Methods and systems for treating an aqueous effluent
View Patent ↗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.
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):
wherein R 1 , R 2 , and R 3 are independently a hydrogen atom or a C 1-20 hydrocarbyl group, wherein one or more of the carbon atoms in the hydrocarbyl group can be replaced by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, and oxidized forms thereof;
wherein at least one of R 1 , R 2 , and R 3 is not a hydrogen atom.
3. The method of claim 2 , wherein the organic phosphonium compound is a compound according to formula (Ib):
wherein R 4 , R 5 , R 6 , and R 7 are independently a hydrogen atom or a C 1-20 hydrocarbyl group, wherein one or more of the carbon atoms in the hydrocarbyl group can be replaced by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, and oxidized forms thereof;
wherein at least one of R 4 , R 5 , R 6 , and R 7 is not a hydrogen atom.
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.