Continuous process for recovering pure, concentrated ammonia

• US 4,060,591 A
• Filed: 05/25/1976
• Issued: 11/29/1977
• Est. Priority Date: 06/24/1975
• Status: Expired due to Term

• Current Assignee: Metallgesellschaft AG (GEA Group AG), Chemie Linz AG (Thermo Fisher Scientific Incorporated)
• Original Assignee: Metallgesellschaft AG (GEA Group AG), Chemie Linz AG (Thermo Fisher Scientific Incorporated)
• Inventors: Wiesner, Paul, Stonner, Hans-Martin, Schmidt, Alfred, Sinclair, Alan, Garber, Alfred
• Primary Examiner(s): Meros, Edward J.
• Application Number:
  US05/690,203
• Time in Patent Office: 553 Days
• Field of Search: 423/352, 423/234, 423/237, 423/238, 423/236, 55/36, 55/38, 55/39, 55/70
• US Class Current: 423/352
• CPC Class Codes: C01C 1/10 Separation of ammonia from ammonia liquors, e.g. gas liquors as part of the ammonia synthesis process C01C1/04

Abstract

Pure, concentrated ammonia is recovered from aqueous liquors by stripping off gas water, de-acidifications, scrubbing and withdrawing ammonia from the top of a scrubbing column.

Claims

1. In a continuous process of recovering pure, concentrated ammonia, which contains not more than 0.2% H₂ O, 0.1% CO₂, 10 ppm H₂ S, and 10 ppm HCN, from aqueous liquors from which dust, tar, oil, and phenols have been removed, said aqueous liquors being condensates formed during the gasification or degasification of coal, or from aqueous liquors of similar compositions which contain free and/or combined ammonia in concentrations between 0.1 and 12 n carbon dioxide in concentrations between 0.1 and 12 n, hydrogen sulfide in concentrations between 0.003 and 3 n hydrocyanic acid in concentrations between 0.001 to 1 g/l, and residual organic substances introduced during a preceding dephenolation, which process includes the steps of stripping off gas water, de-acidification, scrubbing, and withdrawing ammonia from the top of a scrubbing column, the improvement which comprises the following steps:

a. stripping ammonia from the aqueous liquor in a stripping column having 15-80 actual plates or equivalent packing columns operated under a pressure of 1-2 bars with an inlet temperature of 30°

-90°

C, the ammonia and the acid constituents being jointly withdrawn overhead and waste water being withdrawn from the sump of the column,

b. scrubbing the overhead product from (a) with an aqueous solution containing surplus ammonia from which the acid constituents have been substantially removed under a pressure of 1-2 bars and at temperatures of 30°

-70°

C withdrawing pure ammonia overhead and subjecting it to a fine purification by liquification and treatment to remove inert constituents;

c. stripping most of the residual ammonia from the spent scrubbing liquor from (b) in a stripping column having 3-25 plates, or equivalent packing columns, operated under 1-2 bars, top temperatures of 50°

-80°

C, and sump temperatures of 60°

-90°

C, and withdrawing ammonia overhead and recycling it to (b); and

d. de-acidifying aqueous solutions having a (CO₂ + H₂ S) ;

NH ratio ≧

1 under superatmospheric pressure by stripping the acid constituents in a pressure de-acidification column operated under a pressure of 3-25 bars, and sump temperatures of 110°

-180°

C, and withdrawing same from the top of said column;

said steps being carried out in the sequence a), b), c), d), with the sump product of step c) being subjected to step d) in the processing of solutions in which the (CO₂ + H₂ S) ;

NH₃ weight ratio ≦

1 whereas the feed solution is subjected to the pressure de-acidification step d) and this is succeeded by steps a), b), c) in the processing of solutions having a (CO₂ + H₂ S) ;

NH₃ weight ratio >

1.

2. Process of claim 1 werein the sump product from the pressure de-acidification column used in step d) is used in part as scrubbing liquor in scrubbing step b) and is fed in part to stripping step a).

3. Process of claim 1 wherein 5-20% of the waste water withdrawn from the sump of the stripping column used in step a) is cooled and fed as aqueous scrubbing liquor to the top of the pressure de-acidification column used in step d).

4. Process of claim 1 wherein liquid ammonia is mixed with water, the resulting mixture is cooled to or below 40°

C and is then conducted in a countercurrent to the ammonia vapors in the top portion of the scrubbing column used in step b).

5. Process of claim 1 wherein heat exchangers associated with the pressure de-acidification column are fed with air.

6. Process of claim 1 wherein residual solvent which becomes enriched in the upper portion of the pressure de-acidification column used in step d) are removed by a separator disposed within the pressure de-acidification column recycled to a preceding phenol extraction process.

7. Process of claim 1 wherein 5-25%, by weight of the feed for the pressure de-acidification column used in step d) are branched off and cooled and fed to said column in an intermediate portion thereof disposed above the inlet for the major part of the mixture to be processed and below the scrubbing section of the column used in step d) whereas a major part of the mixture to be processed is heated in a heat exchanger by means of the sump product of the column.

8. Process of claim 1 wherein the stripping of ammonia from the aqueous liquor in step (a) is performed in a stripping column having 40 to 60 actual plates;

9. Process of claim 1 wherein the stripping column in step (a) is operated with an inlet temperature of 40°

to 60°

C;

10. Process of claim 1 wherein the stripping of ammonia from the spent scrubbing liquor in step (c) is performed in a column having 5 to 15 plates;

11. Process of claim 1 wherein the top temperatures of the column in step (c) is 55°

to 70°

C and the sump temperature 70°

to 80°

C;

12. Process of claim 1 wherein the stripping of the acid constituents in step (d) is performed in a pressure deacidification column under a pressure of 3 to 7 bars and sump temperature of 135°

to 150°

C.

13. Process of claim 4 wherein liquid ammonia is mixed with water in a weight ratio of 1:

4 before cooling of the resulting mixture and conducting to the ammonia vapors in the top portion of scrubbing column used in step (b).

14. Process of claim 5 wherein heat exchangers associated with the pressure de-acidification column are fed with air in an O₂ :

HCN molar ratio below 1.

15. Process of claim 6 wherein the enriched residual solvent in the upper portion of the pressure de-acidification column used in step (d) is removed by a side stream flow path.

16. Process of claim 7 wherein 10% by weight of the feed for the pressure de-acidification column used in step (d) are branched off, cooled and fed to said column.

17. In a continuous process of recovering pure, concentrated ammonia, which contains not more than 0.2% H₂ O, 0.1% CO₂, 10 ppm H₂ S, and 10 ppm HCN, from aqueous liquors from which dust, tar, oil, and phenols have been removed, said aqueous liquors being condensates formed during the gasification or degasification of coal, or from aqueous liquors of similar compositions which contain free and/or combined ammonia in concentrations between 0.1 and 12 n, carbon dioxide in concentrations between 0.1 and 12 n, hydrogen sulfide in concentrations between 0.003 and 3 n, hydrocyanic acid in concentrations between 0.001 to 1 g/l, and residual organic substances introduced during a preceding dephenolation, which process includes the steps of stripping off gas water, de-acidification, scrubbing, and withdrawing ammonia from the top of a scrubbing column, the improvement which comprises the following steps:

a. stripping ammonia from the aqueous liquor in a stripping column having 15-80 actual plates or equivalent packing columns operated under a pressure of 1-2 bars with an inlet temperature of 30°

-90°

C, the ammonia and the acid constituents being jointly withdrawn overhead and waste water being withdrawn from the sump of the column,

b. scrubbing the overhead product from (a) with an aqueous solution containing surplus ammonia from which the acid constituents have been substantially removed under a pressure of 1-2 bars and at temperatures of 30°

-70°

C withdrawing pure ammonia overhead and

c. stripping most of the residual ammonia from the spent scrubbing liquor from (b) in a stripping column having 3-25 plates, or equivalent packing columns, operated under 1-2 bars, top temperatures of 50°

-80°

C, and sump temperatures of 60°

-90°

C, and withdrawing ammonia overhead and recycling it to (b); and

d. de-acidifying aqueous solutions having a (CO₂ + H₂ S);

NH ratio ≧

1 under superatmospheric pressure by stripping the acid constituents in a pressure de-acidification column operated under a pressure of 3-25 bars, and sump temperatures of 110°

-180°

C, and withdrawing same from the top of said column;

said steps being carried out in the sequence a), b), c), d), with the sump product of step c) being subjected to step d) in the processing of solutions in which the (CO₂ + H₂ S) ;

NH₃ weight ratio ≦

1 whereas the feed solution is subjected to the pressure de-acidification step d) and this is succeeded by steps a), b), c) in the processing of solutions having a (CO₂ + H₂ S) ;

NH₃ weight ratio >

1.