Condensing sulfuric acid vapors to produce sulfuric acid

• US 5,198,206 A
• Filed: 12/06/1990
• Issued: 03/30/1993
• Est. Priority Date: 06/09/1988
• Status: Expired due to Term

• Current Assignee: Haldor Topsã¸E A/S (Haldor Topsã¸E Holding A/S)
• Original Assignee: Haldor Topsã¸E A/S (Haldor Topsã¸E Holding A/S)
• Inventors: Schoubye, Peter
• Primary Examiner(s): HELLER, GREGORY
• Application Number:
  US07/623,409
• Time in Patent Office: 845 Days
• Field of Search: 434/522, 434/528, 434/529
• US Class Current: 423/522
• CPC Class Codes: B01D 53/8609 Sulfur oxides
• CPC Class Codes: C01B 17/76 by contact processes
• CPC Class Codes: C01B 17/806 Absorbers; Heat exchangers

Abstract

When condensing sulfuric acid from gases containing sulfuric acid vapor and steam in excess, e.g. originating from a power station, a substantial decrease of the amount minute droplets of sulfuric acid (the so-called acid mist) escaping to the surroundings is obtained, even in cases where the sulfuric acid plant is equipped with an aerosol filter, if minute nucleation cores are incorporated into the gas in an amount of 10⁹ to 10¹² solid particles per Nm³ per 0.1 % H₂ SO₄ -vapor in the gas. The nucelation cores may, e.g., be generated by combusting hydrocarbons with>2 carbon atoms or silicones, or added as smoke from an electric arc or welding.

Claims

1. A process for producing sulfuric acid comprising condensing sulfuric acid vapors from a gas mixture containing 0.01 to 10% by vol. of H₂ SO₄ vapor, calculated under the assumption that SO₃ is fully hydrated, and 0 to 50% by vol. of aqueous vapor, by direct or indirect cooling in a sulfuric acid tower, including the step of adding before inflow of the gas into the tower a smoke or an aerosol of solid particles having a content of 10⁹ to 10¹² solid particles per Nm³ per 0.1% H₂ SO₄ vapor in the gas at entry thereof into the tower, calculated under the assumption that SO₃ in the tower is completely hydrated to H₂ SO₄.

2. A process as claimed in claim 1, wherein the cooling of the gas mixture takes place in a packed sulfuric acid tower countercurrently with circulating sulfuric acid as coolant.

3. A process as claimed in claim 1, wherein the cooling of the gas mixture takes place in substantially vertical, externally cooled tubes in which the gas mixture flows from a bottom of the tubes in an upward direction in countercurrent with an external coolant.

4. A process as claimed in claim 3, wherein a gaseous coolant is employed.

5. A process as claimed in claim 3, further comprising condensing the sulfuric acid vapors which after the condensing flow downwards through the tubes as liquid, highly concentrated sulfuric acid, said sulfuric acid vapors originating from a feed gas containing 0.01 to 10% by vol. of H₂ SO₄ vapor, calculated under the assumption that SO₃ in the tower is completely hydrated to H₂ SO₄, and 0 to 50% by vol. of H₂ O vapor, the feed gas being admitted from the bottom at a temperature of at least the dew point of sulfuric acid at the conditions of pressure and temperature prevailing in the tube, the feed gas being cooled during the flow in the upward direction to an exit temperature T₂ which is lower than the temperature at which the vapor pressure of H₂ SO₄ is about 2×

10^-6 bar in equilibrium with the partial pressure of aqueous vapor prevailing at the outlet of the tubes in the top, the tubes being cooled externally with a gaseous medium flowing substantially countercurrently with the sulfuric acid-containing gas, said gaseous medium thereby being heated from an inlet temperature TA₁ of 0°

to 50°

C. to an outlet temperature TA₂ satisfying the condition

space="preserve" listing-type="equation">TA.sub.2 <

T.sub.4 -30-10α

°

C.

where T₄ is the sulfuric acid dew point, expressed in °

C., of the gas passed to the tubes and α

is % by vol. of sulfuric acid vapor, calculated under the assumption that SO₃ in the gas is completely hydrated to H₂ SO₄.

6. A process as claimed in claim 5, further comprising means for separating droplets of sulfuric acid present in the gas mounted near, in or on top of each tube in gas tight connection therewith, said droplets flowing back from said means, downwards through the tube.

7. A process as claimed in claim 1, wherein solid particles having a diameter below 1μ

m are added to the gas.

8. A process as claimed in claim 7, wherein solid particles having a diameter of 0.002 to 0.1μ

m are added to the gas.

9. A process as claimed in claim 1, further comprising the step of purifying feed gas for contents of solid particles originally present before adding the solid particles.

10. A process as claimed in claim 1, wherein the step of adding the solid particles comprises adding the solid particles to a feed gas stream containing SO₂ and a stoichiometric excess of H₂ O, said gas stream thereafter being passed through a layer of a sulfuric acid catalyst at a temperature of 360°

to 500°

C. to oxidize SO₂ to SO₃, the SO₃ being hydrated under the influence of aqueous vapor.

11. A process is claimed in claim 10, further comprising the step of cooling the gas stream to a temperature in the range of 0°

to 200°

C. above the sulfuric acid dew point of the gas stream before admitting the gas stream into the sulfuric acid tower.

12. A process as claimed in claim 1, wherein the step of adding the solid particles comprises adding smoke from combustion of hydrocarbons in a burner to the gas mixture, the air fuel ratio in the burner being continually adjusted by means of an automatic regulation loop containing an analyzer for measuring sulfuric acid droplets content in the gas mixture after the gas has left the sulfuric acid tower, signals from the analyzer continually adjusting and correcting the air/fuel ratio.

13. A process as claimed in claim 1, wherein the step of adding the solid particles comprises adding smoke from the combustion of hydrocarbons to the gas mixture, the amount of smoke from the combustion of hydrocarbons added being continually adjusted by means of an automatic regulation loop containing an analyzer for measuring sulfuric acid droplets content in the gas mixture after it has left the sulfuric acid tower, signals from the analyzer continually adjusting and correcting the amount of smoke admitted.

14. A process as claimed in claim 12, wherein the smoke from the combustion of hydrocarbons contains at least 2 carbon atoms per molecule.

15. A process as claimed in claim 1, wherein the step of adding the solid particles comprises adding the particles in the form of smoke from metal or metal oxides generated in an electric arc.

16. A process as claimed in claim 1, further comprising the step of setting the automatic regulation loop so as to ensure a sulfuric acid droplets content in discharge gas below 10 ppm of H₂ SO₄.

17. A process as claimed in claim 1, wherein the step of adding the solid particles comprises adding the particles as an aerosol of a solution of a metal salt or a suspension of particles, liquid present in the aerosol being evaporated before the aerosol reaches the sulfuric acid tower.

18. A process as claimed in claim 10 wherein the feed gas stream is a stream of dust-containing fuel gas from combustion of fossil fuel, and

(i) the gas stream is divided before reaching the catalyst or between the catalyst and the sulfuric acid tower into a first stream from which substantially all particles are removed and a second stream from which at most particles having a diameter above about 0.5 μ

m are removed, and

(ii) the first and second streams are united before reaching the sulfuric acid tower.

19. A process as claimed in claim 1, wherein the step of adding the solid particles comprises providing the particles by combusting together with a fluid fuel, a silicon-containing component selected from the group consisting of silicone oils and siloxanes, smoke from the combustion of the silicon-containing component being admixed into the gas mixture.