more subtle. This is because the atomizing air pressure can be adjusted along with the feed pressure in order to help
maintain more consistent performance across a wider range of flow rates. Refer to the four images in Fig. 2. The upper left image shows a BA WhirlJet® hydraulic nozzle spraying at 5 gpm (19 lpm) and the upper right shows a FloMax® air atomizing nozzle spraying at 5 gpm (19 lpm) which represents normal operating conditions. As production decreases, there is a need to decrease the flow rate in the furnace which is sometimes accomplished by lowering pressure. The image on the lower left shows the same BA hydraulic nozzle lowered to spraying 2 gpm
Solutions: Evaluate air atomizing nozzles, hydraulic nozzles with clean-out ports and/or purge with steam or air Plugged nozzles are another frequent and disruptive problem, not unique to sulfur spraying. Whenever there is a set orifice size, there is potential for something to build up or lodge within that orifice. Installing properly sized strainers upstream of the nozzle is important and can often eliminate plugging. Plugging can also be caused by contaminants, such as carsul, in the sulfur, or molten sulfur may solidify inside the nozzle when operating at lower flow rates or when sulfur guns are removed. The solidification is caused by the loss of velocity that is present when operating at higher pressures. Possible remedies to these plugging problems are to use a sulfur gun that has a cleanout port, or purge with steam or air. Another approach is to use air-atomizing nozzles. The atomizing air pressure continually moves any low flow sulfur through the gun and minimizes plugging. Simply using hydraulic nozzles with larger orifices can result in performance problems as larger orifices require less pressure drop. The outcome is larger droplets and turndown is limited. For more information on optimizing sulfur spraying, visit www.spray.com or contact your local Spraying Systems Co. representative. In the U.S. and Canada, call (800) 95-SPRAY. In other regions, call (630) 665-5000. q
Sulfuric Acid Today • Spring/Summer 2016
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Feature
Dry and wet precipitators–the yin/yang of off-gas acid production By: Hardik Shah, Applications Engineer, Southern Environmental, Inc.
In non-ferrous metals plants, materials such as molybdenum, copper, zinc and lead are separated from the ore through a roasting or smelting process. The ore contains sulfur impurities along with other components. The sulfur is used downstream to manufacture concentrated sulfuric acid. For example, in a molybdenum roaster application, the molybdenum sulfide (MOS2) ore is converted to MOO3. During this conversion, the sulfur is liberated through the off-gas in the form of SO2 and SO3 along with other solid particulate. The SO2 is used to produce concentrated sulfuric acid after the off-gas is cleaned and made “SO2 rich.” In order to make the off-gas “SO2 rich” it is passed through a series of pollution control and process equipment, referred to as the gas cleaning system. The gas cleaning system removes solid particulate, SO3 and moisture. The off-gas exiting from the gas cleaning system is sent to a sulfuric acid production plant. The gas cleaning system typically consists of the equipment shown in Fig 1. Each component of this gas cleaning system has a specific purpose in order to make the off-gas “SO2 rich.” All of the components have to function in harmony to ensure maximum removal efficiency. The spray cooler cools the off-gas to approximately 600 degrees F. The cyclone and the dry electrostatic precipitator (dry ESP) are used to capture solid particulate and recover raw material, which is usually recycled back to the roaster for further recovery. The saturator and the gas cooler saturate and subcool the off-gas to remove moisture. During this saturation and subcooling process, the SO3 vapor is converted to H2SO4 mist. The wet electrostatic precipitator (WESP) captures the H2SO4 mist and the second-stage gas cooler sub-cools the gas further. The off-gas exiting from the second-stage gas cooler is “SO2 rich” and is sent downstream for sulfuric acid production. It is important to note that the H2SO4 mist is removed from the off-gas, not only to make it “SO2 rich,” but also to prevent corrosion in the sulfuric acid production plant. As noted in Fig. 1, the dry ESP performance has a significant PAGE 14
Fig. 1: Typical gas cleaning process.
Fig. 2: Dry ESP (left) and wet ESP (right).
impact on the performance of the downstream components. An underperforming dry ESP will mean higher carry-over of solid particulate and otherwise recoverable material to the saturator and WESP. This valuable particulate will now be transferred from the off-gas into the weak acid solution or other liquid, and the recovery of marketable material becomes almost economically impossible. In addition to the loss of marketable material, the H2SO4 mist removal efficiency in the WESP is significantly compromised. Increasing unnecessary solid particulate loading that is carried over from an underperforming dry ESP reduces the effectiveness of the WESP to capture H2SO4, thereby negatively impacting the downstream production of concentrated sulfuric acid. Both dry and wet ESPs work on the same principle whereby solid particulate and H2SO4 mist
are charged and collected under the influence of an electric field. In order to maximize removal efficiency within the boundaries of this equipment, the highest possible values for secondary voltage (kV) and secondary current (mA) are employed. The inlet particulate loading, in the case of the WESP, will be a total of the solid particulate plus H2SO4 mist. This total inlet loading is one of the parameters that dictate the maximum attainable values of secondary voltage and current. A higher particulate loading will directly result in a lower secondary current. Therefore, an underperforming dry ESP could have a severe detrimental impact on the WESP’s performance in this application. Fundamentally, the higher the recovery percentages the dry ESP can attain, the better a given WESP will perform downstream in the off gas process. Additionally, given any particular WESP design, it should be noted
that it is a constant efficiency device, therefore increases in unwanted particulate from the dry ESP will cause increases in downstream particulate loading to the sulfuric acid production plant. A reduction in WESP performance is often attributed to design or maintenance problems with the WESP. But frequently, the problem begins upstream at the dry ESP. Whenever a WESP suffers from a sudden and unexpected drop in performance, evaluating a variety of variables including the operational characteristics of the upstream equipment is recommended. The dry ESP electrical characteristics are a good place to start, to ensure the root cause is not upstream of the WESP. When the performance of a WESP is degraded, the solid particulate and H2SO4 mist loading to the downstream acid plant also increases. This increase in loading downstream of the WESP can
cause a variety of maintenance issues ranging from build-up on the process fan blades to corrosion in various areas. The build-up on the fan blades often unbalances the fan, forcing either a reduction in production or worse, complete shutdown. Therefore, it is critical to monitor and maintain the WESP performance on a continuous basis. Since the performance of the WESP is affected by the performance of the upstream gas cleaning components, especially the dry ESP, it is critical to always monitor, evaluate and maintain the gas cleaning equipment as a complete system. Once it has been established that the performance of the dry and wet ESPs are degraded due to aged components or an increase in process flow parameters, a modification to the system will be necessary. There are numerous ways to determine the most economical way to achieve performance improvements. Dry ESP technology has seen many significant technological advancements in the last 30 years. Advancements such as use of high frequency power supplies and wide plate spacing have resulted in relatively small dry ESPs achieving extremely high collection efficiencies. These technology advancements can be economically retrofitted into the existing ESP casing. Some upgrade concepts include performing partial or complete upgrades using prefabricated components to reduce process down time and field construction costs. There have also been advancements with regard to materials of construction. The use of fiberglass reinforced plastic (FRP) and polypropylene fabrictype collecting electrodes provides a viable option over lead when replacing or upgrading WESPs. In summary, economical upgrade strategies can be devised in order to ensure continuous and reliable operation of both dry and wet ESPs, but those upgrades need to be evaluated in the context of the whole system rather than individual component evaluation. For more information, please contact Michael Johnson of Southern Environmental, Inc. at (850) 944-4475 or mjohnson@ sei-group.com or visit www. southernenvironmental.com. q
Sulfuric Acid Today • Spring/Summer 2016
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Feature
Fiber bed mist eliminator refresher: theoretical fundamentals vs. real world
By: Steve Ziebold, Principal Consultant, and Douglas Azwell, Senior Consultant of MECS, Inc. and Evan Uchaker, PHD Research Engineer of DuPont Clean Technologies
This article provides insight on how mist particles are captured in diffusion fiber beds and what is required to assure sustained state-of-the-art fiber bed mist eliminator performance. The first part of this article briefly discusses the theory of mist capture mechanisms, and the second part describes real world design and quality control. There are three main mist collection mechanisms utilized by high efficiency diffusion fiber bed mist eliminators, as illustrated in Fig. 1. They are: Impaction, Interception and Brownian Diffusion.
motion (also known as particle diffusivity) and the more likely an incident particle will collide with a fiber and stick (collect) by weak Van der Waals forces during transit through the fiber bed. For describing mist capture by diffusion, the modified Stokes-Einstein equation for diffusivity is used:
Impaction
The inertial impaction mechanism collects a mist particle in a gas stream when it impacts a fiber. A particle has volume and density. The bigger the particle, the more mass it contains. If the gas velocity is fast enough, the mass of the particle moving within the gas will have adequate momentum to cause it to impact a fiber and stick by weak Van der Waals forces rather than continue following the gas streamline around it. The larger the particle diameter, the more momentum it has, and the easier it is for capture by the impaction mechanism. From a theoretical view, it is true that particles can be collected by impaction if momentum, as represented by the Stokes number, overcomes the drag force in a gas stream where no eddies are present downstream of the collecting fiber. The Stokes number is represented as:
Where dp = mist diameter, ρp = mist density, V = mist velocity, μg= gas viscosity and df = fiber diameter. Note “V” is the interstitial velocity, which is the velocity between the fibers that are present within the matrix of the fiber bed, so it must be corrected for the void space of the fiber bed in the fully wetted, steady state condition during operation to accurately calculate the Stokes number. Thus, the Stokes number is difficult to derive because it requires an understanding of how collected mist is distributed on individual fibers within the fiber bed. Further complicating this is that collecting fibers have a nominal fiber size distribution, so the Stokes number will vary as a function of the diameter of the fiber that the incident particle collides with. The gas drag force is represented as:
Where ρg = gas density, v = speed of the mist particle relative to the gas, CD = gas drag coefficient and A = cross sectional area of Sulfuric Acid Today • Spring/Summer 2016
Fig 1: Illustration of mist capture mechanisms.
the collecting fiber. As such, the formulas described earlier can give a crude approximation of collection efficiency due to impaction. However, flow streams in a fiber bed are much more complicated than shown in Fig. 1 due to the complexity of the fiber matrix in the actual fiber bed and how coalesced mist is retained and/or migrates within the collecting fibers.
Interception
The second mist collection mechanism is direct interception. This means the mist particle is intercepted from the gas stream if it cannot squeeze between two fibers (or if it touches the tangent of a fiber as it passes within the barrier layer between the freely moving gas and the fiber surface, sticking to the fiber by means of weak Van der Waals forces). Consider a particle 1.0 micron in diameter that follows a gas streamline passing within 0.5 micron of a fiber. The particle will touch the fiber and be collected by interception. This mechanism is similar
to the action of a mesh filter or sieve.
Brownian diffusion
Impaction and interception are the primary collection methods employed by devices that are designed to remove larger mists from a gas stream. In order to remove sub-micron mist particles out of a gas stream, however, a third mist capture mechanism called “Brownian Motion” or “Brownian Diffusion” must be utilized. All molecules in a gas stream are in constant, random, thermally induced motion. This molecular motion causes collisions between gas molecules and suspended mist particles. As mist particles are bumped by surrounding molecules of gas, the momentum exchange causes a randomly oriented “zigzag” effect on mist particle motion. Since these collisions have little energy, this mechanism is effective for only very small particles (typically less than 1 micron) and decreases in intensity as the particle size increases. Therefore, the smaller the particle, the greater its random
Where kB = Boltzmann constant, T = temperature, C = Cunningham slip correction factor, μg= dynamic gas viscosity, and dp = mist particle diameter The Stokes-Einstein equation is the theoretical diffusivity of a particle and predicts only the intensity of the random motion a particle exhibits. It should not be inferred that this equation predicts mist collection, which would be true if a fiber bed consisted of a single fiber and the flow stream around the fiber were a “textbook” flow pattern, as shown in Fig. 1. In reality, the flow of process gas through a fiber bed is much more complex and the path the process gas takes through a fiber bed is torturous. (A single fiber bed for some sulfuric applications contains a length of glass fiber equal to the distance between the Earth and the Moon). Additionally, many other factors contribute to determining mist capture, including the amount of collected mist retained within the fiber bed at steady state, mist residence time as it passes through collecting fibers, mist properties, fiber bed uniformity and general fiber bed properties to name a few. Many academia-based fiber bed mist elimination research studies have been performed in an effort to evaluate mist collection using very small scale filters, often in a dry operating state with very low inlet mist levels. These studies often assume homogeneous liquid distribution to simplify the prediction of mist collection when the filter is saturated. In reality, large diffusion fiber beds in sulfuric acid plant service are not homogeneously saturated, which adds another level of complexity in predicting performance. Therefore, technology provider experience, based on development of semiempirical models supported by rigorous field measurements, is critical to accurate prediction of diffusion fiber bed collection efficiency and operating pressure drop. The MECS sulfuric acid field mist sampling database has over 50 years of field acid mist measurements in support of Brink® fiber bed design models.
Real world design & quality control Fig 2: Example of a fiber bed thermographic image.
Diffusion fiber bed mist eliminators used in sulfuric acid plants are very large compared to, for example, cartridge filters. One of the product attributes that is very important to PAGE 17
Feature
control is fiber bed packing uniformity (or homogeneity). As a means of obtaining a visual “qualitative” perspective of homogeneity, MECS developed a thermographic imaging technique in the 1970s. The test is performed by blowing a controlled flow rate of warm air through the fiber bed while using a forward looking infrared radiometer (FLIR) system to detect temperature variations (hot and cold spots) on the downstream side of the fiber bed as a function of position. Thermographs, however, are only a qualitative indication to determining whether there are fiber bed non-uniformities. To be effective, they must be performed at close range to the element surface using a small temperature gradient with high color contrast. Fig. 2 is a thermographic image demonstrating a significant “hot spot” observed on a parallel packed fiber bed at a weak spot in the packing. This is likely where parallel glass fiber rovings happened to line up when the element was hand wrapped. The only sure way to quantify fiber bed uniformity is with velocity profiles using a velometer. A velometer also is shown in the Fig. 2 thermograph image directly measuring actual gas velocity at the hot spot. Complete velometry measurements are often carried out by MECS to allow for continuous improvement of Brink® fiber beds as these measurements relate to variance of raw material supplies and fiber bed manufacturing process. With the same parallel wrapped element shown in Fig. 2, a velocity profile was taken along the entire length of the element that crossed the “hot spot” (Fig. 3). Measurements indicated gas velocities over some areas were very high (3990 fpm, 340 fpm and 370 fpm) compared to the average over the rest of the length of the fiber bed (~ 50+ fpm). High velocity spikes can significantly reduce theoretical capture of mist particles discussed earlier. When this type of element is placed in service, velocity spikes contribute to poor mist eliminator performance in two ways: penetration of submicron mist particles due to reduced contact time with collecting fibers, and formation of re-entrainment (large particle regeneration) due to increased shear of collected mist draining from the downstream exit gas surface of the fiber bed. Another routine quality control mea-
Fig 3: Example of a fiber bed velocity profile. PAGE 18
surement is dry element pressure drop taken at a controlled gas flow rate, which is a means of determining the fiber bed dry gas flow resistance. This QC measurement is a good quality check to ensure all elements have the same individual gas flows when placed in service, which ensures all elements work equally together. An imbalance in gas flow between elements will result in less than ideal performance. If one looks at the difference between fiber beds manufactured with identical dry gas flow resistance, one that is wrapped with computer controlled placement versus another that is hand packed, the difference is apparent. The hand wound element will contain velocity spikes as described earlier, while a properly packed fiber bed that was manufactured with the computer controlled placement technique will not. Thus, not only is it important to select a fiber bed with matched dry bed flow resistances, it is also important to manufacture the fiber bed with uniform packing density (high homogeneity) to assure best-in-class performance is achieved for protection of downstream equipment. Also, even if angle and parallel wrapped roving fiber beds are made to the same dry bed resistance, this does not result in the same operating pressure drop in process service under identical inlet conditions. MECS developed the angle roving wrapped diffusion fiber bed mist eliminator in the 1970s as part of an extensive research program using sulfuric acid mist. It was discovered that equilibrium retention of collected mist (and steady state saturated operating pressure drop) is reduced by wrapping glass fiber roving at an angle instead of a parallel orientation (relative to the ground or support tubesheet). With less liquid retained in the fiber bed, this resulted in lower operating pressure drop, lower re-entrainment and higher overall collection efficiency of submicron mist. For many applications, even those outside sulfuric acid, angle wrapped roving diffusion fiber beds typically provide up to 20 percent more gas throughput compared to bulk packed fiber beds for the same operating pressure drop and collection efficiency (or equivalent reduction in pressure drop for the same number of elements). This is due to the fact that a fiber bed that is packed with
Fig. 4: Demonstration of effective gas/liquid separation using a drainage layer.
computer controlled precision with the fiber at an angle is more uniform than a fiber bed that is packed by hand. Additionally, the angle wrapped interlocking roving is a more stable and uniform pack when compared to parallel hand wrapped roving, bulk packed or donutstyle fiber beds. Mullins et. al. (Mullins, 2003) clearly demonstrates that fibers oriented at an angle relative to grade show a marked tendency to allow liquid droplets to flow when the mass of the liquid droplets on the fiber allows them to overcome adhesive forces. This paper supports MECS’s research and development findings that a fiber bed with angle wrapping operates with lower liquid retention and lower operating pressure drop. Another innovation developed with the angle wrapped diffusion fiber bed is the bi-component fiber bed design, which virtually eliminates particle regeneration (reentrainment). A drainage layer comprised of proprietary coarse fiber media is oriented downstream of the collecting layer. Even with the most uniform fiber bed mist eliminator, if only collecting fibers are used, liquid films will easily form between fibers among the interstitial spaces. When these films break, droplets can be produced that add to emissions from the fiber bed. More importantly, if these films form on the gas discharge side of the fiber bed, the result will be particle regeneration of some portion of the collected mist back into the gas stream. The result of reentrainment is normally mist particles a few microns in diameter or larger. The quantity of re-entrainment depends on several parameters,
especially inlet mist loading, bed velocity and exit velocity. MECS bi-component fiber bed offers a means of reducing the amount of reentrainment by providing a downstream gasliquid disengagement zone to allow collected liquid to drain away without further interaction with the gas phase. Re-entrainment control is very important to sulfuric acid customers to minimize downstream corrosion of ductwork, to protect catalyst and prevent high stack emissions. Unfortunately, since re-entrainment is difficult to measure, often clients will use fiber beds without a drain layer and realize only years later the effects of downstream equipment corrosion. Additionally, not all re-entrainment control materials are created equal. MECS experimented with many different materials as part of its research and development program in the 1980s to determine the proper orientation, fiber size and density for this material to achieve proper re-entrainment protection. To illustrate the effectiveness of using a bi-component fiber bed design, two portions of a drain layer were removed from a standing research element shown on the left side of Fig. 4. Gas was pushed through the fiber bed from the inside to outside. When a water solution containing a small amount of soap was injected into the inside of the element, bubble formation was observed on the outside of the element coming from the two areas where the drain layer was removed. This illustrates the effectiveness of the drain layer under flow conditions in reducing formation of bubbles
Fig. 5: Brink® XP™ Mist Eliminators. Sulfuric Acid Today • Spring/Summer 2016
Recent diffusion fiber bed innovations
As a result of MECS’ continuous improvement through research and development, there have been recent significant advancements in Brink® diffusion fiber bed technology with the introduction of the eXTra Performance XP™ mist eliminator and AutoDrain™. Following a decade of research and development along with over 10 years of acid plant experience, MECS now designs and builds the XP for all acid towers (Fig. 5). For typical tower acid mist loadings, the XP offers the lowest pressure drop available in one-to-one match-ups when compared to other elements. Due to its patented uniform collecting fiber arrangement, XP operating pressure drop is up to 50 percent less compared to the original HE style hand packed fiber bed mist eliminator invented by Dr. Joe Brink in the 1950s. Thus, the new XP fiber bed technology can provide sulfuric acid plant installations with significantly lower operating pressure drop or fewer elements compared to conventional designs. Beginning with the original Brink® hanging HE style fiber bed mist eliminator, element seal legs have been used since the 1950s. Another recently patented and demonstrated innovation is the Brink® AutoDrain™ for hanging style diffusion fiber bed mist eliminators. A novel arrangement integrated into the bottom of the element allows for collected mist to drain on the upstream gas side of the element, thus eliminating the need for seal legs.
Feature
and films at the gas discharge surface of a fiber bed and how significant performance improvement can be realized in sulfuric acid plant service using bi-component fiber beds.
As shown in Fig. 6, seal legs from hanging fiber beds routed to open distribution troughs result in a very congested space making maintenance very difficult. Fig. 7 shows the area under elements that use AutoDrain™. It is apparent the working space around the distributor is significantly more open for maintenance. In addition, using AutoDrain™ saves significant expense by eliminating element seal legs, plant downtime, and labor required for seal leg installation.
Wrap-Up
Providing outstanding diffusion fiber bed mist eliminators is not as simple as just using a theory-driven approach to design. In addition to theory, it is important to use field experience in actual sulfuric acid service to provide a product that will consistently meet or exceed industry needs. Since 1958, MECS, Inc., has been the pioneer in development, and improvement of successful Brink® Mist Eliminators. Along the way, MECS has improved semi-empirical design models upon which its invention is based. Beyond theory, in order to attain predictable, reliable performance, it is important to assure raw materials are always within specification and elements are made with consistent uniformity using the latest in manufacturing techniques. MECS QC relies on various methodologies to measure fiber bed properties, including but not limited to: velocity profiles, matched flow resistances, and dry bed manufacturing pressure drop measurements. Finally, continued investment in research and development programs help create new inventions and innovations that bring more value to clients. In conclusion, world-class mist eliminator performance in sulfuric acid service is a result of using theoretically sound, semi-empirical design models that have been field-verified over many years. Optimum performance is maintained by providing proper designs, unwavering attention to manufacturing techniques, quality control, continuous improvement and customer support. For more information, please visit www. mecs.com. q References Dzyaloshinskii,
I.
E.;
Lifshitz,
E.
M.;
Pitaevskii, Lev P. (1961). “General theory of van der waals’ forces,” Soviet Physics
Fig. 6: Element seal legs routed to distributor troughs.
Uspekhi 4 (2): 153. Mullin, Benjamin J.; Agranovski, Roger D.; Ho, Chi M., “Effect of Fiber Orientation on Fiber wetting processes,” Journal of Collid and Interface Science, July 2003, pp. 449-458. Einstein,
Albert,
“Investigations
on
the
Theory of the Brownian Movement,” 1905, BN Publishing, 2011 edition, pp. 10-12. Mills, Anthony, “Heat and Mass Transfer,” CRC Press, 1995, pp. 899-900. Cheng,
Yung-Sung;
Allen,
Michael
D.;
Gallegos, David P.; Yeh, Hsu-Chi; Peterson, Kristin, “Drag Force and Slip Correction of
Fig. 7: More space under elements using AutoDrain. Sulfuric Acid Today • Spring/Summer 2016
Aggregate Particles,” Aerosol Science and Technology, 1988, pp. 199-214.
PAGE 19
Feature
Aggressive corrosion and demanding conditions need aggressive solutions By: Luis F. Granes and John E. Davis, Sauereisen
Sulfur pits are a common sight at oil refineries, sulfuric acid plants, petrochemical plants, fertilizer plants and chemical facilities. Sulfur is melted in the pits to prepare it for manufacturing sulfuric acid or other by-products, as an aggregate for fertilizer products or simply for sale on its own. No matter what the reason for the sulfur pit, it needs a protective lining to make sure the sulfur, as well as the gases generated at the pit, do not attack and destroy the containment structure. Most sulfur pits are made of concrete, although steel is another option. The gases generated at a sulfur pit, when mixed with the humidity in the environment, will condense into sulfuric acid (H2SO4), which is very harmful to unprotected concrete or steel. When burned and exposed to oxygen, sulfur creates sulfur dioxide (SO2), a yellowish, viscous liquid that is soluble in water at all concentrations. It can also come in the form of a toxic gas. The classic protective lining installed at a sulfur pit uses a high-temperature resistant membrane, acid resistant brick and an acid resistant mortar. Duro-Type III brick is the best for any acid immersion conditions, due to its low porosity and low water absorption. The mortar needs to both be acid resistant and have the ability to resist high temperatures that are common in sulfur pits. Potassium silicate-based mortars are the best in this situation. There are also gunite versions of the potassium silicate mortar, which make the application process much faster and less expensive than the brick lining system. Either can be an effective solution. In some cases, the selection of a calcium aluminate mortar/gunite system is dependent on the pH level in the pit. A commonly used practice is the addition of limestone and other alkaline products to curb the pH of the pit and assist with controlling the acidity as a means to protect the concrete/steel surface. There are disadvantages to this system, however. In these cases, because the pH of the pit has been raised above 7 on the pH scale, the use of potassium silicate products are not recommended, because the potassium silicate is resistant to exposure to pH from 0 to 7. But when the pH is higher than 7, the potassium silicate is damaged and the lining will fail prematurely. Another option is a calcium aluminate mortar/gunite product. Calcium aluminate will resist any exposure to pH from 3.5 up to 13, which makes it the preferred solution to replace potassium silicate as a protective lining. Why not use sodium silicate, which was the original solution so many years ago? Sodium silicate, when exposed to sulfuric acid, will react and create a globular salt, which has the tendency to keep growing inside the matrix of the sodium PAGE 20
Sulfur pit after one year of continuous service. Effects from an improperly lined sulfur pit.
Gunite lining no. 35 over high temperature membrane no. 89.
Spray-applied membrane no. 89.
Sulfur pit restored completely with Sauereisen no. 89 & no. 35 gunite. Potassium silicate lining no. 54-gunite.
Potassium silicate lining showing signs of deterioration due to higher levels of pH in a sulfur pit.
silicate exposed to the sulfuric acid. When the salt grows, it generates cracks in the lining. The lining will spall and fail, exposing the surface to attack by sulfur on one side and acidic condensates on the other. Sodium silicates have been surpassed as a mortar for acidic applications since the late 1940s early 1950s, when potassium silicates became the preferred mortar for this application. Although potassium silicate is also a silicate, and therefore reacts with sulfuric acid to form a salt, it is a stable salt that doesn’t grow, and therefore will not damage the lining. Pittsburgh-based Sauereisen is known as the source for references and engineered solutions for the restoration and corrosion prevention of sulfur pits. With 117 years of experience, this third-generation com-
pany has grown into one of the best-known corrosion-resistant materials manufacturers in the world, with a product portfolio that includes a complete line of organic and inorganic corrosion-resistant materials for new and rehabilitation applications. A customer in Israel had experienced repeated problems maintaining several large sulfur pits. Restoration attempts included removing all the deteriorated concrete, placing forms and pouring new portland-based concrete. This was a large and expensive undertaking requiring extended periods of downtime. More importantly, the solution would often last for only one or two years, before it needed to be repeated. They finally contacted Israel Paycher, owner of Sealtec Construction Co. Ltd of Israel and a Sauereisen representative, for a long-term solution for rehabilitation and corrosion protection. Paycher contacted Luis Granes, the Sauereisen International Sales Manager for Israel, to come up with a viable solution to the corrosion issues at this sulfuric acid facility. After taking into consideration maximum service temperatures, exterior climate, humidity, structural components and pH levels, Granes recommended a dual lining system of Sauereisen Membrane No. 89 and Sauereisen Gunite Lining No. 35 castable, due to their excellent performance in such adverse, corrosive and demanding conditions. The recommended dual lining system included a high temperature single component, asphaltic membrane for a corrosion resistant monolithic lining at 125 mils (1/8inch thickness). No. 89 is easily applied by airless spray equipment, and provides a second layer of defense for penetration of gasses and liquids to the substrate. This flexible coating is resistant to acids, alkalis and salts associated with flue gas environments and substrate movement from temperature changes or other causes. It also maintains excellent elasticity and adhesion to both concrete and steel substrates over a temperature range of 60-300 degrees F (53-149 degrees C). Sauereisen chemical-resistant castable no. 35 is a gunite-grade, hydraulicallysetting, calcium-aluminate cement. No. 35 is recommended for protection of concrete and steel surfaces from high temperatures, thermal shock, abrasion and chemical attack by mild acids or alkalies. It can eliminate costly acid-brick linings and is equally effective for new construction or rehabilitation projects. This chemicalresistant lining resists alkalis over a pH range of 3.5 to 12.0 and withstands temperatures up to 2100 degrees F (1149 degrees C). No. 35 has excellent thermal shock resistance, develops high strength quickly with low shrinkage and is non-corrosive in direct contact with concrete, iron and steel. Continued on page 21
Sulfuric Acid Today • Spring/Summer 2016
By: Andres Mahecha-Botero, Brad Morrison, Brian Ferris, Hongtao Lu, J.P. Sandhu, C. Guy Cooper and Nestor Chan, NORAM Engineering and Constructors Ltd.
Vancouver-based NORAM Engineering and Constructors Limited worked with a client located in southern California to develop a project execution strategy to modernize a sulfuric acid plant. The plant had a number of pieces of equipment approaching end of life and suffered from some technical issues. The plant, a 450 STPD (as 100 percent H2SO4) sulfuric acid regeneration plant, utilizes single absorption technology followed by a tail-gas scrubber. Gas handling and conversion equipment was replaced in three separate shutdowns over a period of over five years (the final step of the project was completed in November 2015). The plant required the replacement/ upgrade of a four-bed catalytic converter, three gas-to-gas heat exchangers, a gas preheater, a preheater gas-to-gas heat exchanger, most of the gas ducting, acid tower packing, instrumentation, SO2 con-
3-D model of the upgrade strategy for steps 1 and 2.
version catalyst, as well as other ancillary equipment. Essentially all the gas handling equipment was replaced by modern equipment designs that provide higher reliability, lower pressure drop and lower SO2 emissions. This paper focuses on the results of the most recent project step.
Upgrade strategy Defining the scope and schedule of a
major plant upgrade was a complex task. Several factors were taken into consideration, including budgetary constraints, turnaround planning, duration of plant shutdown, lost production, technical risk, mechanical conditions of existing equipment, space availability, permitting, logis-
tic considerations and the time required for fabrication and installation of major equipment. The plant upgrade strategy was developed to replace the equipment that was in the worst mechanical conditions. The following was considered as the basis for the upgrade: 1. New equipment to be fabricated utilizing better materials than existing: a. Gas handling equipment was built with stainless steel alloys such as SS 304H, which provide higher corrosion resistance than carbon steel.
b. Replacement acid tower packing was made of slip cast ceramic, which is mechanically stronger than conventional packing. 2. New equipment to be safer and more ergonomic than existing: a. Utilized improved design, reducing the chances of developing leaks. b. When possible, due to permitting issues, the new equipment allowed for better access. 3. New equipment to have lower pressure drop, thus saving electrical consumption of the main blower:
3-D model of the upgrade strategy for step 3.
Continued from page 20
Also, no. 35 is safe to use and does not emit toxic or hazardous fumes or odors during mixing, application or setting. Visual inspections were done on sulfur pit no. 10 over the next few years, which showed the pit to be in good condition. When the customer’s maintenance personnel opened pit no. 10 for inspection and maintenance five years after Sealtec restored it using Sauereisen no. 89 and no. 35 dual protective lining system, they were pleasantly surprised by what they found. The pit was in excellent condition. After the inspection was complete, the pit showed no damages or deterioration, a far cry from the normal rehabilitation needed every 1-2 years with previous materials. The only problem to be found was a crack in the floor, which, according to Paycher, was never protected. The facility is currently setting up to fix this problem, again employing Sauereisen products. This plant has been using Sauereisen materials for the last 10 years in other production areas
Sulfuric Acid Today • Spring/Summer 2016
of the plant without a single complaint or failure. Currently the facility is constructing a new, larger sulfur pit and plans to institute a corrosion-preventative program. After construction, the pit will be lined with the Sauereisen dual-lining system that was used in the rehabilitation earlier, before placing the pit into service. Sauereisen’s 117 years of experience in corrosion control is working for customers. The company maintains a global presence with a network of technical sales representatives throughout the world, and with manufacturing and warehouse facilities located in the United States, Europe, the Pacific Rim and Latin America providing worldwide product distribution. Sauereisen remains dedicated to solving problems requiring specialty materials with expertise in infrastructure restoration and corrosion prevention. For more information, please visit www.sauereisen.com. q
NORAM Hot Heat Exchanger NORAM Preheat Heat Exchanger
Ducting
NORAM Cold Heat Exchanger
Steps 1 and 2 involved replacement of several key pieces of equipment. PAGE 21
Feature
Modernization of a sulfuric acid plant in three easy steps
Feature
Completed converter walls.
The catalyst support plate for the new converter.
The bottom of the newly-constructed, all stainless steel converter.
Loading the newly constructed converter at the dock.
The converter was placed on a barge for transportation.
The converter was lifted from the barge by crane.
Site erection of the new converter.
Completed converter in the NORAM fabrication shop.
a. Used gas-to-gas heat exchangers with radial flow designs that provide lower pressure drop than older designs. b. Ducting sizes were reviewed for lower gas pressure drop. c. Used high performance (HP) packing to reduce gas side pressure drop to half of the existing saddle packing. 4. New equipment to provide better reliability, longer on-stream time and lower maintenance requirements than existing: a. All pieces of equipment utilized modern designs. b. All-welded equipment used to eliminate leak points. c. Thermal expansion strategies reviewed to eliminate trouble areas. d. Split-flow gas-to-gas heat exchangers utilized for improved equipment reliability. 5. New equipment to allow for lower emissions of SO2: a. The catalyst loadings of the converter were increased. b. All the old catalyst in the converter was replaced by new. c. Some cesium promoted catalyst was added to the converter to increase the SO2 conversion at low temperatures. d. The converter preheater was improved to allow for faster preheat-
PAGE 22
ing at higher temperatures. e. A multi-bed preheating system was installed to allow for the reduction of start-time and up emissions. f. All these lower emissions have a side benefit of better operability of an existing tail gas scrubber. With all the considerations above, and taking into account the conditions of the existing equipment, shut-down time and maintenance budgets, the following staged approach was developed: Step 1 (2010) • Installed one SF™ Split Flow Preheat heat exchanger and ancillaries. • Installed one RF™ Radial Flow Hot heat exchanger. • Installed all stainless steel ducting to/ from converter. Step 2 (2013) • Installed one RF™ Radial Flow Cold heat exchanger. • Installed one RF™ Radial Flow Intermediate heat exchanger. • Installed all stainless steel ducting between heat exchangers. Step 3 (2015) • Installed stainless steel converter with new catalyst and improved instrumentation. • Installed converter preheat ducting system. • Installed HP packing in the dry tower. NORAM completed an acid plant opti
The old converter, after removal from the site.
The new NORAM converter after installation.
mization study for the facility. Moreover, NORAM provided the basic design, detailed engineering, site services and fabrication advisory services for all the equipment replacement projects.
the main port. The converter was lifted by the on-board cranes of a cargo ship. The old converter was removed in one piece and the new converter was successfully installed during a regular plant turnaround.
Execution of step 3
Conclusion
The final step took place in 2015. This step focused on the upgrade of the conversion system. A new converter was fabricated by NORAM’s own fabrication shop in Axton, Vancouver. The converter was made of all-welded stainless steel 304H with catenary plates (no posts). The walls of the converter were ½-inch thick. The new converter was crafted to match the existing permits and tie-points. The converter, grillage and ducting were transported in one piece to the site. The vessel was lifted at the fabrication shop and rolled into a barge at the shop dock. The barge was then towed by a tug boat to
This project highlights NORAM’s ability to meet and exceed the client’s expectations to modernize the complete gasside of a sulfuric acid plant. In this case, the project was successfully executed in three steps, achieving improved reliability, lower pressure drop, improved ergonomics and lower emissions. NORAM Engineering and Constructors Limited performs engineering studies and training and supplies improved equipment at attractive prices for sulfuric acid plants. For more information, please visit www.noram-eng.com. q Sulfuric Acid Today • Spring/Summer 2016
Feature
Acid mist elimination in sulfuric acid plants
By: B. B. Ferraro, V. A. Sturm, M. D. Montani and N. P. Clark, Clark Solutions
Mist eliminators are essential pieces of equipment in a sulfuric acid plant and will help guarantee trouble free operation. Acid entrained in process gas causes violent and accelerated damage to equipment downstream of the mist formation, and also contributes to harmful emissions to the environment, making proper selection and design of mist eliminators for an adequate removal of acid mists and liquid carryover very important. In sulfuric acid plants, two main mist eliminators are used: the MaxiMesh®, which are (co-) knitted wire mesh pads or cylinders, generally designed to remove droplets of micrometric diameters in drying towers, and the Fiberbed®, a candle-type mist eliminator capable of removing particles of submicron diameter, usually found in final absorption towers and interpass absorption towers. This article will focus on the latter. Acid mists, in which liquid sulfuric acid is present in a gas flow, can be formed by two major mechanisms. The first is a result of dynamic shear stress due to contact between the liquid phase and solid surfaces or mechanical drag of the acid by the gas stream, generating droplets of micrometric diameters. The second mechanism involves liquid acid formation through condensation due to thermodynamic changes in the system or chemical reactions in the gas stream, such as acid produced from the reaction between sulfur trioxide and water or the rapid change in temperature due to fast cooling of a SO3-rich gas, generating droplets of submicron diameters. When a gaseous stream carrying entrained acid droplets passes through a mist eliminator, the gas moves freely through the fibers and the liquid is captured due to three different capture mechanisms: inertial impaction, Brownian diffusion and direct interception. When a gas stream carrying liquid particles passes through a fiber, the gas moves freely around the fiber but those particles with sufficient inertia will not follow the gas stream and will impact on the fiber. This mechanism is known as inertial impaction (Fig. 1). The broadest class of impaction devices is wire mesh pads, known as Clark Solutions MaxiMesh®, shown in Fig. 2. Some liquid droplets will follow gas stream paths that pass at a distance smaller than ½ of the particle diameter from the mist elimiPAGE 24
Fig. 4: Typical collection efficiency for different capture mechanisms.
Fig. 1: Droplet capture mechanisms.
Fig. 2: MaxiMesh mist eliminator. ®
nator fibers. When this happens, the particles are collected as the gas passes around the fibers. This effect is called direct interception (Fig. 1). On the other hand, particles of submicron scale will neither have enough inertia nor be big enough to be collected by the former mechanisms. However, due to their small size and inertia, they will acquire a random movement—known as Brownian motion—due to the energy transfer caused by their collision with the randomly moving gas molecules. This movement will drive these particles to collide with the mist eliminator fibers (Fig. 1). Brownian diffusion capture will be favorably affected by the reduction in fiber diameter and bed void fraction. Lower gas velocities will increase particle residence time in the mist eliminator bed, which results in a higher probability for the random movement collection, increasing the overall efficiency of the mist eliminator. The Fiberbed®, depicted in Fig. 3, works best in these cases. A typical efficiency curve behavior for each capture mechanism, including Fiberbed® by Clark Solutions, in a in a generic process condition is shown
Fig. 3: Fiberbed® mist eliminators.
Fig. 6: Inlet and outlet distribution for condensed mist with oleum.
in Fig. 4. Independent of the collection mechanism, once particles are retained by the mist eliminator bed, they will coalesce, leaving the gaseous current free from the liquid. Mist eliminators have geometry, materials and construction details that are designed to retain a certain range of droplets with a certain efficiency, to precisely fit the process they’re designed for. Fiberbed® eliminators are often used in the absorption towers because conditions at the inlet of the tower make formation of sulfuric acid (either by chemical reaction between water and SO3 molecules or by condensation of sulfuric acid molecules) likely to occur, generating a substantial amount of fine acid mist. This condensation is even finer when the plant is operating an oleum tower. The fiber density and layer width of candle-type fiber filters such as Fiberbed® are specially designed to improve the Brownian diffusion capture mechanism and collect this mist, and are responsible for extending the plant’s life and uptime.
Droplet size influence
The average estimated droplet size distribution of sulfuric acid mist generated at an Interpass tower of a typical 3/1 absorption plant is shown in Fig. 5. However, numerous factors and process conditions can alter the droplet distribution, such as proper air drying, leaky water
Fig. 5: Inlet and outlet distribution for condensed mist without oleum.
or steam piping, poorly designed or installed acid distributors and low packing heights, increasing the liquid load on the mist eliminators. One of the most frequent unnoticed occurrences that shifts the droplet size is the presence of mist due to oleum production. Because oleum is formed through a chemical reaction between sulfuric acid and SO3 at low temperatures, many submicron-sized droplets are formed during condensation when an oleum tower effluent stream comes in contact with the hot gas main stream flowing into the Interpass tower, distorting the Gaussian-like estimated droplet distribution curve for the absorption tower. The result is an estimated wavy distribution which peaks at very small diameter sizes, as shown in Fig. 6.
Mist elimination design
As discussed, Fiberbed® mist eliminators are designed to capture submicron particles that behave in Brownian motion. However, it is important to select the right fiber diameter, bed density, bed thickness and bed layers to efficiently remove acid mist content in the expected distribution range. Not only efficiency must be taken into account, but also available pressure drop during clean and dirty plant conditions. Threeinch beds will generate on average 50 percent more pressure drop than two-inch beds, as pressure drop is proportional to bed thickness given all other variables are constant. An estimated efficiency comparison between two- and three- inch bed thicknesses is shown in Fig. 7. Fiber bed mist eliminators such as Clark Solutions Fiberbed® are a unique class of equipment. Unlike many other mist eliminator devices, they are designed and built to provide nearly 100 percent efficiency in all range of particle sizes. This performance can only be achieved with strict quality control and fabrication standards. After manufacturing, a dry pressure drop plot (Fig. 8) followed by a hot air thermography
Fig. 7: Total collection efficiency comparison for 2” and 3” bed thicknesses.
Fig. 8: Online dry pressure drop plot.
Fig. 9: Thermography to evaluate filter bed homogeneity.
(Fig. 9) will ensure that the equipment is properly manufactured and will perform to the expected levels.
Conclusion
In Fig. 7, where efficiencies were measured for beds with similar characteristics with exception to thickness, it is possible to assess that a three-inch bed thickness brings much more efficiency, which results in an almost flat outlet distribution shown in Figs. 5 and 6, whereas a two-inch bed thickness shows an inefficiency for oleum production, resulting in a small peak outlet in Fig. 6, which may be observed in a stick test or in acid draining at downstream equipment. For plants without oleum, a two-inch bed thickness may bring a better trade-off in efficiency and pressure drop, becoming a better option in situations with lower acid mist generation or in conditions with higher droplet diameters. Finally, when observing acid content downstream from towers, it may be necessary to inspect and evaluate the plant, considering dry tower inefficiency, water leaks and bad acid or gas distributions inside towers, as well as other problems. Clark Solutions is available to conduct such inspections. For more information, please visit www.clarksolutions.com.br. q Reference:
Louie,
Douglas
K.
“Handbook of Sulphuric Acid Manufacturing,” 2005.
Sulfuric Acid Today • Spring/Summer 2016
INDUSTRIAL LININGS AND EQUIPMENT FOR SULPHURIC ACID PLANTS ENGINEERING + PRODUCTION + INSTALLATION REFRACTORY LININGS AND CORROSION PROTECTION SYSTEMS FOR: SULPHUR FURNACE SPENT ACID FURNACE FLUID BED ROASTERS ABSORPTION TOWERS PUMP TANKS SULPHUR PITS GAS CLEANING VESSELS CONVERTERS ACID RESISTANT LININGS
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Sulphuric Acid Today.indd 1
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Feature
Weir Minerals Lewis Pumps manufactures API 610 11th edition qualified pumps as standard By: Fred Hugill, Weir Minerals Lewis Pumps Product Manager
Weir Minerals Lewis Pumps has been manufacturing vertical sump pumps for molten sulfur applications since the 1940s. For many years, all that was required for use in chemical, oil and gas plants was a standard sulfur duty pump. In 2000, however, it became necessary for sulfur pumps to meet more stringent specifications as set forth in the API 610 standards. Regulated by the American Petroleum Institute, the standards cover all centrifugal pumps in the petroleum, heavy duty chemical and gas industry services. “In response to the new standards, Weir Minerals Lewis Pumps added enhanced construction features and began to offer various tests and inspections that enabled us to respond to our customer’s needs,” said Fred Hugill, product manager of Weir Minerals Lewis Pumps. “In 2015, Weir Minerals Lewis Pumps reviewed the most recent API 610 11th edition specifications against the products that we had upgraded for the oil and gas industries.
We performed an extensive gap analysis to identify what design changes were needed, the special test and inspection capabilities required and the detailed documentation necessary to ensure our vertical pump products complied with the current API 610 standards.” In addition, Weir Minerals Lewis Pumps recently built a state-of-the-art deep-pump test pit, fully instrumented, to complete performance tests on assembled pumps. This advanced deep-pump test pit enables Weir Minerals Lewis Pumps to accurately measure pump head capacity, power and NPSH, pump vibration, bearing temperature rise, overall sound pressure levels and resonance, among other things. In addition, the contract department is staffed with engineers who have intimate knowledge of the API standards and prepare the documents that are mandated by the API 610 code. As a result of this process Weir Minerals Lewis Pumps now offers
standard Lewis® sulfur pumps, as well as API 610 compliant Lewis® sulfur pumps, VS 4 and VS 5 style pumps. The API 610 compliant pumps are available in any material of construction class listed in the specifications with S1, S6 and A8 being the more standard configurations. All of this, with the same standards and quality product that customers recognize Lewis® pumps for worldwide, is now available as API 610 compliant. For a completely qualified unit, API 610 compliant Lewis® pumps can be
combined with a high efficiency motor to meet project specifications, an API 682 mechanical seal and an API coupling. Weir Minerals Lewis Pumps continues to enhance its product portfolio and is proud to offer a product that meets the API 610 (ISO 13709) specification as standard. This product is recognized and used around the world in molten sulfur service in refineries, gas plants and some chemical plants. For additional information about Weir Minerals Lewis® Pumps product range, please visit www.global.weir. q
Weir Minerals Lewis Pumps now offers API 610 compliant sulfur pumps.
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Sulfuric Acid Today • Spring/Summer 2016
Benchmark.
We’ve raised the bar with best-in-class solutions for oil and gas applications. Welcome to a new standard of innovation and technology. As you have come to expect, Dresser-Rand provides safe, reliable and efficient rotating equipment for nearly every application in the oil and gas market. But there’s more. The new Dresser-Rand business now has expanded resources and more experience as a member of the global Siemens family. The Dresser-Rand business combines one of the industry’s most extensive portfolios of rotating
equipment with a universe of intelligent solutions and one of the world’s largest technical support and service center networks. We offer more choices—where you need us— all from a single supplier. So what can you expect from us? High-quality products and services that turn longer run times for your equipment into an everyday experience. This, combined with local around-the-clock support, is the new standard.
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Department
in the news Dow, DuPont merger—a duo of equals
WILMINGTON, Del.—DuPont and The Dow Chemical Company announced late last year that they will combine in an allstock merger of equals forming a new company to be named DowDuPont. The new entity plans to spin off three independent, publicly traded companies within two years. The spin-off companies will include an agriculture company, a material science company and a technology and innovation-driven specialty products company. Each of the businesses will have a clear focus, an appropriate capital structure, a distinct and compelling investment thesis, scale advantages and focused investments in innovation to better deliver superior solutions and choices for customers. “This transaction is a game-changer for our industry and reflects the culmination of a vision we have had for more than a decade to bring together these two powerful innovation and material science leaders,” said Andrew N. Liveris, Dow’s chairman and chief executive officer. “Over the last decade our entire industry has experienced tectonic shifts as an evolving world presented complex challenges and opportunities…. This merger of equals significantly enhances the growth profile for both companies, while driving value for all of our shareholders and our customers.” “This is an extraordinary opportunity to deliver long-term, sustainable shareholder value through the combination of two highly complementary global leaders and the creation of three strong, focused, industry-leading businesses,” said Edward D. Breen, chairman and chief executive officer of DuPont. The combined company will have a market capitalization of approximately $130 billion. The transaction is expected to deliver approximately $3 billion in cost synergies and about $1 billion from growth synergies. The merger is targeted to close in the second half of 2016. Separation of DowDuPont into the three spin-offs is expected to occur 18-24 months following the merger’s close.
For more information on The Dow Chemical Company, please visit www.dow.com. For more information on DuPont, please visit www.dupont.com.
Blasch Precision Ceramics on course for strongest year
MENANDS, N.Y.—A new distribution agreement with chemical giant DuPont is just one of the factors that helped set Blasch Precision Ceramics on a course to finish this year with record sales. The Menands-based ceramic parts maker supplies refineries and manufacturers of jet engines, gas-fired turbines, semiconductors and paper. New business in India, Russia, Taiwan and Australia, and a distribution deal with DuPont Clean Technologies prompted Blasch to increase its payroll from 97 to 120 employees over the past year. Chairman and CEO Dave Bobrek says he may hire up to 30 more employees in 2016, including administrative and personnel management staff, engineers, designers and production workers. The company, which was founded in 1979, saw revenue grow from $14.2 million in 2013 to $20 million in 2014. Bobrek projects a 15 percent increase in revenue when the current fiscal year ends in June. That would put annual revenue at about $23 million, nearly double the amount of business the company was doing five years ago. Blasch took big strides four years ago when the company reached a distribution agreement with MECS Inc., a subsidiary of DuPont. The companies had worked together for decades but expanded their relationship when MECS agreed to use Blasch products in sulfuric acid plants, giving the company a path into a large market. Last fall, Blasch announced another distribution deal with DuPont Clean Technologies. Through that agreement,
Blasch makes ceramic parts used by refineries in Asia, Europe and Canada to remove sulfur from petroleum. The distribution agreement could bring more growth in an industry where Blasch has already established itself. The company has installed hundreds of parts in refineries operated by ExxonMobil, BP, Phillips and Petrobras of Brazil. For more information, please visit www.blaschceramics.com.
Argan completes acquisition of The Roberts Company
ROCKVILLE, Md.—Last December, Argan, Inc., completed its acquisition of TRC Acquisition LLC, which owns 100 percent of The Roberts Company, a fully integrated fabrication, construction and plant services company. The purchase price of the acquisition is $500,000, in addition to the assumption of approximately $17 million in debt obligations, which Argan expects to retire in the short term. Rainer Bosselmann, Chairman and CEO of Argan, stated, “With substantial revenue and the reengagement and leadership of founder John Roberts, we believe the acquisition of Roberts enhances and diversifies our portfolio of companies.” Founded in 1977 and headquartered near Greenville, N.C., Roberts is designed to work specifically with heavy and light industrial clients. Its fabrication services offer unlimited steel plate fabrication specializing in custom complex ASME code pressure vessels and heat exchangers. In addition, Roberts provides a full service project solutions group for grass roots projects, as well as a plant services group to handle maintenance turnarounds, shutdowns and emergency mobilizations. Roberts will operate as a wholly owned subsidiary of Argan. Argan’s primary business is designing and building energy plants through its Gemma Power Systems subsidiary. For more information on The Roberts Company, please visit www.robertscompany.com. For more information on Argan, Inc., please visit www.arganinc.com. q
Radial Flow Stainless Steel Converters Experience: • Introduced in 1981 • Originally developed and patented by Chemetics • Industry standard best in class design • More than 50 designed, fabricated and supplied by Chemetics Features and Benefits: • Radial flow design – Uniform gas distribution results in optimal catalyst performance • All welded, contoured separation and support elements – Eliminates gas bypassing – Low mechanical stress design uses up to 30% less stainless steel • No ‘Posts and Grates’ for ease of access and catalyst installation • Round gas nozzles eliminates leaks, over 1000 years of leak free operation • Modular construction options to reduce cost and schedule risk Flexible configurations, such as internal heat exchangers, for easy retrofits.
Innovative solutions for your Sulphuric Acid Plant needs Chemetics Inc.
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Chemetics Inc., a Jacobs company
(headquarters) Vancouver, British Columbia, Canada Tel: +1.604.734.1200 Fax: +1.604.734.0340 email: chemetics.info@jacobs.com
PAGE 28
(fabrication facility) Pickering, Ontario, Canada Tel: +1.905.619.5200 Fax: +1.905.619.5345 email: chemetics.equipment@jacobs.com
Sulfuric Acid Today • Spring/Summer 2016
Feature
Creating reliable, durable seals in glass-lined steel equipment Equipment made of glass-lined steel is used when manufacturing or processing aggressive chemicals such as aniline derivatives and strong acids such as sulfuric, nitric or hydrochloric acid. The Achilles heel of such glass-lined systems is the gaskets needed to seal the joints between components. Exposure to aggressive media causes the seals to degrade over time, resulting in damage to equipment and posing a health risk to operators. Replacing the seals costs a great deal of time and effort, with a corresponding drop in production output. A newly developed gasket tape made of ePTFE (expanded polytetrafluoroethylene) is specifically designed to address the challenges of creating reliable seals in large glass-lined steel equipment. Operators of chemical plants choose sealing materials according to a wide range of criteria such as process media, flange type, sealing performance, pressure and heat resistance, cost and longevity. Other important selection criteria include time required for installation and inventory management considerations. And of course, a plant operator’s prior gasket experience weighs in as well. Gaskets for glass-lined steel equipment are safety-critical parts because their failure can endanger human lives and/ or harm the environment, yet they are often managed as parts of minor significance.
Sealing challenges
Glass-lined steel presents the advantage of being highly resistant to corrosive and/or abrasive media, as well as being biologically and catalytically inert. Another characteristic feature of this material is its smooth, easy-to-clean, low adhesion surface (Fig. 1). For these reasons, the use of glasslined steel is uniquely advantageous in some applications, despite the challenges to sealing the flanges of glass-lined vessels (Fig. 2) and piping. Reliably sealing glass-lined steel equipment is particularly challenging relative to standard steel equipment. One contributing factor is the limited load available to seal the gasket. The glass lining is more fragile than the metal, and can therefore split or splinter if handled incorrectly. As a result, the gasket load that can be applied to the seal is lower than that for an all-steel flange. Care must be taken to limit the pressure applied when installing gaskets between interconnecting parts of the system. Another challenge is that of achieving a reliable seal when the flange’s glass surface is uneven or has surface deviations. Once the glass lining has fused, its surface cannot be reworked. In addition to these sealing challenges resulting from PAGE 30
Fig. 1: Close-up of glass-lined steel flange.
the glass-lined surface itself, an additional challenge and limiting factor is that of choosing a suitable sealant material for glass-lined steel systems, because these involve the use of aggressive media such as aniline derivatives and strong acids under demanding conditions. The challenges posed by these characteristics of glass-lined steel, combined with the exposure to aggressive chemicals and high temperatures, must be met by the chosen sealant. In practice, these difficult conditions often lead to premature sealing failure and a greater risk of equipment corrosion. The further consequences of sealing failure include leaks and uncontrolled emissions, damage to equipment, high replacement and repair costs, production losses, unplanned maintenance and downtime and potential risks to employees’ health and safety and to the environment.
Chemically resistant sealing material Because of its high chemical resistance, polytetrafluoroethylene (PTFE) is often used as gasket material in applications involving highly aggressive media. It resists attack by almost all media (pH range 0-14), and supports an extremely wide range of temperatures, from -269˚C to +315˚C. The non-aging material is weather and UV-resistant, has a low coefficient of friction, is physiologically harmless and is suitable for a wide range of different applications. The molecular structure of PTFE consists of a chain or backbone of carbon atoms saturated with fluorine atoms. The strong covalent bonds between the fluorine and carbon atoms explain this polymer’s quasi-inert reactivity to other chemicals. This is the reason why it is an ideally suited sealant material for aggressive chemical applications. On the other hand, its low reactivity means that, unlike certain elastomers, PTFE is unable to form molecular networks. As a result, traditional PTFE gaskets have a pronounced tendency
Fig. 2: Example of a large scale glass-lined steel vessel.
to deform, or “creep,” when under stress, and particularly when exposed to thermal cycling.
Existing solutions
PTFE is widely accepted and valued for its chemical resistance. However, the PTFE polymer—without further modification— has notable shortcomings when used as a sealing material. Due to its hardness, it lacks the ability to easily conform to surface imperfections and reliably provide a tight initial seal. Additionally PTFE lacks the dimensional stability to reliably provide a long-term seal, due to its tendency to “creep” under stress and thermal cycling. Thus, commonly used sealing solutions such as envelope gaskets or filled PTFE gaskets attempt to overcome these shortcomings by incorporating a core of compressible material or a homogenous blend of PTFE and friction-creating fillers, respectively. However, each of these common sealing solutions now generates its own problems. In the case of the PTFE envelope, a thin outer skin of PTFE allows permeation of some media, or worst case can even have or develop defects (porosity or small holes in the PTFE envelope), both resulting in degradation over time of the non-PTFE gasket interior. Additionally, high temperatures can lead to a loss in sealing effectiveness with lower grade inlays, such as compressed synthetic fiber (CSF) sheets, that can become hard and brittle. The need to shim envelope gaskets can also lead to costly delays. Filled PTFE gaskets typically contain
glass spheres or fibers to provide friction within the material and improve creep resistance. This is not enough in all cases, though. High temperatures, especially cycling temperatures, combined with the low load capability of glass-lined steel lead to gasket force loss (due to creep) resulting in higher leakage. Extra complexity is added with large flanges (> DN 600 / ASME 24”) due to the need for offsite gasket fabrication. This often results in long lead times, shipping, handling and inventory challenges. Furthermore, inconsistent quality across manufacturers and product lines, as well as time consuming and complex installation, may lead to troublesome and delayed facility start-up.
Alternative solution based on expanded PTFE (ePTFE) An alternative solution is to use expanded PTFE (ePTFE), a material that Bob Gore discovered in 1969 while experimenting with ways of heating and stretching PTFE rods. The combination of heat and rapid expansion significantly improves the material’s mechanical properties while at the same time preserving the original chemical resistance properties of PTFE. The added mechanical advantages of ePTFE include: • high resistance to creep and cold flow, resulting in longer service life • good conformability resulting in tight seals • outstanding blowout performance • superior high-temperature performance Sulfuric Acid Today • Spring/Summer 2016
NL-HECC Ad SAT 1-2.qxp_1/4 Page 2/10/16 9:35 AM Page 1
Novel gasket tape
GORE® Gasket Tape Series 1000 (Fig. 3) was specifically designed to address the challenges of reliably sealing large glasslined steel flanges (> DN 600 / ASME 24”). The tape uses a highly advanced version of Gore ePTFE with extraordinary resistance to the gasket creep that could take place in the service conditions of glass-lined steel vessels. Additionally, GORE® Gasket Tape Series 1000 contains a new proprietary barrier core of compressed, high-density ePTFE, which provides effective protection against leakage, optimized for the range and limitations of load available to seal glass-lined steel flanges.
Fig. 3: Cross section of GORE® Gasket Tape Series 1000.
Fig. 4: Cut-away of GORE® Gasket Tape Series 1000 in use. Sulfuric Acid Today • Spring/Summer 2016
The barrier core enables an area of very high density ePTFE to be produced rapidly and reliably as the bolts are tightened. Thus, even when a relatively low contact pressure is applied, as is the case with glasslined steel flanges, an optimum seal can be achieved. GORE® Gasket Tape Series 1000 prevents the diffusion of highly permeating chemicals, providing reliable protection from such emissions across the width of the flange (Fig. 4). With this technology, the resulting seal is more than ten times tighter than when using conventional ePTFE gasket tapes without the proprietary barrier core. The tape is supplied in a convenient spool format that simplifies handling, and reduces delivery lead times by facilitating rapid shipment of a standard and compactly packaged product. This format also significantly simplifies the task of applying the sealant during flange assembly. The length of tape required is simply reeled off from the spool and fitted to the shape of the flange at the assembly location. The adhesive backing facilitates placement of the gasket tape on the flange, enabling it to be installed in one step by a single operator. The sealing performance, along with the installation and logistical advantages of the gasket tape format, combine to make GORE® Gasket Tape Series 1000 a preferred sealing option for GLS vessels. De Dietrich Process Systems, for example, has endorsed the use of this gasket tape in its glass-lined steel reactors.
Conclusion
The new GORE® Gasket Tape Series 1000 is specifically designed to meet the challenges of sealing flanges in large glasslined vessels. It combines an advanced generation ePTFE tape with a new proprietary barrier core of compressed ePTFE. This provides all the numerous sealing benefits relative to other PTFE-type materials, notably including extraordinary resistance to creep and cold flow. The proprietary barrier core prevents the diffusion of highly permeable media, and provides reliable protection against emission across the width of the flange even at moderate loads available in glass-lined steel flanges. The tape is entirely fabricated from chemically inert ePTFE, and does not incorporate less chemically resistant fillers or components. GORE® Gasket Tape Series 1000 is designed to provide an effective and long-term reliable seal, specifically optimized for use within the specification range of flanges for glasslined steel equipment. This may facilitate either longer maintenance cycles or higher reliability within a fixed maintenance cycle– both of which increase operational efficiency and reduce maintenance costs as demanded by leading operators of chemical plants. For more information, please visit gore.com. q
Feature
Thanks to its conformability, ePTFE is more suitable than rigid materials to sealing flange surfaces of different qualities. This is because the sealant is capable of adapting its shape to surface irregularities on the flange, further complementing the tightness of the seal. The result is a tight initial seal that reliably maintains its sealing performance. Over the past several decades, W.L. Gore & Associates has introduced further advancements to this technology. These include extending and optimizing the expansion and resultant material properties in more than one axis, as well as significant optimization of the expanded PTFE. Each of these improvements has provided a step change in one or more of the material property advantages, and therefore the sealing performance advantage of ePTFE over non-expanded forms of PTFE, as well as the original ePTFE innovation itself.
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Department
lessons learned: Case histories from the sulfuric acid industry
Inspection, maintenance key to avoiding problems Collapse of tower packing
Acid plants have traditionally used packed columns as drying and absorbing towers. Many of these towers are made of brick-lined steel, with either arch/pier support or a self-supporting dome to hold up the ceramic packing. The gas enters below the packing support, travels up the packing, and moisture or SO3 are absorbed by the circulating sulfuric acid. The arch/pier support is made of acid brick and silicate mortar, and is designed to support the heavy load of alumina beams, partition rings or grid blocks, ceramic packing and the circulating sulfuric acid. While this type of support system is designed to withstand a high compressive or vertical load, it cannot take much transverse or horizontal load. A number of packing collapses have been reported in the industry, usually resulting in several weeks of plant outage. This is caused by high liquid level at the bottom of an absorbing tower, rising up to the gas inlet duct. This in turn creates a “wave action” of the accumulated acid, which knocks down the arch/pier support. What causes the acid level to rise in the first place is usually a blockage of the acid return line with packing or brick chips. This may stem from an improper plant shutdown of failing to close a gas block valve, allowing hot converter gas to flow to the absorbing tower. The hot gas overheats the ceramic packing and
support. Upon restarting the tower circulation, the cold acid contacts hot ceramic components, shocks, cracks and drops the “chips,” plugging the return line. An emergency shutdown from a power failure, coupled with not blocking the gas flow, may be a cause for the initial packing breakage. In self-supporting dome towers, high liquid level can also cause high localized gas velocity in the packing, flooding, “bumping” and shattering of the ceramic packing. Improper shutdowns allowing hot gas to overheat the ceramic packing can also shock and break the ceramic packing. Although not as drastic a failure as in an arch/pier type tower, this can create voids in the packed bed, reduce absorption efficiency and cause downstream issues. The root cause for this type of failure may stem from poor acid level detection at the bottom of the tower, as well as not blocking the process gas during a shut down. Lessons learned: Close a process gas block valve at shut down, especially if the tower circulation is lost, to prevent hot gas from reaching the tower. Monitor the liquid level at the bottom of the tower, and routinely test for proper level indication.
Blower dead head
Acid plants typically use a centrifugal compressor (aka blower) to transport the
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23/02/2016 13:28
process gas through the plant. These are extremely powerful blowers with turbines or motors, sized for several thousand horsepower, driving the unit. The blower is located at or near the front of the train in sulfur burning plants and in the middle of the train in spent acid or metallurgical plants. The best practice in an acid plant is to design all vessels to the maximum conceivable vacuum upstream of the blower, and maximum conceivable pressure downstream of the blower (preferably dead head), with associated safety interlocks to prevent exceeding the design. Things change, however, during the life of an acid plant. As the unit is debottlenecked, equipment is added for environmental reasons or antiquated equipment is replaced with the “latest and greatest” design. It is conceivable that extreme pressures are overlooked during the redesign. Such was the case for an acid plant where a new stainless steel converter with internal heat exchangers replaced the existing antiquated unit. As was discussed in the previous article, many plants are equipped with a process gas block valve, usually near the stack, that is closed during shutdowns to prevent hot converter gas from reaching the absorbing tower. During a startup, however, the valve needs to be reopened before the blower is started. In this case, the operator failed to open the block valve, the blower was started and dead headed, causing it to surge. The result was equipment damage in the upper part of the new converter, where unanticipated static and differential pressures “buckled” the upper parts of the converter. Lessons learned: Follow procedures to open the process gas block valve, i. e., establish a flow path, before the blower is started. Valve position switches and interlocks can help prevent mishaps. Review, during the design phase and hazard analysis, the maximum pressure and differential pressure a vessel and its internals can withstand. If deemed too costly to design to the dead head pressure or surging of the blower, include proper pressure interlocks to prevent equipment damage. Upon installation, routinely test the safety interlock systems for functionality.
Strain the packing chips
Most drying and absorbing towers in acid plants are packed columns using ceramic packing. Ceramic packing provides corrosion-resistant contact between the acid and gas, but they are brittle in nature, and broken pieces can plug equipment in the circulating system. Packing breakage results from: • Low quality, high-breakage packing. • Improper installation—dumping and breaking. • Normal wear and tear. • High temperature shocking/high liquid level incidents as described in the previous article. Broken packing first collects in the acidside (typically shell-side) of anodically-protected stainless shell and tube acid coolers, silicon stainless coolers and plate coolers. Cooler plugging is undesirable as it accelerates corrosion
from highly localized acid velocity and reduces tower circulation rate. Because most coolers are equipped with a bypass on the acid-side for temperature control, the packing chips have a direct path to the next tight spot where they can collect—the acid distributor at the top of the tower. If the distribution points plug, the packed bed may develop dry spots and cause gas bypass—slippage of moisture in drying towers and SO3 in absorbing towers. Silicon stainless trough distributors, conventional cast iron trough distributors with Teflon® inserts and pipe distributors of all materials are vulnerable to this type of plugging, because of the small openings at the distribution points. There have been a number of cases of accelerated cooler corrosion and plugged distributors from packing chips seen in the industry. In one case, an acid cooler needed premature replacement because of accelerated tube corrosion. Cleaning of plugged distributors was also reported, requiring entry into an inhospitable confined space. Lessons learned: Use a permanently installed strainer upstream of the acid cooler. This strainer should be sized properly with the correct materials of construction. Remove accumulated chips routinely during a shut down, and inspect the strainer for signs of corrosion—replace as required.
Strain the cooling water too!
Acid plants typically operate a cooling tower and associated cooling water circulation system for acid cooling, steam condensing and other miscellaneous cooling needs. The cooling water piping is typically made of carbon steel, and requires a good water treatment program to minimize corrosion. Over time, however, piping corrosion may occur as a result of acid leaks into the cooling water system, inattention to the water treatment program and general aging. Piping corrosion products can result in “rust chips” of up to ½-inch diameter flaking off the piping system. Without removal, these chips can plug the water-side of acid coolers, condensers and cooling tower distributor nozzles. Water-side plugging of acid coolers can cause accelerated corrosion of tubes because of increased tube wall temperature, as well as reduced heat transfer. Plugging of cooling water distributors can result in dry spots in the fill, increasing the cold water temperature the cooling tower can produce. A number of older acid plants have experienced this type of rust chip plugging, requiring cleaning of the water side of heat exchangers and cooling tower distributors. Some have installed strainers to help alleviate the problem. Lessons learned: Review the water treatment program and practices to minimize cooling water system corrosion. Install permanent cooling water strainers at the inlet to the acid coolers, condensers and cooling tower, if rust chips become a problem. Remove accumulated debris and check the integrity of the strainer routinely. q Sulfuric Acid Today • Spring/Summer 2016
Feature
“Quick Fit” pre-assembled acid-proof lined equipment By: Roland Günther and Oliver Schmidt, Senior Project Managers, Export Sales STEULER-KCH GmbH
The following case study describes the production of a large steel vessel with rubber and brick lining in a Steuler shop and delivering it to the customer site to minimize the shutdown period and reduce the costs of onsite mobilization and loss of production.
Scope of work / job definition / inquiry
A nonferrous metal winning plant in Europe requested to renew its more than 25-year old existing Venturi scrubber in the gas cleaning unit that cleans the off gases after the ore roaster. Not only the brick lining and the membrane had to be replaced, but also the steel shell. Other considerations were that the repair had to be completed during a short 10-day shutdown period and the new Venturi scrubber had to fit into the existing steel frame. Also, the narrow and complicated plant layout made it difficult to maneuver a big crane that was required to lift out the existing Venturi scrubber and lift in the new one. Additionally, the client facility had no place next to the existing Venturi scrubber to erect the new one and the only possibility was to line the new one 200 meters away from the job site.
Solution
After evaluating all the given parameters, the Steuler team determined that the best way to replace the Venturi scrubber within the short period of ten days was to send a new rubber lined and brick lined Venturi scrubber to the site, lift the old one out and put the new one in.
Execution of work
According to the dimensions of the existing Venturi scrubber, the Steuler team prepared a new steel drawing which incorporated the statistical calculations as well as the details of the brick lining, as shown in Fig. 1. Total weight of the Venturi scrubber was 31.5 tons. The team took special care to ensure that the connections to the existing gas duct, spray nozzles and lower part of the Venturi scrubber fit the existing onsite
Fig. 1: Drawing of the new Venturi scrubber.
PAGE 34
Fig. 2: Autoclave dimensions: diameter of 6 m and length of 15.3 m.
equipment. Also, the team constructed the necessary lifting lugs for transportation and lifting on site. For the scrubber’s membrane, the team used Steuler’s own graphite-filled hard rubber lining, Vulcoferran 2190, thickness 4 mm, with excellent chemical and diffusion resistance and a maximum service temperature of 100 degrees C. Vulcoferran is based on natural rubber (NR) and is vulcanized in an autoclave. The rubber lining produced in the shop and the vulcanization in the autoclave ensures a definite universal high quality with minimum risk of failure. Steuler’s autoclave can accommodate vessel sizes as large as 5.8 m in diameter by 15 m long. See Fig. 2. After the vulcanization and quality assurance test for the rubber lining, e.g. thickness, hardness, spark test etc., the Venturi scrubber was transported to the brick lining workshop, where the installation of the brick lining was completed. In order to avoid exposing the rubber lining membrane to temperatures higher than 80 degrees C in operation, the team constructed the thickness of the brick lining according to a thermal heat calculation, as shown in Fig. 3. During construction, holes were drilled for the 4 tangential spray nozzles with a special drilling machine. This was done in this way because there are very critical areas where the bricks are very small and thin,
Fig. 3: Thermal heat calculation.
Fig. 4: Drilling nozzle openings.
Fig. 5: Drilled nozzle opening in inner layer of nitride bonded silicon carbide bricks.
and cutting them would be very difficult. Drilling ensures that the openings for the spray nozzles are in the correct orientation and that the brick lining is made without cavities. With regard to the drilling, see Fig. 4 and Fig. 5. During the brick lining construction, Steuler’s experienced fitters maintained defined temperatures in the workshop. The bricks and mortars were selected to withstand chemical attack as well as mechanical and thermal shock stress. Fig. 6 shows the construction of a typical brick lining in a Venturi scrubber. After finishing the brick lining work and a hardening time of six days, the team and client together made the final acceptance and closed all nozzles with wood or plastic. On the upper gas inlet flange, the team installed a 20 mm thick counter flange which was required on site and also made the vessel stiff and inflexible for transport and lifting. That prevented damage during the transport via truck to the site through three countries as well as lifting to the final position. Upon the client’s request, Steuler delivered the Venturi scrubber just in time to the site on a special air sprung flatbed truck. The lifting out of the existing Venturi scrubber and the lifting in of the new one, performed by a client subcontractor but supervised by Steuler, was completed in a very short time (see Fig. 7). After all nozzles and ducts were connected to the plant, Steuler made the final inspection together with the customer to ensure that no damages had occurred during the transport, lifting and connection work. Sulfuric Acid Today • Spring/Summer 2016
Hengli Petrochemical Company selects DuPont alkylation technology
Fig. 6: Construction of a typical brick lining in a Venturi scrubber.
Benefits of “Quick fit” preassembled brick lined equipment •
• • • • •
•
Maintaining proper working conditions during preassembly in the workshop, including quality assurance. Using an autoclave rubber lining instead of field rubber lining. No traveling and hotel costs for the fitters. Using experienced, skilled fitters. Providing just-in-time delivery. Saving costs on site for: tenting, sandblasting, acclimatization and heating, site mobilization, scaffolding, electrical power, water, etc. Reducing shutdown period and production loss.
Fig. 7: Transportation and lifting of the Venturi scrubber.
•
Fewer interactions with onsite personnel, such as contractors, operating personnel, security staff, etc. • Less space required on site due to pre-assembly. The services of Steuler-KCH cover the fields of surface protection, refractory systems and plastics engineering. Especially in the field of industrial linings and equipment for sulfuric acid plants, we serve our customers all over the world with engineering, production, delivery and installation of the materials. Steuler-KCH is a single source solution for sulfur, spent acid furnaces and fluid bed roasters, gas cleaning vessels, absorption towers and pump tanks, sulfur pits, converters and acid resistant floor linings. For more information, see www.steuler-kch. steuler.com/en/industries/sulphuric-acid-industrie. q
WILMINGTON, Del.–Hengli Petrochemical Company (Hengli) of Dalian, China recently awarded DuPont Clean Technologies (DuPont) a contract to supply the alkylation and spent acid regeneration technologies for a new refinery in the Changxing Island Harbor Industrial Zone. The contract includes the license and engineering design for the STRATCO® alkylation and MECS® SAR units. Installation at Hengli is planned for 2018 with start-up expected in 2019. With the STRATCO® alkylation technology, the refinery will allow Hengli to produce a high quality alkylate product (used as a blending component in the gasoline pool) from a 100 percent isobutylene feed stream. “DuPont is pleased to provide Hengli Petrochemical with our world-class sulfuric acid alkylation technology to improve the overall gasoline pool from the refinery,” said Kevin Bockwinkel, global business manager for the STRATCO® Alkylation Technology. “The unique feed stream (100-percent isobutylene) available from the Hengli Petrochemical facility marks the beginning of a new era for alkylation in the gasoline market….” The alkylation unit at Hengli will utilize the patented XP2 technology in the STRATCO®Contactor™ reactor. The XP2 technology is one of the latest enhancements to ensure the most efficient use of the tube bundle heat transfer area, providing significant process benefits and improved alkylate product quality. For additional information, please visit www. dupont.com. q
Powell Sulfuric Acid Dilution System The Powell Sulfuric Acid Dilution Systems are engineered to continuously dilute 93% or 98% sulfuric acid to any lower strength. The systems are automatic and include pumps and cooling water systems for the safe, accurate dilution of the concentrated acid. Systems are available for all flow rates and diluted acid strengths. Features • Automatic Dilution • PLC Based Control System • Adjustable Batch Amounts or Flow Rates • Strong Acid and Water Supply Pumps • Skid Mounted, Fully Assembled
740 E. Monroe Road, St. Louis, MI 48880 Ph: 888.800.2310 www.powellfab.com email: info@powellfab.com Sulfuric Acid Today • Spring/Summer 2016
PAGE 35
Feature
news bits
Feature
Moisture-free surface cleaning technology: NitroLance™
By: William Putman, NitroLance™ application specialist, Conco Services Corp.
For decades, traditional industrial tube cleaning methods that brought renewed vigor to plant equipment have used water to either propel mechanical cleaners or flush out debris with high-pressure streams. In nature, as in industry, water is a powerful driver and mechanism for change. But in 2016, we’re wisely rethinking our use of water: water is valuable; in some places, scarce; increasingly regulated and always vulnerable to contamination. Consequently, a heightened emphasis on good stewardship of water, the need for a safe method of removing toxic tube deposits, combined with regulatory concerns over the secondary waste streams that water-driven cleaning methods produce, motivated Conco Services Corp. to invest in a safe and effective alternative: a moisture-free, waterless cleaning method using liquid nitrogen. Others have laid the groundwork for the use of liquid nitrogen as an effective catalyst, and Conco has brought this technology to industrial cleaning applications with the NitroLance™. In the 1990s, the United States Department of Energy developed the use of high-pressure liquid nitrogen as a tool for cleaning and cutting when it needed to cut into storage tanks that contained radioactive materials. Pressurized liquid nitrogen was a smart choice because it did not spark, allaying concerns about the contents of the storage tanks catching fire or exploding. Disposal concerns were simplified when using liquid nitrogen because after use it evaporated into the atmosphere. The absence of water in the cleaning process eliminated any secondary waste stream or cross contamination issues. In 2003, NASA went on to use liquid nitrogen to safely clean the surface of the
Hot heat exchanger before and after cleaning with NitroLance.™
NitroLance™ nozzle inside tube.
Space Shuttle. Sandstone rubble lifted off of the Shuttle like powder, revealing a clean surface. NitroLance, developed by Verona, Pa., based Conco, uses pressurized liquid nitrogen in a supercritical state to clean a variety of heat exchangers, boilers, reactors, economizers and other industrial surfaces. Liquid nitrogen is highly effective at removing tenacious fouling deposits found in petroleum refinery process equipment and power generation condensers and heat exchangers. Through three
mechanisms of action—mechanical pressure, super cooling and thermal/volumetric expansion—units that are cleaned with pressurized liquid nitrogen, as compared to highpressure water, see significant improvements in process flow rates and control, process energy and pollution management and downtime reduction. During two recent applications, the NitroLance demonstrated the benefit of using a moisture free waterless cleaning system, saving time and money. The first application was conducted on a heat exchanger within the catalytic converter at an acid plant located in the Southwestern United States. The acid plant needed an efficient, waterless cleaning solution for the heat exchanger that would eliminate the need to remove the catalyst from the converter for fear of damage from moisture. The NitroLance effectively removed all of the caustic deposits in and on the tubes, so there was little if any effluent to be collected. At a sulfur recovery unit in the Northwestern United States, two waste heat boilers were cleaned with the NitroLance. The NitroLance completely removed the coke-like iron pyrite deposit from the tube walls, and the tubesheet refractory and ceramic ferrules were left in good working order after cleaning. Follow-up remote field testing resulted in the retubing of one of the waste heat boilers. The boiler cleaned with the NitroLance performed as well as the completely retubed boiler. For more information, including case studies and videos, please see www.conco.net. q
conference review
Info sharing at CRU’s conference, Sulphur 2015
Sulphur 2015, last year’s edition of an annual sulfur conference hosted by industry analyst CRU, took place November 9-12 in Toronto, Canada. The yearly meeting gathers sulfur and sulfuric acid professionals to meet, learn and network. Held at the Sheraton Centre Toronto Hotel, the conference offered delegates in-depth programing and numerous networking opportunities. The event also included a large scale exhibition in which 70 companies demonstrated the latest technologies and engineering services. Mike Gallagher, CRU general manager, fertilizers, welcomed attendees to the conference while CRU industry experts discussed global market developments and the outlook for both sulfur and sulfuric acid. Technical engineers working in production facilities took advantage of 18 sulfur sessions covering: sulfur handling, sulfur degassing and corrosion, burners and waste heat boiler design and sulfur recovery. There were also PAGE 36
Matthew Viergutz of DuPont MECS, Inc., presented his paper on MECS® SolvR™ technology during the sulfuric acid session at the Sulphur 2015 conference.
Kleber Jurado of Southern Peru Copper Corp. presented a paper on his company’s successful, two-decade long operation of a metallurgical sulfuric acid plant.
Herbert Lee of Chemetics gave a comprehensive comparison between anodically-protected stainless steel coolers and alloy coolers to help plant operators make the right choice.
15 sulfuric acid sessions covering: sulfuric acid operations and catalyst, metallurgical acid operations and heat recovery. The informative sulfuric acid presentations included: —“Stabilization and capacity increase of sulfuric acid plants and sulfur recovery units: Use of skidmounted sulfur burners for SO2 supplementation,” presented by Guy Cooper, NORAM Engineering & Constructors — “Novel design of WSA technology for smelter operations,” presented by Morten Thellefsen, Haldor Topsøe, A/S —“Zambia’s newest copper smelt-
er and sulfuric acid plant,” Stefan Mohsler, Outotec GmbH and Doug Louis, DKL Engineering, Inc. —“Decreasing ore grades: How to maintain the acid quality?” presented by Karl-Heinz Scherer, Outotec GmbH —“Enhancing sulfuric acid production with configurations of Cansolv SO2 and Bayqik technology,” presented by Laurent Thomas, Shell Cansolv —“20 years of successful operation of a metallurgical sulfuric acid plant at Southern Peru Copper Corporation,” presented by Kleber Jurado, Southern Peru
Copper Corporation —“BASF’s sulfuric acid catalysts: New catalyst developments,” presented by Christine Schmitt, BASF —“Understanding dynamics and emissions during sulfuric acid converter startup,” presented by Per Aggerholm Sørensen, Haldor Topsøe, A/S — “Heat recovery: Efficiency at any price?” presented by Stefan Braeuner, Outotec GmbH —“MECS® SolvR™ Technology: A platform for the next generation of sulfuric acid technology,” presented by Matthew Viergutz, DuPont MECS, Inc. —“Thermodynamic analysis of a
sulphur combustion turbine in a sulphuric acid plant,” presented by Robert Buckingham, General Atomics —“Anodically-protected stainless cooler vs alloy cooler: Making an informed decision,” presented by Herbert Lee, Chemetics Inc. —“Case studies in next-generation furnace designs for sulfuric acid plants,” presented by Brian Lamb, MECS, Inc. —“Hydrogen incidents in sulfuric acid plants: Why now? What can we do?” presented by Leonard J. Friedman, Acid Engineering & Consulting Inc. As in past years, the conference offered an interactive sulfuric acid workshop, which for 2015 delved into turnaround planning. Following the presentations, participants were given an opportunity to have their questions answered by presenters. Plans are underway for Sulphur 2016, which will be held November 7-10 in London. For more information, visit the event’s website at www.crugroup.com/events/ sulfur. q
Sulfuric Acid Today • Spring/Summer 2016
Faces & Places
Alvaro Stegmann of AST Aptus Sulphur Technologies, left, Garry Warren of SNC-Lavalin, center, and Owen Kellow of SNC-Lavalin, right, enjoyed networking during SNC-Lavalin’s hospitality reception held in conjunction with the Sulphur 2015 conference.
Ossama Jamal Al Ghamdi of Ma’aden Phosphate, left, and Hannes Storch of Outotec catch up during Outotec’s hospitality reception held in conjunction with the Sulphur 2015 conference.
Mick Cooke, left, Randy Stanfill, center, and Fred Hugill, all of Weir Minerals Lewis Pumps, catch up with one another in their booth at the Sulphur 2015 conference.
Fiona Lavery, left, and Graeme Cousland, center, both of Begg Cousland Envirotec, catch up with Kleber Jurado of Southern Copper Peru Corp., right, during one of Sulphur 2015’s hospitality receptions.
John Orlando of NORAM Engineering & Constructors, left, and Dan Himmel of Langeloth Metallurgical enjoyed a hospitality reception at the Sulphur 2015 conference.
Enjoying SNC-Lavalin’s hospitality reception held in conjunction with the Sulphur 2015 conference are, from left, Trevor Van Daele of SNC-Lavalin, Candice Johns of Shell Cansolv, Laurent Thomas of Shell Cansolv and Doug Azwell and Garrett Palmquist, both of DuPont MECS Inc.
Enjoying Outotec’s hospitality reception at the Sulphur 2015 conference are, from left, Michael Borchwaldt of Friatec Rheinhütte, Juergen Stauss of Hugo Petersen GmbH, Dirk Hensel of BASF Corp., Gregor Staerke of W.L. Gore & Associates and Matthias Born and Roland Guenter, both of STUELER-KCH.
Pictured are, from left, David Bailey of CMW, Gregor Staerke of WL Gore & Assoicates, Craig Jongsma of Chemtrade Logistics and Brad Varnum of CMW at the DuPont MECS Inc. dinner held at the Hockey Hall of Fame.
Charlotte Davis, left, Rick Davis of Davis & Associates, center, and Christian Roempler of Noracid SA, right, network during a hospitality reception held at the Sulphur 2015 conference.
Outotec hosted a jazz reception at the Sulphur 2015 conference in Toronto. Pictured are, from left, Nick Henneberry of Aecometric Corp., Mike Josten of Protea Chemicals, Michael McFarthing of Aecometric Corp. and Thys Claassens, Hannes Storch and Stefan Mohsler of Outotec.
Enjoying the dinner hosted by Haldor Topsøe at The CN Tower in Toronto are, from left, Dan Himmel of Langeloth Metallurgical Co.; Patrick Polk of Haldor Topsøe A/S; Michael Ben Ari of Rotem, Israel; Craig Jongsma of Chemtrade Logistics; Hanno Hintze of Aurubis AG Germany; Per Aggerholm Sørensen of Haldor Topsøe A/S; Goldwyn Parker of Honeywell International and Bill Choate of J.R. Simplot.
Enjoying the DuPont MECS Inc. dinner at the Hockey Hall of Fame are, from left, Tom de Groot of Teck Metals, Chris Locke of George Locke Enterprises and Chris Lock of Border Chemical.
Thomas Alligood, left, and John Robinson, both of PCS Phosphate, enjoyed the evening functions at the Sulphur 2015 conference.
Bernd Viehoever of Siemens Turbomachinery Equipment, left, Guy Cooper of NORAM Engineering & Constructors, center, and Jacque Shultz, right, of Siemens Turbomachinery Equipment catch up during Outotec’s reception at the Sulphur 2015 conference.
Haldor Topsøe hosted a dinner at The CN Tower in Toronto during the Sulphur 2015 conference. Enjoying the view and delicious food are, from left, Sam Chidester of Haldor Topsøe Inc., Finn Stålesen and Oeyvind Ommundsen of Glencore Nikkelverk A/S Norway, Dennis Smerchanski of Border Chemical, William Goodell of Haldor Topsøe Inc., Chris Lock of Border Chemical, Marie Vognsen of Haldor Topsøe A/S, Kathy Hayward of Sulfuric Acid Today, Tom Degroot of Teck Metals and Kleber Jurado of Southern Copper Peru Corp.
Department
calendar of events AIChE Clearwater Conference celebrates 40th year
CLEARWATER, Fla.—Each year, members of the AIChE Central Florida Section and colleagues from all over the world gather at Clearwater Beach to share ideas concerning chemical process technology, specifically the production of phosphoric acid, phosphate fertilizers and sulfuric acid. This year marks the event’s 40th year at the Sheraton Sand Key Resort in Clearwater, and will take place June 10-11, 2016. Friday will include two sessions. The first will be a sulfuric acid technology session, chaired by Rick Davis of Davis & Associates and Jim Dougherty of Mosaic Co. The second session will be a workshop on Florida P.E. Laws and Rules. PDH certification is available for those who attend the full session for which credit is needed. P.E. numbers must be supplied on or before June 10, and attendance must be verified by proctors. As always, the convention provides a relaxing getaway for friends and family to enjoy 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.
For hotel information, presentation and paper deadlines, travel details and other relevant information, see www. mesaredondachile.com or email info@ holtec.cl.
Chilean sulfuric acid roundtable to meet in October
SULPHUR 2016 set for London
SAN FELIPE, Chile—Holtec Ltda. is pleased to announce the 11th Round Table for Sulphuric Acid Plants to be held in Chile from October 23-26, 2016. This year the conference will take place at the Rosa Agustina Conference Resort in Olmué, about 60 miles northwest of Santiago. Operators, maintenance experts, technology providers, plant owners, consultants and engineering firms specializing in sulfuric acid technology will discuss the latest developments in technology, projects, operations and sulfuric acid markets. As usual, delegates from most sulfuric acid plants in Central and South America will present operations and maintenance topics during the three-day conference. At the same time, technology providers will have a chance to chat with customers and present new developments and products. Simultaneous translation in English and Spanish will be provided.
LONDON—Now firmly established as one of the premier industry events for the sulfur and sulfuric acid markets, SULPHUR 2016 will take place November 7-10 in London. Attracting over 500 professionals from around the globe, the conference offers the opportunity for industry leaders to meet, learn and network. Each year, the extensive program covers key market trends, project updates and supply and demand forecasts in the commercial sessions, with presentations from respected industry figures, as well as and high level analysis from CRU’s Sulphur Team. The two day split-stream technical program showcases the latest technological developments to improve efficiency and compliance, and provides a high-level forum for engineers from the sulfur and sulfuric acid industries to share experiences and develop solutions to
2017
Sulfuric Acid
R O U N D T A B L E
April 3-6, 2017 Woodlands Resort The Woodlands, TX
common operational problems. For more information, please visit www.crugroup.com/events/sulphur.
2017 Sulfuric Acid Roundtable slated for Houston
COVINGTON, La.—Sulfuric Acid Today magazine is pleased to announce that the 2017 Sulfuric Acid Roundtable will take place April 3-6, 2017. It will be held at The Woodlands Resort in The Woodlands (Houston), Texas. The 2015 Workshop attracted more than 180 participants from around the world, and 2017 is shaping up to be an even bigger event. As in years past, sulfuric acid insiders will gather to attend presentations given by event cosponsors on a variety of topics relevant to the industry. Panel discussions and co-sponsor booths will provide more opportunities for information sharing, while social events will ensure that participants get to enjoy the beautiful area while building relationships that promote beneficial business exchanges in the future. For more information, please contact Kathy Hayward at (985) 807-3868 or email kathy@h2so4today.com. q
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Sulfuric Acid Today • Spring/Summer 2016
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