Process for separating acid gases and ammonia from dilute aqueous solutions thereof

• US 4,260,462 A
• Filed: 05/26/1978
• Issued: 04/07/1981
• Est. Priority Date: 05/26/1978
• Status: Expired due to Term

• Current Assignee: Aristech Chemical Corporation (Energy Transfer Operating, L.P.)
• Original Assignee: United States Steel Corporation (U.S. Steel)
• Inventors: Didycz, William J., Glassman, Donald, Maier, Edward E., Saniga, George T.
• Primary Examiner(s): BASCOMB JR, WILBUR
• Application Number:
  US05/909,861
• Time in Patent Office: 1,047 Days
• Field of Search: 203/22, 203/24, 203/26, 203/23, 203/25, 203/36, 203/37, 203/DIG. 9, 203/92, 203/96, 203/71, 203/73, 203/79, 203/85, 203/83, 203/80, 203/10, 203/11, 203/12, 203/27, 202/180, 202/154, 423/356, 423/357, 210/42 R
• US Class Current: 203/22
• CPC Class Codes: C02F 1/048 Purification of waste water by evaporation
• CPC Class Codes: C02F 1/586 by removing ammoniacal nitrogen for biological methods C02F3/00
• CPC Class Codes: C02F 3/1231 Treatments of toxic sewage
• CPC Class Codes: Y02W 10/10 Biological treatment of water, waste water, or sewage

Abstract

A process is described for the removal of acid gases and ammonia from dilute aqueous solutions. This is achieved by two separate and successive distillations. In the first distillation, substantially all of the acid gases and free ammonia are removed. In the second distillation, substantially all of the fixed ammonia is removed. Exemplary aqueous solutions are waste waters from coke oven and coal conversion plants.

Claims

1. A process for achieving substantially complete removal of acid gases and ammonia from a dilute aqueous solution thereof, said solution also containing free and fixed ammonia salts, said process comprising:

(a) subjecting said solution to a first counter-current multi-stage continuous distillation, said distillation being conducted by heating said solution, at least in part by means of a stripping vapor, and by having a gradient of ammonia concentration decreasing towards the region of bottom liquid withdrawal which results in said bottom liquid having a pH of less than about 8.0,

(i) withdrawing from this first distillation an overhead vapor stream containing a major proportion of stripping vapor, substantially all of said acid gases in said solution, and substantially all of the ammonia from said free ammonia salts,

(ii) withdrawing from this distillation an aqueous bottom stream which contains substantially all of said fixed ammonia salts;

(b) adding alkali to said withdrawn bottom stream, said alkali being added in an amount sufficient to evolve ammonia contained in the fixed ammonia salts during subsequent distillation of said mixture,

(c) subjecting said withdrawn bottom stream to a second counter-current multi-stage continuous distillation,

(i) withdrawing from this second distillation an overhead vapor stream said vapor stream containing a portion of the ammonia from the fixed ammonia salts,

(ii) withdrawing from this second distillation an aqueous bottom stream,

(d) vaporizing the aqueous bottom stream of step (a) at least in part, (1) by heating said bottom stream by means of indirect heat exchange with at least a portion of the overhead vapor stream being withdrawn in step (c) and (2) by conducting said first distillation at a pressure substantially less than the pressure of the second distillation.

2. The process of claim 1 wherein said indirect heat exchange includes the condensation of the overhead vapors from step (c) into a liquid fraction and a vapor fraction.

3. The process of claim 2 wherein said liquid fraction is returned to step (c) as reflux for said second distillation.

4. A process for achieving substantially complete removal of acid gases and ammonia from a dilute aqueous solution thereof, said solution also containing free and fixed ammonia salts, said process comprising:

(a) subjecting said solution to a first countercurrent multi-stage continuous distillation, said distillation being conducted by heating said solution, at least in part by means of a stripping vapor, and by having a gradient of ammonia concentration decreasing towards the region of bottom liquid withdrawal which results in said bottom liquid being in the acid range and wherein said distillation is conducted at a pressure in the range of about 0.3 to about 3 atmospheres absolute,

(i) withdrawing from this first distillation an overhead vapor stream containing a major proportion of stripping vapor comprising steam having a temperature in the range of about 140°

to 265°

F., substantially all of said acid gases in said solution and substantially all of the ammonia from said free ammonia salts,

(ii) withdrawing from this first distillation an aqueous bottom stream which contains substantially all of said fixed ammonia salts and has a temperature in the range of about 160°

to about 275°

F.,

(b) adding alkali to said withdrawn bottom stream and heating said bottom stream to a temperature in the range of about 155°

to about 270°

F., said alkali being added in an amount sufficient to evolve ammonia contained in the fixed ammonia salts during subsequent distillation of said mixture,

(c) subjecting said withdrawn bottom stream to a second, countercurrent multi-stage continuous distillation,

(i) withdrawing from this second distillation an overhead vapor stream having a temperature in the range of about 140°

to about 295°

F., said vapor stream comprising steam and a portion of the ammonia from the fixed ammonia salts,

(ii) withdrawing from this second distillation an aqueous bottom stream, said bottom stream being substantially free of acid gases and ammonia, and having a temperature in the range of about 160°

to about 185°

F.,

(d) vaporizing at least a portion of the aqueous bottom stream of step (a) to form a stripping vapor for use in step (a) by indirect heat exchange with at least a portion of the streams being withdrawn in step (c) to thereby achieve substantially complete removal of the free ammonia and acid gases from the liquid that is to be treated in the second distillation of step (c), and

wherein the ratio of solution flow to vapor flow within the columns is in the range of about 10/1 to 2/1 and wherein the first distillation is conducted at a pressure sufficiently less than the pressure of the second distillation to permit the overhead vapors of step (c) to provide sufficient heat by indirect heat exchange to vaporize the aqueous bottom stream of step (a).

5. A process according to claim 4 wherein said indirect heat exchange is by condensation of the overhead vapors from step (c) into a liquid fraction and a vapor fraction.

6. A process according to claim 5 wherein said liquid fraction is returned to step (c) as reflux for said second distillation.

7. A process according to claim 4 including an initial step of heating said aqueous solution by indirect heat exchange with at least a part of the heat contained in the overhead vapors from step (a) so that said solution has a temperature in the range of about 60°

to 212°

F.

8. A process according to claim 4 wherein said acid gases include at least one member selected from the group consisting of CO₂, SO₂, H₂ S, and HCN.

9. A process according to claim 8 wherein said member is HCN.

10. A process according to claim 4 wherein said aqueous solution includes a flushing liquor.

11. A process according to claim 4 wherein said aqueous solution is an effluent collected from the processing of coke-oven gas.

12. A process according to claim 4 wherein the said aqueous bottom stream from step (c) is subjected to biological degradation to reduce the content of toxic substances in said bottom water stream.

13. A process according to claim 4 wherein said overhead vapor stream withdrawn in step (a) comprises about 90 percent steam.

14. A process according to claim 4 wherein a portion of the heat required to step (a) is supplied by (i) direct injection of a stream comprising steam or (ii) indirect heat exchange with the liquids in step (a) or (iii) a combination of (i) and (ii).

15. A process according to claim 4 including the additional step of removing readily separable solids while adding said alkali to said withdrawn bottoms stream in step (b).

16. A method according to claim 4 wherein at least a portion of the heat required in the distillation of step (c) is supplied by direct injection of a stream comprising steam.

17. A process according to claim 4 wherein said acid gases and said free and fixed ammonia comprise up to 10 percent by weight of said aqueous solution.

18. A process according to claim 4 wherein said aqueous solution also contains tars, phenols, fluorides, chlorides, sulfates, thiosulfates, and thiocyanates, and includes the preliminary step of removing the tars prior to step (a).

19. A process according to claim 18 wherein said tars and phenols are in a concentration of from about 0.3 to about 15 grams per liter of solution.

20. A process according to claim 4 wherein said free ammonia is present in the range of about 50 to 50,000 parts per million.

21. A process according to claim 4 wherein said fixed ammonia is present in the range of about 50 to 50,000 parts per million.

22. A process according to claim 4 wherein said aqueous bottom stream in step (a) has a pH range of about 5 to about 6 when measured at 50°

C.

23. A process according to claim 4 wherein said aqueous bottom stream in step (a) has a concentration of free ammonia of about 40 to about 200 parts per million.

24. A process according to claim 4 wherein the vapor stream withdrawn in step (c) has a stripping vapor consisting essentially of steam.

25. A process according to claim 4 wherein step (c) is conducted at a pressure of up to about 60 psia.

26. A process according to claim 4 wherein said alkali added in step (b) is from the group of calcium hydroxide, sodium hydroxide, or potassium hydroxide.

27. A process according to claim 26 wherein said alkali added in step (b) is calcium hydroxide.

28. A process according to claim 27 wherein said alkali is sodium hydroxide.