Production and purification of contaminated effluent streams containing ammonium sulfate and ammonia

• US 5,536,385 A
• Filed: 03/03/1995
• Issued: 07/16/1996
• Est. Priority Date: 03/03/1995
• Status: Expired due to Fees

• Current Assignee: Envirocorp Services & Technology Incorporated
• Original Assignee: Envirocorp Services & Technology Incorporated
• Inventors: Sheldon, Joseph P., Applegath, Fred, Stanton, Walter H., Malachosky, Edward
• Primary Examiner(s): Phasge, Arun S.
• Application Number:
  US08/398,104
• Time in Patent Office: 501 Days
• Field of Search: 204/182.4, 204/182.5, 204/151
• US Class Current: 204/523
• CPC Class Codes: B01J 2219/185 vertical
• CPC Class Codes: B01J 2219/1943 cylindrical
• CPC Class Codes: B01J 3/008 Processes carried out under supercritical conditions
• CPC Class Codes: B01J 3/04 Pressure vessels, e.g. autoclaves
• CPC Class Codes: C02F 1/469 by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
• CPC Class Codes: C02F 1/586 by removing ammoniacal nitrogen for biological methods C02F3/00
• CPC Class Codes: C02F 1/722 Oxidation by peroxides
• CPC Class Codes: C02F 11/083 using deep well reactors
• CPC Class Codes: C02F 11/086 in the supercritical state
• CPC Class Codes: C02F 2101/16 Nitrogen compounds, e.g. ammonia
• CPC Class Codes: C02F 2201/46115 Electrolytic cell with membranes or diaphragms
• CPC Class Codes: C02F 9/00 Multistage treatment of water, waste water or sewage

Abstract

The present invention, in certain embodiments, teaches a process for treating ammonia or ammonium-sulfate-containing waste effluent from an acrylonitrile, caprolactam or acetonitrile manufacturing facility. In one such process the effluent is fed to a deep well oxidizer, e.g. a water oxidizer vertical tube reactor (super critical or subcritical), to degrade organic contaminants. Certain embodiments of the deep well oxidizer have, according to this invention, an oxygen inlet tube movable by a coil tubing system. The output stream from the vertical tube reactor is, preferably, filtered, and then it is fed to an electrodialysis unit. In one aspect the electrodialysis unit produces an output stream at a pH of about 5 with a concentration of ammonium sulfate at least, preferably, of about 15% by weight, and most preferably between about 20% and about 26% by weight. This output stream may be neutralized and then further treated to remove ammonia and/or ammonium sulfate solids, e.g. by a downstream ammonia stripper, evaporator, and/or crystallizer system or combination thereof.

Claims

1. A process for treating a first aqueous effluent waste stream, the first effluent waste stream containing dissolved ammonium salts at a first concentration and organic contaminants, the process comprising

flowing the first effluent waste stream to a deep well oxidizer for oxidation therein to degrade organic contaminants in the first effluent waste stream producing a second effluent waste stream,

flowing the second effluent waste stream to an electrodialysis unit, and

producing with the electrodialysis unit a third stream containing ammonium salt in solution at a second concentration higher than that of the first concentration of ammonium salts of the first effluent waste stream.

2. The process of claim 1 wherein the deep well oxidizer has a movable oxygen inlet tube disposed therein, the process further comprising

moving the oxygen inlet tube in the deep well oxidizer to enhance oxidation of the first effluent waste stream.

3. The process of claim 2 further comprising

connecting the oxygen inlet tube to a coil tubing unit having coil tubing removably disposed thereon, and

moving the oxygen inlet tube in the deep well oxidizer by moving the coil tubing on the coil tubing unit.

4. The process of claim 2 wherein the oxygen inlet tube has a lower ceramic portion and the process further comprising

flowing oxygen out from the lower ceramic portion of the oxygen inlet tube.

5. The process of claim 1 wherein the second effluent waste stream is by weight about 4% ammonium sulfate and about 96% water.

6. The process of claim 1 wherein the deep well oxidizer is a subcritical vertical tube reactor.

7. The process of claim 1 wherein the first effluent stream is by weight about 10% ammonium sulfate, about 0.5 to 5% contaminants, and the remainder water.

8. The process of claim 7 wherein the contaminants are from the group comprising acrylic acid, acrylamide, maleimide, maleonitrile, fumaronitrile, caprolactam, and cyanide salts.

9. The process of claim 1 wherein the second concentration is at least 15% by weight.

10. The process of claim 9 wherein the second concentration is between about 20% to about 26% by weight.

11. The process of claim 1 further comprising

feeding the third stream containing ammonium salt in solution to a stripper tower,

producing in the stripper tower a stream of liquid ammonia, and

flowing the stream of liquid ammonia from the tripper tower.

12. The process of claim 1 further comprising

feeding the third stream containing ammonium salt in solution to a pH adjusting system to raise its pH.

13. The process of claim 2 wherein the pH is raised to at least 10 to facilitate recovery of ammonia in a stripper tower.

14. The process of claim 1 further comprising

flowing the third stream from the electrodialysis unit to an evaporator, and

producing an output stream in the evaporator with a higher concentration of ammonium salt than the third stream containing ammonium salt from the electrodialysis unit.

15. The process of claim 14 further comprising

flowing the output stream from the evaporator to a crystallization unit,

producing solid ammonium salts in the crystallizing unit, and

flowing the solid ammonium salts from the crystallizing unit.

16. The process of claim 1 further comprising

flowing the third stream from the electrodialysis unit to a crystallization unit,

producing solid ammonium salts in the crystallizing unit, and

flowing the solid ammonium salts from the crystallizing unit.

17. A process for treating a first effluent waste stream from an acrylonitrile or acetonitrile manufacturing process, the first effluent waste stream being an aqueous stream and containing dissolved ammonium salts at a first concentration and organic contaminants, the first effluent stream is by weight about 10% ammonium sulfate, about 0.5 to 5% contaminants, and the remainder water, the second effluent waste stream is by weight about 4% ammonium sulfate and about 96% water, the process comprising

flowing the first effluent waste stream to a deep well oxidizer for oxidation therein to degrade organic contaminants producing a second effluent waste stream, the deep well oxidizer having a movable oxygen inlet tube disposed therein,

connecting the oxygen inlet tube to a coil tubing unit having coil tubing removably disposed thereon, and

moving the oxygen inlet tube in the deep well oxidizer by moving the coil tubing on the coil tubing unit,

moving the oxygen inlet tube in the deep well oxidizer to enhance oxidation of the first effluent waste stream,

flowing the second effluent waste stream to an electrodialysis unit,

producing with the electrodialysis unit a third stream containing ammonium salt in solution at a second concentration higher than that of the first concentration of ammonium salts of the first effluent waste stream,

feeding the third stream containing ammonium salt in solution to a pH adjusting system to raise its pH, to at least 10 to facilitate recovery of ammonia in a stripper tower,

feeding the third stream containing ammonium salt in solution to a stripper tower,

producing in the stripper tower a stream of liquid ammonia, and

flowing the stream of liquid ammonia from the stripper tower.