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Lecture Outline - Sulfuric Acid

- History of Manufacture Development

- Manufacture

- Oleum Production

- Heat Integration Issues / By-products

- Markets

- Usage in Caprolactam Manufacture

- Manufacture - Oleum Production - Heat Integration Issues / By-products - Markets - Usage in
- Manufacture - Oleum Production - Heat Integration Issues / By-products - Markets - Usage in

History of Manufacture of Sulfuric Acid

History of Manufacture of Sulfuric Acid • One of the oldest industrially applied processes. Discovered by

One of the oldest industrially applied processes. Discovered by a Persian alchemist in the tenth century.

Saltpeter and sulfur were mixed in a glass container and burned in a moist atmosphere. Acid was collected from the condensed vapors.

In England, 1746, the lead chamber reactor was invented. This invention allowed for higher production rates (<78%).

In England, 1831, a patent was filed that described the oxidation of sulfur dioxide over a platinum catalyst, the Contact Process. This new process increased yields of reaction from 70 to above 95%.

In 1913, BASF was granted a patent for the use of vanadium pentoxide as a catalyst for the Contact Process

By the 1930’s, vanadium pentoxide was becoming the dominate catalyst used because of insensitivities to poisons and lower cost.

In 1960 a patent application was filed by Bayer using the so called double-catalyst process (double absorption).

Manufacture

Three Step Process

1)

2)

3)

S

+

SO

SO

2

3

O 2

Manufacture Three Step Process 1) 2) 3) S + SO SO 2 3 O 2 SO

SO 2

+ 1/2O 2

Manufacture Three Step Process 1) 2) 3) S + SO SO 2 3 O 2 SO

+

H 2 O

Manufacture Three Step Process 1) 2) 3) S + SO SO 2 3 O 2 SO

SO 3

H 2 SO 4

Manufacture Three Step Process 1) 2) 3) S + SO SO 2 3 O 2 SO
Oxidation of Sulfur 1) S + O 2 SO 2 Air
Oxidation of Sulfur
1)
S
+
O 2
SO 2
Air

Sulfur

Oxidation of Sulfur 1) S + O 2 SO 2 Air Sulfur Steam Water 10-12% SO

Steam

Water
Water
of Sulfur 1) S + O 2 SO 2 Air Sulfur Steam Water 10-12% SO 2

10-12% SO2

93% H2SO4

O 2 SO 2 Air Sulfur Steam Water 10-12% SO 2 93% H 2 SO 4

Primary Generation of SO 2

-79% Combustion of Sulfur -9% Recovery from Metallurgic Processes - 5% Regeneration of Spent Acids

Process:

- Air drying tower with acid

- Sulfur is injected into burner

- Reaction Temperature 2000°F

- Exothermic reaction must be cooled

- Steam recovered

Oxidation of Sulfur Dioxide

Oxidation of Sulfur Dioxide Contact Process: -Vanadium pentoxide catalyst - Exothermic Reaction - Multiple Steps with

Contact Process:

-Vanadium pentoxide catalyst

- Exothermic Reaction

- Multiple Steps with cooling in between

- Double absorption

- Heat integration

SO2 Gas

Gas Cooling
Gas
Cooling

SO3 Gas

Oxidation of Sulfur Dioxide

Oxidation of Sulfur Dioxide  Because of the large effect temperature plays on the reaction, multiple

Because of the large effect temperature plays on the reaction, multiple catalyst layers are used, with cooling between each step.

Additionally, as the partial pressure of SO 3 increases, further reaction is limited.

This is overcome by removing the SO 3 after the third stage to drive the reaction to completion.

SO2 Gas

Gas Cooling
Gas
Cooling

SO3 Gas

SO2 Gas

after the third stage to drive the reaction to completion. SO 2 Gas Gas Cooling SO
after the third stage to drive the reaction to completion. SO 2 Gas Gas Cooling SO
after the third stage to drive the reaction to completion. SO 2 Gas Gas Cooling SO
after the third stage to drive the reaction to completion. SO 2 Gas Gas Cooling SO
after the third stage to drive the reaction to completion. SO 2 Gas Gas Cooling SO
after the third stage to drive the reaction to completion. SO 2 Gas Gas Cooling SO
after the third stage to drive the reaction to completion. SO 2 Gas Gas Cooling SO
after the third stage to drive the reaction to completion. SO 2 Gas Gas Cooling SO
SO3 Gas
SO3 Gas

93% H2SO4

Oxidation of Sulfur Dioxide

Oxidation of Sulfur Dioxide • Kinetic Effects - Oxidation of sulfur dioxide is slow and reversible

Kinetic Effects - Oxidation of sulfur dioxide is slow and reversible - The reaction requires a catalyst and 426.7°C temperatures

-The reaction is exothermic and sensitive to excessive heat

• Equilibrium Constant (The degree at which the reaction proceeds is temp. dependent)

log Kp = 4.956 - 4.678

T

T = absolute temp. in kelvin Kp = equilibrium constant as a function of partial pressure of gases

Kp =

( PSO 3 ) PSO 2 PO 2
( PSO 3 )
PSO 2 PO 2

0.5

Oxidation of Sulfur Dioxide

Temperature Profile

Oxidation of Sulfur Dioxide Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2

SO2 Gas

Gas Cooling
Gas
Cooling

SO3 Gas

SO2 Gas

Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas
Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas
Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas
Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas
Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas
Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas
Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas
Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas
Temperature Profile SO 2 Gas Gas Cooling SO 3 Gas SO 2 Gas SO 3 Gas

SO3 Gas

510 C 430 C
510 C
430 C

200 C

75 C

125 C

93% H2SO4

Oxidation of Sulfur Dioxide

Temperature Profile

Oxidation of Sulfur Dioxide Temperature Profile

Oxidation of Sulfur Dioxide

Typical Catalyst Distribution

Catalyst

Bed

% Catalyst

Conversion %

1

19.4

56

2

25.0

87

3

26.7

99.1

4

28.9

99.7

Catalyst Bed % Catalyst Conversion % 1 19.4 56 2 25.0 87 3 26.7 99.1 4

Overall Production Scheme

Overall Production Scheme
Overall Production Scheme

Oleum Production

Oleum Production  Sulfuric acid with additional SO 3 absorbed  20% Oleum contains 20% SO

Sulfuric acid with additional SO 3 absorbed

20% Oleum contains 20% SO 3 by weight in the oleum

Common strengths of oleum are 20, 30, 40, 65 percent.

To produce 20 and 30 percent oleum, only requires an additional absorption tower.

Oleum is used in reactions where water is excluded

SO 3 + H 2 SO 4

 Oleum is used in reactions where water is excluded SO 3 + H 2 SO

H 2 S 2 O 7

(disulfuric acid)

Reaction By-products / Heat Integration

By-products

Reaction By-products / Heat Integration By-products  57 to 64% of the energy input generates steam

57 to 64% of the energy input generates steam

Steam energy is used to drive the turbine that supplies power to the main air blower

Additional steam remaining is tolled internally for other plant operations

SO2/SO3 is vented in small amounts and is federally regulated.

Heat Integration

Steam is used to pre-heat and vapor from the absorption towers used to cool

Minimizes the cost of manufacturing to maximize the profit.

Production Considerations

Production Considerations  Metal corrosion is a big issue in the manufacture of sulfuric acid. 

Metal corrosion is a big issue in the manufacture of sulfuric acid.

Special alloy metals must be used to guard against excessive corrosion.

Nickel, chromium, molybdenum, copper, an silicon are the most important elements that enhance corrosion resistance of alloys.

Important variables for corrosion Concentration of the acid Temperature of service Speed of flow in pipes and equipment Alloy element make-up

World Production of Sulfuric Acid

World Production of Sulfuric Acid Canada Mexico Others Japan Latin F-USSR Europe Africa U.S. Asia 0.0
Canada Mexico Others Japan Latin F-USSR Europe Africa U.S. Asia 0.0 5.0 10.0 15.0 20.0
Canada
Mexico
Others
Japan
Latin
F-USSR
Europe
Africa
U.S.
Asia
0.0
5.0
10.0
15.0
20.0
25.0
30.0

Share (percent)

World Supply / Demand for Sulfuric Acid

(thousands of metric tons, 100% H 2 SO 4 )

Acid (thousands of metric tons, 100% H 2 SO 4 ) 2000 1997 1994 1991 1988

2000
1997
1994
1991

1988
1985

250,000

200,000

150,000

100,000

50,000

2000 1997 1994 1991 1988 1985 250,000 200,000 150,000 100,000 50,000 0 Annual Capacity Production
2000 1997 1994 1991 1988 1985 250,000 200,000 150,000 100,000 50,000 0 Annual Capacity Production
2000 1997 1994 1991 1988 1985 250,000 200,000 150,000 100,000 50,000 0 Annual Capacity Production
2000 1997 1994 1991 1988 1985 250,000 200,000 150,000 100,000 50,000 0 Annual Capacity Production
2000 1997 1994 1991 1988 1985 250,000 200,000 150,000 100,000 50,000 0 Annual Capacity Production
0
0
2000 1997 1994 1991 1988 1985 250,000 200,000 150,000 100,000 50,000 0 Annual Capacity Production

Annual Capacity

2000 1997 1994 1991 1988 1985 250,000 200,000 150,000 100,000 50,000 0 Annual Capacity Production

Production

Markets for Sulfuric Acid

Markets for Sulfuric Acid  The fertilizer market is the largest U.S. single use for sulfuric

The fertilizer market is the largest U.S. single use for sulfuric acid and consumes 50-65 percent of all produced.

Second is the organic chemical industry. Production of plastics and synthetic fibers are examples.

Production of TiO2 consumes large quantities of sulfuric acid. TiO2 is a white pigment used in paints and plastics.

In the metal industry, sulfuric acid is used for pickling ferrous and non- ferrous materials and in the recovery of copper, nickel, and zinc from low-grade ores.

Finally, the petroleum industry uses acid as a catalyst for various reactions.

Acid Strengths

Associated End Uses

Acid Strengths Associated End Uses Percent H 2 SO 4 Uses 35.67 Storage batteries, electric utilities

Percent H 2 SO 4

Uses

35.67 Storage batteries, electric utilities

62.18 Normal superphosphate and other fertilizers 69.65

62.18

Normal superphosphate and other fertilizers

69.65

77.67 Normal superphosphate and other fertilizers, isopropyl and sec-butyl alcohols

80.00 Copper leaching

93.19 Phosphoric acid, tianium dioxide, steel pickling, regenerating ion exchange resins of utilities

98-99

Chlorine drying, alkylation, boric acid

104.50 Surfactants, nitrations, hydrofluoric acid 106.75

104.50

Surfactants, nitrations, hydrofluoric acid

106.75

109.00

Explosives

111.25 113.50 114.63 Reagent manufacture, organic sulfonations, blending with weaker acids

111.25

113.50

114.63

Reagent manufacture, organic sulfonations, blending with weaker acids

Usage in Caprolactam Manufacture

Usage in Caprolactam Manufacture Production and consumption figures for caprolactam manufacture Caprolactam Production

Production and consumption figures for caprolactam manufacture

Caprolactam Production Rate H2SO4 Consumption (100% Acid) Oleum Consumption Ammonium Sulfate Production

120,000 ton/yr 636 kg per ton of CPL 1300kg per ton of CPL 312,000 ton/yr

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