SS7: Sulfuric Acid Plants Brief Summary: Sulfuric acid is used as ...
SS7: Sulfuric Acid Plants Brief Summary: Sulfuric acid is used as a catalyst in alkylation units at petroleum refineries. Over time, sulfuric acid is contaminated with petroleum products and needs to be regenerated. The first step in the process is thermal decomposition of spent sulfuric acid in a furnace, producing sulfur dioxide (SO2). The catalytic reaction oxidizing SO2 to SO3 (which then reacts with water to form fresh sulfuric acid) is an equilibrium reaction which is never 100 percent efficient. As a result, there is always some unreacted SO2 that is vented to the atmosphere. There are three acid plants associated with Bay Area refineries. The Tesoro Refinery near Martinez operates an acid plant; Eco Services in Martinez operates an acid plant as a support facility for the Shell and Valero refineries on a regular basis and serves as a backup facility for the Tesoro Refinery when Tesoro’s acid plant is shut down; and Chemtrade West in Richmond operates an acid plant as a support facility for Chevron Products. Purpose: Reduce SO2 emissions from sulfuric acid regeneration associated with petroleum refining. Source Category: Permitted Sources – sulfuric acid plants Regulatory Context and Background: In 1977, the United States Environmental Protection Agency (EPA) promulgated 40 CFR part 60, subpart H, Standards of Performance for Sulfuric Acid Plants. The regulation limits SO2 emissions to 4 pounds per ton of acid produced and limits sulfuric acid mist emissions to 0.15 pounds per ton of acid produced. Air District Regulation 9, Rule 1 establishes emission limits for sulfur dioxide from all sources including ships, and limits ground level concentrations of sulfur dioxide. In 1992, the Air District amended Regulation 9-1, establishing an SO2 emission limit of 300 parts per million-volume (ppmv) for sulfuric acid plants, calculated at 12 percent oxygen. In 2007, Rhodia, Inc. entered into a consent decree with EPA and the United States Department of Justice limiting SO2 emissions from the acid plant (now operated by Eco Services) to 2.2 pounds per ton of 100 percent sulfuric acid produced, 365-day average, and 3.0 pounds per ton of 100 percent sulfuric acid produced, three-hour average.1 In their November 2010, RECLAIM Report, South Coast Air Quality Management District (SCAQMD) staff recommended a limit of 0.14 lbs per ton of acid produced (10 ppmv), which was adopted by SCAQMD. A review of EPA’s RACT/BACT/LAER Clearinghouse2 (RBLC) revealed a 2006 synthetic minor permit from New Jersey with an SO2 limit of 0.2 lbs per ton of acid produced and a 2012 PSD 1
This was part of a nation-wide consent decree and was not limited to the Martinez acid plant. The RBLC is a national database of case-by-case emission limitations made by permitting authorities when authorizing new sources of air pollution. 2
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permit from Indiana with an SO2 BACT limit of 0.25 lbs per ton of acid produced, 24-hour average. The New Jersey Department of Environmental Protection provided the Air District with two recent source test reports for the facility in Union County, New Jersey with the 0.2 pound per ton limit. The State of New Jersey confirmed that the facility was in compliance with its emission limits. Implementation Actions: Consider amendments to Rule 9-1, Sulfur Dioxide, that would limit SO2 emissions from acid plants associated with petroleum refining. Consider establishing BARCT limits of 0.2 lbs. of acid mist per ton of acid produced. Emission Reductions: Pollutants (tons per day) SO2
2020 1.40
Emission Reduction Trade-Offs: None Costs: BARCT limits of 0.2 lbs per ton of acid produced will require wet scrubbers at each of the three acid plants. One acid plant already has a wet scrubber, but it may need to be upgraded or replaced to meet the new standards. Capital costs are estimated at $7,000,000 for each facility, amortized to $700,000 annually. Operating costs are estimated at $200,000 per year at two facilities, and $300,000 per year for the third (higher caustic costs for higher SO2 reductions). Total costs are $2,800,000 per year. Co-Benefits: There will be less secondary PM2.5 formation from reduced sulfates. Issue/Impediments: None Sources (references): 1. 40 CFR part 60, subpart H, Standards of Performance for Sulfuric Acid Plants [42 FR 37936, July 25, 1977] 2. South Coast Air Quality Management District, Final Staff Report: Sox RECLAIM, Part 1, BARCT Assessment & RTC Analysis, November 2, 2010 3. US Environmental Protection Agency, RACT/BACT/LAER Clearinghouse (RBLC) Clean Air Technology Center 4. Bay Area Air Quality Management District, Regulation 9: Rule 1, Inorganic Gaseous Pollutants: Sulfur Dioxide, last amended March 1995
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This was part of a nation-wide consent decree and was not limited to the Martinez acid plant. The RBLC is a national database of case-by-case emission limitations made by permitting authorities when authorizing new sources of air pollution. 2
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permit from Indiana with an SO2 BACT limit of 0.25 lbs per ton of acid produced, 24-hour average. The New Jersey Department of Environmental Protection provided the Air District with two recent source test reports for the facility in Union County, New Jersey with the 0.2 pound per ton limit. The State of New Jersey confirmed that the facility was in compliance with its emission limits. Implementation Actions: Consider amendments to Rule 9-1, Sulfur Dioxide, that would limit SO2 emissions from acid plants associated with petroleum refining. Consider establishing BARCT limits of 0.2 lbs. of acid mist per ton of acid produced. Emission Reductions: Pollutants (tons per day) SO2
2020 1.40
Emission Reduction Trade-Offs: None Costs: BARCT limits of 0.2 lbs per ton of acid produced will require wet scrubbers at each of the three acid plants. One acid plant already has a wet scrubber, but it may need to be upgraded or replaced to meet the new standards. Capital costs are estimated at $7,000,000 for each facility, amortized to $700,000 annually. Operating costs are estimated at $200,000 per year at two facilities, and $300,000 per year for the third (higher caustic costs for higher SO2 reductions). Total costs are $2,800,000 per year. Co-Benefits: There will be less secondary PM2.5 formation from reduced sulfates. Issue/Impediments: None Sources (references): 1. 40 CFR part 60, subpart H, Standards of Performance for Sulfuric Acid Plants [42 FR 37936, July 25, 1977] 2. South Coast Air Quality Management District, Final Staff Report: Sox RECLAIM, Part 1, BARCT Assessment & RTC Analysis, November 2, 2010 3. US Environmental Protection Agency, RACT/BACT/LAER Clearinghouse (RBLC) Clean Air Technology Center 4. Bay Area Air Quality Management District, Regulation 9: Rule 1, Inorganic Gaseous Pollutants: Sulfur Dioxide, last amended March 1995
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