Methods and systems for treating an aqueous effluent

• US 9,359,234 B2
• Filed: 01/21/2015
• Issued: 06/07/2016
• Est. Priority Date: 01/30/2014
• Status: Active Grant

• Current Assignee: Wilmar Trading Pte., Ltd. (Wilmar International Limited)
• Original Assignee: Elevance Renewable Sciences Incorporated
• Inventors: Kirk, Sharon, Pease, Brian, Firth, Bruce, Dreyer, Bradon
• Primary Examiner(s): STELLING, LUCAS A
• Application Number:
  US14/601,443
• Publication Number:
  US 20150210568A1
• Time in Patent Office: 503 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 2231/54 Metathesis reactions, e.g. olefin metathesis
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 31/2265 Carbenes or carbynes, i.e.(image)
• CPC Class Codes: B01J 31/4015 of catalysts containing metals
• 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 1/72 by oxidation C02F1/4672 takes precedence
• CPC Class Codes: C02F 1/722 Oxidation by peroxides
• CPC Class Codes: C02F 1/725 by catalytic oxidation
• CPC Class Codes: C02F 2101/105 Phosphorus compounds
• CPC Class Codes: C02F 2101/30 Organic compounds
• CPC Class Codes: C02F 2101/34 containing oxygen
• CPC Class Codes: C02F 2103/36 from the manufacture of organic compounds
• CPC Class Codes: C02F 2305/02 Specific form of oxidant
• CPC Class Codes: C07F 9/5004 Acyclic saturated phosphines
• CPC Class Codes: C07F 9/5304 Acyclic saturated phosphine oxides or thioxides
• CPC Class Codes: C07F 9/5407 Acyclic saturated phosphonium compounds
• CPC Class Codes: C10G 2300/705 Passivation
• CPC Class Codes: C10G 45/58 to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00
• CPC Class Codes: C10G 50/00 Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

Methods and systems for treating an aqueous effluent from a metathesis reactor, such as a metathesis-based biorefinery, are generally disclosed. In some embodiments, the aqueous effluent is generated from washing the metathesized product with an aqueous medium. In some embodiments, such wash streams are chemically treated to reduce their toxicity and to facilitate disposal. In some embodiments, such wash streams are treated to recover at least a portion of the catalyst residue, so as to facilitate catalyst recovery.

Claims

1. A method of treating a reactor water stream, the method comprising:

providing a first aqueous medium comprising (i) an organic phosphine compound or an organic phosphonium compound, and (ii) a metathesis catalyst residue; and

reacting the organic phosphine compound or the organic phosphonium compound with an oxidizing agent to form a second aqueous medium comprising an organic phosphine oxide.

2. The method of claim 1, wherein the organic phosphine compound is a compound according to formula (Ia):

3. The method of claim 2, wherein the organic phosphonium compound is a compound according to formula (Ib):

4. The method of claim 1, wherein the first aqueous medium comprises the organic phosphonium compound and one or more counterions to the organic phosphonium compound.

5. The method of claim 4, wherein the one or more counterions are selected from the group consisting of:

a halide anion, a sulfate anion, a hydrogen sulfate anion, a phosphate anion, a hydrogen phosphate anion, a dihydrogen phosphate anion, a nitrate anion, a hydroxide anion, a carbonate anion, a hydrogen carbonate anion, a cyanide anion, an acetate anion, a formate anion, an oxalate anion, and any mixtures thereof.

6. The method of claim 5, wherein the one or more counteranions are selected from the group consisting of:

a chloride anion, a sulfate anion, and any mixtures thereof.

7. The method of claim 1, further comprising separating at least a portion of the metathesis catalyst residue from the first aqueous medium.

8. The method of claim 1, wherein the second aqueous medium comprises an amount of the metathesis catalyst residue.

9. The method of claim 8, further comprising separating at least a portion of the metathesis catalyst residue from the second aqueous medium.

10. The method of claim 1, wherein the first aqueous medium comprises an aldehyde, and wherein the method further comprises reacting the aldehyde with the oxidizing agent to form (i) an alcohol, and (ii) a carboxylic acid, a carboxylate, or a mixture thereof.

11. The method of claim 10, wherein the aldehyde is formaldehyde, the alcohol is methanol, the carboxylic acid is formic acid, and the carboxylate is formate.

12. The method of claim 1, wherein the oxidizing agent is an organic peroxide.

13. The method of claim 1, wherein the oxidizing agent is hydrogen peroxide, another inorganic peroxide, oxygen, ozone, a hypochlorite, a chlorate, nitric acid, chromium trioxide, a chromate, a dichromate, a manganite, or a permanganate.

14. The method of claim 1, wherein the reacting occurs in a basic medium.

15. The method of claim 14, wherein the pH of the basic medium is from 8 to 12.

16. The method of claim 1, further comprising chemically treating the second aqueous medium.

17. The method of claim 16, wherein the treating comprises introducing an acid to the second aqueous medium.

18. The method of claim 16, wherein the treating comprises introducing a sulfite to the second aqueous medium.

19. The method of claim 16, wherein the treating comprises introducing a peroxide decomposition catalyst to the second aqueous medium.

20. The method of claim 19, wherein the peroxide decomposition catalyst is a transition metal compound, such as palladium, platinum, silver, or manganese dioxide.