PHOSPHORUS CONTROL FOR WASTE STREAMS FROM GLYPHOSATE MANUFACTURING PROCESSES

• US 20200131067A1
• Filed: 06/26/2018
• Published: 04/30/2020
• Est. Priority Date: 06/26/2017
• Status: Active Grant

• Current Assignee: Monsanto Technology LLC (Bayer AG)
• Original Assignee: Monsanto Technology LLC (Bayer AG)
• Inventors: Lei, Peng, Ren, Ming, Vaughn, Anthony E.
• Granted Patent: US 11,279,644 B2
• Time in Patent Office: Days
• CPC Class Codes: C01B 25/26 Phosphates perphosphates C01B15/16
• CPC Class Codes: C02F 1/38 by centrifugal separation
• CPC Class Codes: C02F 1/5245 using basic salts, e.g. of aluminium and iron
• CPC Class Codes: C02F 1/66 by neutralisation; pH adjustment for degassing C02F1/20; using ion-exchange C02F1/42; for flocculation or precipitation of suspended impurities C02F1/52; for removing dissolved compounds C02F1/58
• CPC Class Codes: C02F 1/722 Oxidation by peroxides
• CPC Class Codes: C02F 1/76 with halogens or compounds of halogens C02F1/4674 takes precedence
• CPC Class Codes: C02F 11/16 using drying or composting beds
• CPC Class Codes: C02F 2101/105 Phosphorus compounds
• CPC Class Codes: C02F 2103/36 from the manufacture of organic compounds
• CPC Class Codes: C02F 2303/185 The treatment agent being halogen or a halogenated compound
• CPC Class Codes: C02F 3/1215 Combinations of activated sludge treatment with precipitation, flocculation, coagulation and separation of phosphates
• CPC Class Codes: C02F 9/00 Multistage treatment of water, waste water or sewage
• CPC Class Codes: C07F 9/025 Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds of natural phosphatides C07F9/103; phosphines C07F9/5095
• CPC Class Codes: C07F 9/3808 Acyclic saturated acids which can have further substituents on alkyl
• CPC Class Codes: C07F 9/3813 N-Phosphonomethylglycine; Salts or complexes thereof

Abstract

This invention relates to processes for the removal of phosphorous from aqueous waste streams comprising phosphorous-containing compounds produced in the manufacture of glyphosate, in order to meet and typically exceed environmental regulations. More particularly, various embodiments of the present invention relate to the removal of phosphorous-containing compounds utilizing biological treatment system(s), oxidizing agent(s), and/or precipitant(s). The processes of the invention are also applicable to the removal of phosphorous compounds from phosphorous-containing waste streams other than those waste streams resulting from the manufacture of glyphosate.

Claims

1. A process for recovery of phosphorus from a waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

), wherein the one or more organic phosphorus compounds comprise N-(phosphonomethyl)glycine (glyphosate) and aminomethylphosphonic acid (AMPA), the process comprising;

subjecting at least a portion of the waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

) to biological treatment to form a biologically treated waste stream;

contacting the biologically treated waste stream with a precipitant, thereby forming within the biologically treated waste stream phosphate containing precipitates, wherein the biologically treated waste stream has a pH of less than 7 when initially contacted with the precipitant; and

recovering a phosphate containing cake from the biologically treated waste stream, thereby forming a treated waste stream.

8. The process as set forth in any one of claims 1 to 7 wherein the precipitant comprises a metal selected from the group consisting of calcium, aluminum, iron, magnesium, and mixtures thereof.

9. The process as set forth in claim 8 wherein the precipitant is selected from the group consisting of FeCl₃, Al₂(SO₄)₃, CaO, and combinations thereof.

10. The process as set forth in any one of claims 1 to 9 wherein the biologically treated waste stream and/or oxidized treated waste stream is contacted with the precipitant at a rate of from about 0.05 g/l to about 2 g/l, from about 0.1 g/l to about 1.75 g/l, from about 0.1 g/l to about 1.5 g/l, from about 0.1 g/l to about 1.25 g/l, or from about 0.1 g/l to about 1.15 g/l.

11. The process as set forth in any one of claims 1 to 9 wherein the biologically treated waste stream and/or oxidized treated waste stream is contacted with the precipitant at a weight ratio of precipitant to oxidizing agent of from about 50:

1 to about 500;

1, from about 100;

1 to about 500;

1, from about 200;

1 to about 400;

1, from about 250;

1 to about 300;

1, or from about 275;

1 to about 300;

1.

12. The process as set forth in any one of claims 1 to 11 wherein the treated waste stream comprises no more than about 3 ppm, no more than about 2 ppm, no more than about 1.5 ppm, no more than about 1.25 ppm, no more than about 1.1 ppm, no more than about 1 ppm, no more than about 0.9 ppm, no more than about 0.8 ppm, no more than about 0.7 ppm, no more than about 0.6 ppm, no more than about 0.5 ppm, no more than about 0.4 ppm, no more than about 0.3 ppm, no more than about 0.25 ppm, no more than about 0.2 ppm, no more than about 0.15 ppm, no more than about 0.1 ppm, or no more than about 0.05 ppm phosphorous.

13. The process as set forth in any one of claims 1 to 12 wherein the total phosphorous removal [(weight P_{waste stream}−

weight P_{treated waste stream})/(weight P_{waste stream})×

100] is at least about 50%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 90%, or at least about 95%.

14. The process as set forth in any one of claims 1 to 13 wherein the total COD removal [(COD_{waste stream}−

COD_{treated waste stream})(COD_{waste stream})×

100] is at least about 50%, at least about 60%, at least about 70%, at least about 75%, at least about 80%, at least about 90%, or at least about 95%.

2. A process for recovery of phosphorus from a waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

), wherein the one or more organic phosphorus compounds comprise N-(phosphonomethyl)glycine (glyphosate) and aminomethylphosphonic acid (AMPA), the process comprising;

subjecting at least a portion of the waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

) to biological treatment to form a biologically treated waste stream;

contacting the biologically treated waste stream with an oxidizing agent to form an oxidized treated waste stream;

contacting the oxidized treated waste stream with a precipitant, thereby forming within the oxidized treated waste stream phosphate containing precipitates; and

recovering a phosphate containing cake from the oxidized treated waste stream, thereby forming a treated waste stream.

3. The process as set forth in claim 2 wherein the oxidizing agent is selected from the group consisting of calcium hypochlorite, sodium hypochlorite, bleach, and combinations thereof.

4. The process as set forth in claim 2 or 3 wherein the oxidizing agent is bleach.

5. The process as set forth in any one of claims 2 to 4 wherein the biologically treated waste stream prior to contact with the oxidizing agent has a pH of from about 1 to about 7.5, from about 1.5 to about 7, from about 2 to about 6.5, from about 2.3 to about 6.5, from about 2.5 to about 6, from about 3 to about 5.5, or from about 3.5 to about 5.

6. The process as set forth in any one of claims 2 to 5 wherein the molar ratio of oxidizing agent to glyphosate present in the biologically treated waste stream is at least about 1:

1, at least about 2;

1, at least about 3;

1, at least about 5;

1, at least about 10;

1, or at least about 15;

1.

7. The process as set forth in any one of claims 2 to 5 wherein the molar ratio of oxidizing agent to AMPA present in the biologically treated waste stream is at least about 1:

1, at least about 2;

1, at least about 3;

1, at least about 5;

1, at least about 10;

1, or at least about 15;

1.

15. A process for recovery of phosphorus from a waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

), wherein the one or more organic phosphorus compounds comprise N-(phosphonomethyl)glycine (glyphosate) and aminomethylphosphonic acid (AMPA), the process comprising;

contacting at least a portion of the waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

) with a precipitant, thereby forming within the waste stream phosphate containing precipitates, to produce a precipitant treated stream, wherein the waste stream has a pH of less than 7 when initially contacted with the precipitant;

subjecting at least a portion of the precipitant treated stream to biological treatment to form a biologically treated waste stream; and

recovering a phosphate containing cake from the biologically treated waste stream, thereby forming a treated waste stream.

16. The process as set forth in claim 15 wherein at least a portion of the waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

) is contacted with an oxidizing agent prior to contact with a precipitant, to form an oxidized treated stream and thereby oxidizing at least one organic phosphorus compound to form phosphate (PO₄³), and wherein the oxidized treated stream is contacted with the precipitant.

17. The process as set forth in any one of claims 15 to 16 wherein the total phosphorous removal [(weight P_{waste stream}−

weight P_{treated waste stream})/(weight P_{waste stream})×

100] is at least about 50%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 90%, or at least about 95%.

18. The process as set forth in any one of claims 15 to 17 wherein the total COD removal [(COD_{waste stream}−

COD_{treated waste stream})(COD_{waste stream})×

100] is at least about 50%, at least about 60%, at least about 70%, at least about 75%, at least about 80%, at least about 90%, or at least about 95%.

19. A process for recovery of phosphorus from a waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

), wherein the one or more organic phosphorus compounds comprise N-(phosphonomethyl)glycine (glyphosate) and aminomethylphosphonic acid (AMPA), the process comprising;

removing a portion of the waste stream comprising one or more organic phosphorus compounds and phosphate as a precipitation phosphate liquor stream and contacting the precipitation phosphate liquor stream with a precipitant thereby forming within the precipitation phosphate liquor stream phosphate containing precipitates and producing a precipitant treated phosphate stream;

combining the precipitant treated phosphate stream with the waste stream to form a combined precipitant treated phosphate waste stream and subjecting the combined precipitant treated phosphate waste stream to biological treatment to form a biologically treated waste stream; and

recovering a phosphate containing cake from the biologically treated waste stream, thereby forming a treated waste stream.

21. The process as set forth in claim 19 or 20 wherein the treated waste stream comprises no more than about 3 ppm, no more than about 2 ppm, no more than about 1.5 ppm, no more than about 1.25 ppm, no more than about 1.1 ppm, no more than about 1 ppm, no more than about 0.9 ppm, no more than about 0.8 ppm, no more than about 0.7 ppm, no more than about 0.6 ppm, no more than about 0.5 ppm, no more than about 0.4 ppm, no more than about 0.3 ppm, no more than about 0.25 ppm, no more than about 0.2 ppm, no more than about 0.15 ppm, no more than about 0.1 ppm, or no more than about 0.05 ppm phosphorous.

22. The process as set forth in any one of claims 19 to 21 wherein the total phosphorous removal [(weight P_{waste stream}−

weight P_{treated waste stream})/(weight P_{waste stream})×

100] is at least about 50%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 90%, or at least about 95%.

23. The process as set forth in any one of claims 19 to 22 wherein the total COD removal [(COD_{waste stream}−

COD_{treated waste stream})(COD_{waste stream})×

100] is at least about 50%, at least about 60%, at least about 70%, at least about 75%, at least about 80%, at least about 90%, or at least about 95%.

20. A process for recovery of phosphorus from a waste stream comprising one or more organic phosphorus compounds and phosphate (PO₄³⁻

), wherein the one or more organic phosphorus compounds comprise N-(phosphonomethyl)glycine (glyphosate) and aminomethylphosphonic acid (AMPA), the process comprising;

removing a portion of the waste stream comprising one or more organic phosphorus compounds and phosphate as a oxidation phosphate liquor stream and contacting the oxidation phosphate liquor stream with an oxidizing agent to oxidize at least one organic phosphorus compound to form phosphate (PO₄³⁻

) and thereby forming an oxidized phosphate stream;

combining the oxidized phosphate stream with the waste stream to form a combined oxidized phosphate waste stream and contacting the combined oxidized phosphate waste stream with a precipitant, producing a precipitant treated phosphate stream;

subjecting the precipitant treated phosphate stream to biological treatment to form a biologically treated waste stream; and

recovering a phosphate containing cake from the biologically treated waste stream, thereby forming a treated waste stream.

24. A process for recovery of phosphorus from a waste stream comprising inorganic phosphorous, the process comprising:

subjecting at least a portion of the waste stream to biological treatment to form a biologically treated waste stream;

contacting the biologically treated waste stream with a precipitant, thereby forming within the biologically treated waste stream phosphate containing precipitates, wherein the biologically treated waste stream has a pH of less than 7 when initially contacted with the precipitant; and

recovering a phosphate containing cake from the biologically treated waste stream, thereby forming a treated waste stream.

25. A process for recovery of phosphorus from a waste stream comprising inorganic phosphorous, the process comprising:

subjecting at least a portion of the waste stream to biological treatment to form a biologically treated waste stream;

contacting the biologically treated waste stream with an oxidizing agent to form an oxidized treated waste stream;

contacting the oxidized treated waste stream with a precipitant, thereby forming within the oxidized treated waste stream phosphate containing precipitates; and

recovering a phosphate containing cake from the oxidized treated waste stream, thereby forming a treated waste stream.

26. A process for recovery of phosphorus from a waste stream comprising inorganic phosphorous, the process comprising:

contacting at least a portion of the waste stream with a precipitant, thereby forming within the waste stream phosphate containing precipitates, to produce a precipitant treated stream, wherein the waste stream has a pH of less than 7 when initially contacted with the precipitant;

subjecting at least a portion of the precipitant treated stream to biological treatment to form a biologically treated waste stream; and

recovering a phosphate containing cake from the biologically treated waste stream, thereby forming a treated waste stream.

27. The process as set forth in claim 26 wherein at least a portion of the waste stream is contacted with an oxidizing agent prior to contact with a precipitant, to form an oxidized treated stream and thereby oxidizing at least one organic phosphorus compound to form phosphate (PO₄³), and wherein the oxidized treated stream is contacted with the precipitant.

28. A process for recovery of phosphorus from a waste stream comprising inorganic phosphorous, the process comprising:

removing a portion of the waste stream as a precipitation phosphate liquor stream and contacting the precipitation phosphate liquor stream with a precipitant thereby forming within the precipitation phosphate liquor stream phosphate containing precipitates and producing a precipitant treated phosphate stream;

combining the precipitant treated phosphate stream with the waste stream to form a combined precipitant treated phosphate waste stream and subjecting the combined precipitant treated phosphate waste stream to biological treatment to form a biologically treated waste stream; and

recovering a phosphate containing cake from the biologically treated waste stream, thereby forming a treated waste stream.

29. A process for recovery of phosphorus from a waste stream comprising inorganic phosphorous, the process comprising:

removing a portion of the waste stream as a oxidation phosphate liquor stream and contacting the oxidation phosphate liquor stream with an oxidizing agent to oxidize at least one organic phosphorus compound to form phosphate (PO₄³⁻

) and thereby forming an oxidized phosphate stream;

combining the oxidized phosphate stream with the waste stream to form a combined oxidized phosphate waste stream and contacting the combined oxidized phosphate waste stream with a precipitant, producing a precipitant treated phosphate stream;

subjecting the precipitant treated phosphate stream to biological treatment to form a biologically treated waste stream; and

recovering a phosphate containing cake from the biologically treated waste stream, thereby forming a treated waste stream.