2/20/2013. Sulfur and Sulfuric Acid. Sulfur: Production and Use in North America and the World. Sulfur Production Types. Elemental Sulfur Production

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1 Sulfur and Sulfuric Acid Important raw materials for fertilizer and chemical industries Sulfur: and Use in North America and the World D.L. Messick Vice President The Sulphur Institute Sulfuric acid is the world s most widely used chemical Besides phosphate fertilizers, used to produce ammonium sulfate, potassium sulfate, and elemental sulfur-based fertilizers Canadian Rail Sulfur Transport Sulfur Types Elemental Sulfur Elemental Sulfur or Brimstone Frasch/Native Recovered Gas Oil Other (increasingly oil sands and heavy oils) Non-elemental SOF (mostly smelter acid) Pyrites Sulfur and Sulfuric Acid Terminal, Rotterdam, The Netherlands 48 million tons (2009) 47% oil 47% sour gas 1% mined oil sands etc. Sulfur Dynamics: A Changed Industry Non-discretionary: Expanding Recovered SOF Discretionary: Declining Frasch/Native Pyrites Shantz: Canada Sulfur Vats ( 000 tons) World Sulfur YEAR , , , , , ,000 Source: FRC 1

2 ( 000 tons) Source: FRC World Sulfur Consumption YEAR Consumption , , , , , ,000 ( 000 tons) Supply/Demand Balance Year Consumption Balance ,027 49,956-1, ,029 45,269 2, ,065 46,819 1, ,915 52, ,000 69,000 1, ,000 78,000 4,000 Source: FRC Internationally Traded Sulfur Sulfur Consumption by End Use Exports Kuwait 3% UAE Venz. 6% 1% Poland 1% Others Russia 10% Kaz+FSU Mexico U.S. 2% 8% Canada 20% Iran 4% Japan Saudi W. Europe 7% China 43% Imports Oceania Others Morocco 2% 7% Africa 4% U.S. 8% India Tunisia ME Latin Am. Europe 8% 2% Fertilizer (over 50%) Phosphates Phosphoric Acid SSP Non-Phosphates North Carolina, USA Molten Sulfur Unloading for Phosphate Plant Ammonium Sulfate Potassium Sulfate Elemental Sulfur-based fertilizers Source: FRC 28.3 million tons 8% 6% Phosphate Fertilizer Consumption By Country 10% 1 8% 34% 19% Brazil India China other Asia Europe North America other (million tons) Phosphate Fertilizer Demand Forecast 2009 forecast 2010 forecast 08/09 09/10 10/11 11/12 12/13 13/14 14/15 Source: IFA/FRC 2

3 Non-Fertilizer (under 50%) Caprolactam Metallurgical Processing Sulfur Consumption by End Use (Continued) Feed and Industrial Phosphates Titanium Dioxide Petroleum Refining Hydrofluoric Acid Pulp and Paper Industry Other Ore Leaching 7% Ag. Chemicals 10% Click World to Sulfur edit Master - End Uses title 2009 style >90% used for Sulfuric Acid 6% 3% 2% 2% Chemicals Phosphate Fertilizers 56% Phosphate Fertilizers Other Fert./Ag Chem. Ore Leaching Petroleum Ref. Rubber/Plastics Pulp & Paper Pigments Chemicals 14 Approximate percentages Nutrient Source Intermediates Products N N from Air Mineral Fertilizer Processes Ammonia Nitric Acid Urea (N) AN, CAN (N) Sulfuric Acid PR NH 3 MOP PR MAP/DAP (NH 4 ) 2 SO 4 SOP/MgKS SSP/TSP Gypsum ASN; ASP Compound (NPKS) P Phosphate Rock Phosphoric Acid MAP/DAP (N,P) ES Urea SA/S AS (N, S) Compound (NPKS) K S Potash Sulfur Potash Sulfuric Acid MOP/SOP (K,S,Cl) SSP/TSP (P,S) Compound (NPK) Sulfur Fertilizer Dispersible ES S-Coated Fertilizer ATS,APS,KTS Nutrient Content (%) of High Analysis Fertilizers Fertilizer N P 2 O 5 K 2 O S Anhydrous Ammonia DAP Urea Ammonium Nitrate MAP TSP Muriate of Potash Sulfur Fertilizer Materials Fertilizers Containing Sulfate Fertilizers Containing Sulfur Fertilizers Containing Other Forms of Sulfur 3

4 3% 19% Tiger-Sul; H.J. Baker Bros Inc Global Sulfur Fertilizers SSP and Ammonium Sulfate combined are 72% of total Global Sulfur use. New Sulfur fertilizers are gaining ground. 42% 31% Ammonium Sulfate Single Superphosphate Potassium Sulfate Elemental-based & Thiosulfates S-NP/PK/NPK Fertilizer Containing Sulfate Ammonium Sulfate Ammonium Nitrate-Sulfate Urea-Sulfate NPKs with Sulfate Ammonium Phosphate-Sulfate Single Superphosphate Potassium Sulfate Potassium Magnesium Sulfate Various Micronutrient Sulfate Salts Fertilizer Containing Sulfur Elemental Sulfur Micronized Granular Elemental Sulfur Elemental Sulfur Modified/Enriched Nitrogen/Phosphate Fertilizers Sulfur Coated Fertilizers Fertilizer Containing Other Forms of Sulfur (in Solution) Ammonium Thiosulfate ( S) Ammonium Polysulfide ( S) Potassium Polysulfide ( S) Potassium Thiosulfate ( S) Ammonium Sulfate ( S) Ammonium-N and Sulfate-S Fertilizer; Recent World Output: 17 Mt, eq. over 4 Mt S; 2.7 Mt in Western Europe Most are by-products from caprolactam production in synthetic fiber industry and coke oven gas from steel industry. Low Hygroscopicity and High Solubility Acid-Forming Reaction in Soils Good for Saline and Alkaline Soils Good for Acid Requiring Crops Ammonium Nitrate-Sulfate ( S) Increased N/S ratio for direct use by adding ammonium nitrate (AN); popular in Europe Made by granulating AS with AN solution or neutralizing H 2 SO 4 with NH 3 in AN solution Less hygroscopic, with a satisfactory N/S ratio, and a combination of ammonium and nitrate forms of N; and sulfate form of S Good for Direct, Blended, and Solution Uses 4

5 (NH 4 ) 2 SO 4 + Ammonium Nitrate Sulfate 3NH H 2 SO 4 NH 3 4 NO 3 NH 4 NO 3 NH 4 NO 3 *(NH 4 ) 2 SO 4 + Ammonium Nitrate Sulfate ( S) The product is sensitive to caking with an increased moisture content (>0.2%),an internal dessicant is often added to prevent caking. Mixtures of AN and AS are affected by UN transportation classification limits. If the AN content is < 4: product non-hazardous If the AN content is >4 but less than 70% and the total combustible material content is less than 0.4% then UN class 5.1 (an oxidizer) under UN 2069 If the AN content is >70% and the product contains ammonium sulfate: it is prohibited as a fertilizer Other local regulations may also apply. The safety concerns are forcing down the AN content. Urea-Sulfate Materials (38 to to 13S) Single Superphosphate ( to to 14S) Good physical and chemical properties result in considerable flexibility in the correction of N and S deficiencies in most soils; and suitable for various uses. In Europe, products with grades S and S have been released. Fertilizer containing soluble P, sulfate-s and calcium (Ca); produced by reaction of H 2 SO 4 with phosphate rock World output: 34 Mt, eq. 4.0 Mt S, mostly in China, Brazil, India, Australia and New Zealand Good for direct use; also used in manufacture of other sulfur fertilizers; used for crops with high demand of S and Ca Phosphate Fertilizer Ca 10 F 2 (PO 4 ) H 2 SO 4 20H 2 O + Potassium Sulfate ( S) Fertilizer containing K and sulfate-s World annual production: 1.6 Mt, eq. 0.3 Mt S; Half is mined directly; and half is produced by reaction of KCl with sulfuric acid. SSP 10CaSO 4 *2H 2 O + 6H 3 PO 4 + 2HF Cl free, low salt index and high solubility Good for direct use or formulating bulk blending fertilizers for Cl sensitive valuable cash crops 3NH 3 MAP/DAP (N,P) Good for saline and alkaline soils; and salt sensitive crops. 5

6 Potassium Magnesium Sulfate ( S-11Mg) Fertilizer containing K, Mg and sulfate-s; most produced by washing of Cl from langabeinite Cl free, low salt index and high solubility Good for direct use or formulating bulk blending fertilizer for Cl sensitive, valuable cash crops Good for saline, acid and alkaline soils; and salt sensitive crops. Kieserite ( to 23S-15 to 17.5Mg) Fertilizer containing Mg and sulfate-s Neutral soil reaction High solubility Used for direct application, blends and liquid or foliar sprays Available in granular and fine particle sizes Gypsum ( to 24S) Not widely used as a fertilizer because of the poor physical form and low analysis: exception peanuts require Ca for pegging and helps meet sulfur needs Containing sulfate-s and Ca; Good for direct use or incorporation with AN or NPK fertilizers as S source for soils low in these nutrients; and crops with high demand of S and Ca Gypsum, (anhydrite, hemihydrate, and dihydrate), can be used as a S source to produce multinutrient fertilizers. The most common grade produced from gypsum and AN is S. Here again, these materials are subject to transport regulations. Sulfate Containing Compound Fertilizers Sulfate Containing Compound Fertilizers can be produced by the nitrophosphate process and/or the mixed acid route (nitric/phosphoric, and sulfuric acid) physical and chemical properties for both direct application and formulating bulk blends for various soils and crops Elemental Sulfur Concentrated sulfur carrier (90 to 99%S); Water insoluble solid, and must be oxidized to sulfate form before plant uptake Recommended Particle Size Recommended Particle Size Elemental Sulfur for Maximum Agronomic Effectiveness Climatic Zone Cool-Temperate Warm-Humid Effects depends on: Particle Size (<150 ) Method and time of application Soil conditions, e.g. temperature, water, and microorganisms Annual Application Biennial Application <150 m <250 m (50% <150 m) <250 m (50% <150 m) <500 m (50% <250 m) Edmeades,

7 Granular Dispersible Elemental Sulfur High analysis (90 to 99%S) Combined with 5-10% of swelling materials, such as Bentonite and Lignosulfonate Dispersible in soil and water, releasing finely micronized S particles (40 to 150 m), effectively converted into sulfate by soil microorganisms in the early growing season Season long S supply with minimized risk of leaching loss Good physical and chemical properties for both direct and blending uses Region Global Bentonite Sulfur Forecast Forecast 2019 Forecast 2008 Current Oceania 25,000 50,000 75,000 10,000 Europe 50, , ,000 19,000 North America 525, , , ,000 Middle East 150, , ,000 62,000 India 50, , ,000 15,000 Africa 25, , ,000 0 South America 25, , ,000 2,000 Total 850,000 1,680,000 2,230, ,000 Tiger-Sul Elemental Sulfur Enriched Nitrogen/Phosphate Fertilizers Spray liquid S to TSP, Urea, MAP or DAP during drum or pan granulation to provide 5-20% S with N and P nutrients A new sulfate and ES enriched MAP, containing 1S, half ES and half sulfate-s provides crop S nutrition in the entire growing season Sulfur enriched SSP (18-3 S) provides crop with both immediate and reserve availability Good storage and handling properties Good nutrient availability and use efficiency Elemental Sulfur Coated Nitrogen/Phosphate Fertilizers Sulfur-Coated Urea (SCU): Slow or controlled release N and S fertilizer ( S) Sulfur Coated TSP; Sulfur Coated DAP/MAP Good for direct use to meet crop N, P and S needs in a long growing season, S may not be available to correct deficiencies during the early season New products made by coating urea with micronized S using oil and Ca-Lignosulfonate as a binder for use on rice, sugarcane, grass, fruits Elemental Sulfur Fertilizer Market The demand for micronized ES and ESmodified compound fertilizers is increasing worldwide, esp. in Oceania, North America, India and to some degree in West Europe. In North America, ES fertilizer consumption: 200,000 t in 2000, and 400,000 t in 2010 Other markets for ES fertilizer promising Ammonium Thiosulfate ( S) A clear liquid fertilizer containing NH 4 N and both SO 4 -S and S 0 -S, produced by reacting of SO 2 with aqueous ammonia to form (NH 4 ) 2 SO 3, and then further reacts with S0 to form ATS, under low oxygen condition. Widely used in the fluid fertilizer industry to make a wide range of N-P-K-S fertilizers; However, it is not compatible with acidic solutions, and not with anhydrous ammonia. Used directly by drip, sprinkler or flood irrigation It decomposes in the soil to form equal amount of sulfate and ES, suitable to the S uptake patterns for most crops. 7

8 Sulfur Fertilizer Reactions in Soils Additional Information Sulfur oxidation in soils: CO 2 +S+0.5O 2 +2H 2 O CH 2 O + SO 4 +2H+ Provide sulfate for crop uptake and release 2H+ acidifying soil Visit: Reaction rate depending on soil microbial population, sulfur properties and soil conditions: temperature, moisture, ph, oxygen Contact: DMessick@sulphurinstitute.org Weak SO 4 adsorption depends on clay content, type, Fe/Al oxides, ph, cations and anions 8

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