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Sulfur and Sulfuric Acid

• Important raw materials for

fertilizer and chemical industries

Sulfur: Production and Use in North • Sulfuric acid is the world’s most
widely used chemical
America and the World
• Besides phosphate fertilizers,
used to produce ammonium
sulfate, potassium sulfate, and
D.L. Messick elemental sulfur-based fertilizers

Vice President
Canadian Rail Sulfur Transport

The Sulphur Institute

Sulfur Production Types Elemental Sulfur Production

48 million tons (2009)
• Elemental Sulfur or Brimstone
– Frasch/Native 1% mined
– Recovered
5% oil sands etc.
• Gas 47% oil
• Oil
• Other (increasingly oil
sands and heavy oils)

• Non-elemental 47% sour gas

– SOF (mostly smelter acid)
– Pyrites Sulfur and Sulfuric Acid Terminal, Rotterdam, The Netherlands

ICIS PentaSul

Sulfur Production Dynamics:

World Sulfur Production
A Changed Industry
(‘000 tons)

• Non-discretionary: Expanding
YEAR Production
– Recovered
2007 48,027
– SOF
2008 48,029
• Discretionary: Declining 2009 48,065
– Frasch/Native 2010 51,915
– Pyrites 2015 70,000
2020 82,000
Shantz: Canada Sulfur Vats Source: FRC

ICIS PentaSul

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World Sulfur Consumption Supply/Demand Balance

(‘000 tons) (‘000 tons)

YEAR Consumption Year Production Consumption Balance

2007 49,956 2007 48,027 49,956 -1,929
2008 45,269 2008 48,029 45,269 2,760
2009 46,819 2009 48,065 46,819 1,246
2010 52,225 2010 51,915 52,225 -310
2015 69,000 2015 70,000 69,000 1,000
2020 78,000 2020 82,000 78,000 4,000
Source: FRC
Source: FRC

ICIS PentaSul ICIS PentaSul

Internationally Traded Sulfur - 2009

Sulfur Consumption by End Use
Exports Imports
Kuwait
3% UAE Venz.
1%
Others
Oceania
2%
Morocco • Fertilizer (over 50%)
6% Canada 7% 11%

– Phosphates
Poland
20% Africa
1%
4%
Others
11% U.S.
• Phosphoric Acid
Iran
8%
• SSP
4%
India
Japan 5%
Russia

– Non-Phosphates
10% 5%
Tunisia
China
5%
43% North Carolina, USA Molten Sulfur Unloading for Phosphate Plant

Saudi ME • Ammonium Sulfate

5%
11%
Kaz+FSU Latin Am. • Potassium Sulfate
11% Europe 8%
• Elemental Sulfur-based fertilizers
Mexico W. Europe
U.S. 2%
2% 7%
8%
Source: FRC

28.3 million tons

ICIS PentaSul

Phosphate Fertilizer Consumption Phosphate Fertilizer Demand

By Country Forecast
(million tons)
50
8% 2009 forecast 2010 forecast
15%
45
Brazil
8% 19% India
China 40
6% other Asia
Europe
35
10% North America
other
34%
30
08/09 09/10 10/11 11/12 12/13 13/14 14/15

Source: IFA/FRC
ICIS PentaSul ICIS PentaSul

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14
Sulfur Consumption by End Use
(Continued)
Click
WorldtoSulfur
edit Master title 2009
- End Uses style
>90% used for Sulfuric Acid Production
• Non-Fertilizer (under 50%) Chemicals
3% 2% 2% 11%
– Caprolactam Ore Leaching 6%
7%
– Metallurgical Processing Phosphate
Ag. Chemicals
– Feed and Industrial Phosphates 10% Fertilizers
56%
– Titanium Dioxide
– Petroleum Refining
– Hydrofluoric Acid
Phosphate Fertilizers Other Fert./Ag Chem. Ore Leaching
– Pulp and Paper Industry
Petroleum Ref. Rubber/Plastics Pulp & Paper
– Other Pigments Chemicals

Approximate percentages

Mineral Fertilizer Processes MAP/DAP Gypsum

PR
NH3 (NH4)2SO4 ASN; ASP
Nutrient Source Intermediates Products
Sulfuric MOP Compound
Urea (N) SOP/MgKS
N Ammonia Acid PR (NPKS)
N from Air
Nitric Acid
SSP/TSP
AN, CAN (N)

P Phosphate Phosphoric Urea SA/S

Rock MAP/DAP (N,P)
Acid ES
Compound (NPKS)
AS (N, S)
K Potash Potash Dispersible ES
MOP/SOP (K,S,Cl)
Sulfur
Fertilizer S-Coated Fertilizer
SSP/TSP (P,S)
S Sulfur Sulfuric
Acid ATS,APS,KTS
Compound (NPK)

Nutrient Content (%) of High Analysis

Fertilizers
Sulfur Fertilizer Materials
Fertilizer N P2O5 K2O S
Anhydrous 82 0 0 0
• Fertilizers Containing Sulfate
Ammonia
DAP 16-21 46 0 0 • Fertilizers Containing Sulfur
Urea 46 0 0 0
Ammonium Nitrate 33 0 0 0 • Fertilizers Containing Other Forms of
MAP 11 50-51 0 0 Sulfur
TSP 0 45-46 0 0
Muriate of Potash 0 0 60-62 0

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Global Sulfur Fertilizers Fertilizer Containing Sulfate

• SSP and Ammonium Sulfate combined are 72% of total Global • Ammonium Sulfate
Sulfur use.
• Ammonium Nitrate-Sulfate
• New Sulfur fertilizers are gaining ground.
Ammonium Sulfate • Urea-Sulfate

19%
• NPKs with Sulfate
31% Single Superphosphate
5%
3% • Ammonium Phosphate-Sulfate
Potassium Sulfate
42%
• Single Superphosphate
Elemental-based &
Thiosulfates • Potassium Sulfate
S-NP/PK/NPK
• Potassium Magnesium Sulfate
• Various Micronutrient Sulfate Salts
Tiger-Sul; H.J. Baker Bros Inc

Fertilizer Containing Other Forms

Fertilizer Containing Sulfur of Sulfur (in Solution)

• Elemental Sulfur • Ammonium Thiosulfate (12-0-0-26S)

• Micronized Granular Elemental Sulfur • Ammonium Polysulfide (20-0-0-40S)
• Elemental Sulfur Modified/Enriched • Potassium Polysulfide (0-0-22-22S)
Nitrogen/Phosphate Fertilizers • Potassium Thiosulfate (0-0-25-17S)
• Sulfur Coated Fertilizers

Ammonium Sulfate Ammonium Nitrate-Sulfate

(21-0-0-24S) (26-0-0-14S)
• Ammonium-N and Sulfate-S Fertilizer;
• Increased N/S ratio for direct use by adding
• Recent World Output: 17 Mt, eq. over 4 Mt S; 2.7 Mt in
Western Europe ammonium nitrate (AN); popular in Europe
• Most are by-products from caprolactam production in
synthetic fiber industry and coke oven gas from steel • Made by granulating AS with AN solution or
industry. neutralizing H2SO4 with NH3 in AN solution
• Low Hygroscopicity and High Solubility
• Acid-Forming Reaction in Soils • Less hygroscopic, with a satisfactory N/S
ratio, and a combination of ammonium and
• Good for Saline and Alkaline Soils
nitrate forms of N; and sulfate form of S
• Good for Acid Requiring Crops
• Good for Direct, Blended, and Solution Uses

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Ammonium Nitrate Sulfate
(NH4)2SO4 NH4NO3 3NH3
+
NH4NO3*(NH4)2SO4
Urea-Sulfate Materials
(38 to 40-0-0-5 to 13S)
• 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 40-0-0-9S
and 38-0-0-13S have been released.
Phosphate Fertilizer Production
Ca10F2(PO4)6 + 10H2SO4 + 20H2O
SSP
10CaSO4*2H2O + 6H3PO4
3NH3
MAP/DAP (N,P)
2/20/2013
Ammonium Nitrate Sulfate
(26-0-0-14S)
• The product is sensitive to caking with an increased
moisture content (>0.2%),an internal dessicant is often
+ H2SO4
added to prevent caking.
NH4NO3
• Mixtures of AN and AS are affected by UN transportation
classification limits.
– If the AN content is < 45%: product non-hazardous
– If the AN content is >45% 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.
Single Superphosphate
(0-0-12 to 22-10 to 14S)
• Fertilizer containing soluble P, sulfate-S and
calcium (Ca); produced by reaction of H2SO4
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
Potassium Sulfate
(0-0-50-17S)
• 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.
• Cl free, low salt index and high solubility
+ 2HF
• Good for direct use or formulating bulk blending
fertilizers for Cl sensitive valuable cash crops
• Good for saline and alkaline soils; and salt
sensitive crops.
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Potassium Magnesium Sulfate Kieserite

(0-0-22-22S-11Mg) (0-0-0-20 to 23S-15 to 17.5Mg)

• Fertilizer containing K, Mg and sulfate-S; most • Fertilizer containing Mg and sulfate-S

produced by washing of Cl from langabeinite
• Neutral soil reaction
• Cl free, low salt index and high solubility
• High solubility
• Good for direct use or formulating bulk blending
fertilizer for Cl sensitive, valuable cash crops
• Used for direct application, blends and liquid
or foliar sprays
• Good for saline, acid and alkaline soils; and salt
sensitive crops.
• Available in granular and fine particle sizes

Gypsum Sulfate Containing Compound

(0-0-0-17 to 24S) Fertilizers
• 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
• Sulfate Containing Compound Fertilizers
• Containing sulfate-S and Ca; Good for direct use or can be produced by the nitrophosphate
incorporation with AN or NPK fertilizers as S source for process and/or the mixed acid route
soils low in these nutrients; and crops with high
demand of S and Ca (nitric/phosphoric, and sulfuric acid)
physical and chemical properties for both
• Gypsum, (anhydrite, hemihydrate, and dihydrate), can
be used as a S source to produce multinutrient direct application and formulating bulk
fertilizers. The most common grade produced from blends for various soils and crops
gypsum and AN is 24-0-0-6S. Here again, these
materials are subject to transport regulations.

Elemental Sulfur Recommended Particle Size

Recommended Particle Size Elemental Sulfur
• Concentrated sulfur carrier (90 to 99%S); for Maximum Agronomic Effectiveness
Water insoluble solid, and must be oxidized
to sulfate form before plant uptake Climatic Zone Cool-Temperate Warm-Humid

• Effects depends on: Annual <250 m

– Particle Size (<150 ) Application <150 m (50% <150 m)
– Method and time of application
– Soil conditions, e.g. temperature, water, and Biennial <250 m <500 m
microorganisms Application (50% <150 m) (50% <250 m)
Edmeades, 1994.

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Granular Dispersible Elemental Global Bentonite Sulfur

Sulfur Production Forecast - 2019
• High analysis (90 to 99%S) 2014 2019
2009 2008 Current
Region Production Production
Production Production
• Combined with 5-10% of swelling materials, such as Forecast Forecast
Bentonite and Lignosulfonate Oceania 25,000 50,000 75,000 10,000
Europe 50,000 175,000 275,000 19,000
• Dispersible in soil and water, releasing finely micronized North America 525,000 550,000 650,000 241,000
S particles (40 to 150 m), effectively converted into
sulfate by soil microorganisms in the early growing Middle East 150,000 480,000 605,000 62,000
season India 50,000 225,000 275,000 15,000
Africa 25,000 100,000 150,000 0
• Season long S supply with minimized risk of leaching
loss South America 25,000 100,000 200,000 2,000
Total 850,000 1,680,000 2,230,000 349,000
• Good physical and chemical properties for both direct
and blending uses

Tiger-Sul

Elemental Sulfur Enriched Elemental Sulfur Coated

Nitrogen/Phosphate Fertilizers 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 • Sulfur-Coated Urea (SCU): Slow or controlled
nutrients release N and S fertilizer (36-0-0-15S)

• A new sulfate and ES enriched MAP, containing
15%S, half ES and half sulfate-S provides crop S
nutrition in the entire growing season
• Sulfur enriched SSP (18-35% S) provides crop with
both immediate and reserve availability
• Good storage and handling properties
• Good nutrient availability and use efficiency
• 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 Ammonium Thiosulfate

Fertilizer Market
• The demand for micronized ES and ES-
modified 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
(12-0-0-26S)
• A clear liquid fertilizer containing NH 4–N and both SO4-S
and S0-S, produced by reacting of SO2 with aqueous
ammonia to form (NH4)2SO3, 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

• Other markets for ES fertilizer promising and ES, suitable to the S uptake patterns for most crops.

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Sulfur Fertilizer Reactions in Soils Additional Information

• Sulfur oxidation in soils:

CO2+S+0.5O2+2H2O -------CH2O + SO4 +2H+

• Provide sulfate for crop uptake and release 2H+ –Visit: www.sulphurinstitute.org
acidifying soil

• Reaction rate depending on soil microbial population,

sulfur properties and soil conditions: temperature, –Contact: DMessick@sulphurinstitute.org
moisture, pH, oxygen

• Weak SO4 adsorption depends on clay content, type,

Fe/Al oxides, pH, cations and anions