Process for recovery and recycle of ammonia from a vapor stream

• US 7,326,391 B2
• Filed: 07/21/2005
• Issued: 02/05/2008
• Est. Priority Date: 07/22/2004
• Status: Expired due to Fees

• Current Assignee: Ineos USA LLC (Ineos AG)
• Original Assignee: Ineos USA LLC (Ineos AG)
• Inventors: Szabo, Thomas L., Bowman, Thomas L., Keckler, Kenneth P., Shuki, Albert R.
• Primary Examiner(s): Vanoy; Timothy C.
• Application Number:
  US11/186,032
• Publication Number:
  US 20060088461A1
• Time in Patent Office: 929 Days
• Field of Search: 423/237, 423/238, 210/767, 210/150, 210/908, 558/319
• US Class Current: 423/237
• CPC Class Codes: B01D 2257/406 Ammonia
• CPC Class Codes: B01D 53/14 by absorption
• CPC Class Codes: C01C 1/12 Separation of ammonia from gases and vapours as part of the ammonia synthesis process C01C1/04
• CPC Class Codes: C07C 253/26 containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
• CPC Class Codes: C07C 253/34 Separation; Purification
• CPC Class Codes: C07C 255/08 Acrylonitrile; Methacrylonitrile
• CPC Class Codes: Y02P 20/50 Improvements relating to the production of bulk chemicals
• CPC Class Codes: Y10S 210/908 Organic

Abstract

A process for the recovery of unreacted ammonia from the effluent from a reaction zone used to produce acrylonitrile or methacrylonitrile comprising quenching the reactor effluent with an aqueous solution of ammonium phosphate in at least two stages, thereby capturing the ammonia component of the effluent. The captured ammonia may be recovered by heating the aqueous ammonium phosphate, which then may be recycled. Contaminants present in the aqueous ammonium phosphate may be removed, for example by solvent extraction or wet oxidation, prior to recycle.

Claims

1. A process for the recovery of ammonia from a vaporous stream comprising contacting said stream with a first aqueous ammonium phosphate solution comprising ammonium dihydrogen phosphate and diammonium hydrogen phosphate, having a first ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄⁻

3), thereby absorbing ammonia from said stream and forming aqueous quench bottoms having increased ratio of (NH₄⁺) to (PO₄<sup>−

3</sup>) and a depleted vapor stream comprising residual ammonia;

contacting said depleted vapor stream with a second aqueous ammonium phosphate solution comprising ammonium dihydrogen phosphate and diammonium hydrogen phosphate, and having a second ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄<sup>−

3</sup>) that is lower than the first ratio, thereby absorbing substantially all of said residual ammonia from said vapor stream and forming said first aqueous ammonium phosphate solution;

heating said aqueous quench bottoms to an elevated temperature for a time sufficient to decompose at least a portion of the diammonium phosphate and generate a vaporous ammonia stream; and

separating the ammonia from the remaining components of said vaporous ammonia stream.

2. The process of claim 1 wherein the ratio of ammonium ions to phosphate ions in the first aqueous ammonium phosphate solution is greater than about about 1.3.

3. The process of claim 1 wherein the ratio of ammonium ions to phosphate ions in the second aqueous ammonium phosphate solution is from about 0.7 to about 1.3.

4. The process of claim 1 further comprising passing a stripper gas through the aqueous quench bottoms to remove volatile organic components.

5. The process of claim 1 further comprising extracting the aqueous quench bottoms with an immiscible solvent.

6. The process of claim 5 wherein said solvent is selected from nitrile monomers and alkyl nitrites.

7. The process of claim 5 further comprising passing a stripper gas through the extracted aqueous quench bottoms to remove residual solvent.

8. The process of claim 4 or 7 wherein said stripper gas comprises at least one gas selected from the group consisting of propane, nitrogen, carbon dioxide, and carbon monoxide.

9. The process of claim 1 wherein said aqueous quench bottoms are heated for a time sufficient to reduce the ratio of ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄⁻

3) to a value in the range of from about 0.7 to about 1.3.

10. The process of claim 9 further comprising heating said aqueous quench bottoms under wet oxidation conditions.

11. The process of claim 1 wherein said aqueous quench bottoms are heated for a time sufficient to reduce the ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄⁻

3) to a value in the range of from about 0.7 to about 1.3, subjected to wet oxidation, and recycled as said second aqueous ammonium phosphate solution.

12. The process of claim 1 wherein said aqueous quench bottoms are heated under wet oxidation conditions in a wet oxidation reactor for a time sufficient to reduce the ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄⁻

3) to a value in the range of from about 0.7 to about 1.3, and recycled as said second aqueous ammonium phosphate solution.

13. The process of claim 1 wherein the ammonium ion to phosphate ion ratio in the first aqueous ammonium phosphate solution is from about 1.3 to about 2.

14. The process of claim 1 wherein the pH of the second aqueous ammonium phosphate solution is from about 2.5 to about 4.5.

15. The process of claim 1 wherein the pH of the second aqueous ammonium phosphate solution is from 3 to about 4.

16. The process of claim 1 wherein the pH of the first aqueous ammonium phosphate solution is from about 5 to about 7.

22. The process of claim 1 wherein the ratio of ammonium ions to phosphate ions in the second aqueous ammonium phosphate solution is greater than about 0.9 to about 1.2.

23. The process of claim 1 wherein the ratio of ammonium ions to phosphate ions in the second aqueous ammonium phosphate solution is from about 1.0 to about 1.1.

17. In a process for the recovery of unreacted ammonia from a reactor effluent obtained from an ammoxidation reaction zone for the production of an unsaturated nitrile, said process comprising the steps of quenching said reactor effluent with an aqueous ammonium phosphate solution, thereby absorbing unreacted ammonia present in the reactor effluent and forming an ammonia-enriched aqueous solution richer in ammonium ions than said aqueous ammonium phosphate solution;

heating said ammonia-enriched aqueous solution to an elevated temperature sufficient to reduce the amount of ammonium ions, thereby regenerating said aqueous ammonium phosphate solution and generating a vaporous stream containing ammonia; and

recycling said vaporous stream to the ammoxidation reaction zone, the improvement comprising quenching said reactor effluent with a first aqueous ammonium phosphate solution comprising ammonium dihydrogen phosphate and diammonium hydrogen phosphate wherein the ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄<sup>−

3</sup>) is greater than 1.3, thereby absorbing greater than about 90% of the unreacted ammonia present in the reactor effluent and forming said ammonia-enriched solution and depleted effluent comprising residual ammonia; and

contacting said depleted effluent with a second aqueous ammonium phosphate solution comprising ammonium dihydrogen phosphate and diammonium hydrogen phosphate wherein the ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄<sup>−

3</sup>) is from about 0.7 to about 1.3, thereby absorbing said residual ammonia from said reactor effluent and forming said first aqueous ammonium phosphate solution.

18. The process of claim 17 wherein the improvement further comprises extracting said ammonia-enriched solution with an immiscible solvent to remove solvent-soluble soluble contaminants and stripping the extracted solution to remove residual solvent prior to heating ammonia-enriched solution and generating said vaporous stream.

19. The process of claim 17 wherein the improvement further comprises heating said ammonia-enriched solution under wet oxidation conditions to an elevated temperature for a time sufficient to destroy at least a portion of contaminants contained therein and reduce the amount of ammonium ions, thereby regenerating said aqueous ammonium phosphate solution and generating said vaporous stream.

20. The process of claim 17 wherein the improvement comprises quenching said reactor effluent with a first aqueous ammonium phosphate solution comprising ammonium dihydrogen phosphate and diammonium hydrogen phosphate wherein the ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄⁻

3) is greater than 1.3, thereby absorbing greater than about 90% of the unreacted ammonia present in the reactor effluent and forming said ammonia-enriched aqueous solution and a depleted effluent comprising residual ammonia;

contacting said depleted effluent with a second aqueous ammonium phosphate solution comprising ammonium dihydrogen phosphate and diammonium hydrogen phosphate wherein the ratio of ammonium ions (NH₄⁺) to phosphate ions (PO₄<sup>−

3</sup>) is from about 0.7 to about 1.3, thereby absorbing said residual ammonia from said reactor effluent and forming said first aqueous ammonium phosphate solution;

extracting said ammonia-enriched aqueous solution with an immiscible solvent to remove solvent-soluble contaminants;

stripping the extracted ammonia-enriched aqueous solution to remove residual solvent;

heating said ammonia-enriched aqueous solution to an elevated temperature sufficient to reduce the amount of ammonium ions, thereby regenerating said aqueous ammonium phosphate solution and generating a vaporous stream containing ammonia;

stripping said vaporous stream to separate ammonia and contaminants, and dehydrating said ammonia prior to recycle.

21. The process of claim 17 wherein the vaporous stream recycled to the ammoxidation reaction zone comprises anhydrous ammonia.