Process for degrading organic substances in an aqueous composition

• US 8,795,536 B2
• Filed: 01/29/2009
• Issued: 08/05/2014
• Est. Priority Date: 01/31/2008
• Status: Active Grant

• Current Assignee: Solvay SA (Solvac SA)
• Original Assignee: Solvay SA (Solvac SA)
• Inventors: Gilbeau, Patrick, Blancke, Ward
• Primary Examiner(s): Griffin, Walter D
• Assistant Examiner(s): Allen, Cameron J
• Application Number:
  US12/864,211
• Publication Number:
  US 20100294727A1
• Time in Patent Office: 2,014 Days
• Field of Search: 210/748.01, 210/748.04, 210/748.1, 210/748.12, 210/748.13, 210/748.16, 210/748.17, 210/748.19, 210/756, 210/721, 210/723, 210/724, 210/725, 210/727, 210/728, 210/729, 210/743, 210/746, 210/747.8, 210/758, 210/109, 210/243, 210/263, 210/450, 210/554, 210/600, 210/660, 210/662, 210/666, 210/671, 210/269, 210/270, 210/272, 210/228.2, 210/230.2, 210/242, 210/225, 205/687, 205/742, 205/743, 205/751, 205/755, 205/688, 205/698, 205/761, 423/488, 423/155, 423/204, 423/206.R, 423/437, 423/210, 423/168, 423/224, 423/235, 423/236, 423/240.R, 423/243.03, 423/245.1, 422/5, 422/129, 422/243, 422/292, 204/263, 204/283, 204/284, 204/290.F, 204/290.R, 204/291, 204/292, 204/294
• US Class Current: 210/748.13
• CPC Class Codes: C01D 3/14 Purification
• CPC Class Codes: C02F 1/048 Purification of waste water by evaporation
• CPC Class Codes: C02F 1/22 by freezing
• CPC Class Codes: C02F 1/30 by irradiation
• CPC Class Codes: C02F 1/32 with ultraviolet light
• 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 2101/10 Inorganic compounds
• CPC Class Codes: C02F 2101/30 Organic compounds
• CPC Class Codes: C02F 2103/36 from the manufacture of organic compounds
• CPC Class Codes: C02F 2201/46115 Electrolytic cell with membranes or diaphragms
• CPC Class Codes: C02F 2209/02 Temperature
• CPC Class Codes: C02F 2209/03 Pressure
• CPC Class Codes: C02F 2209/06 pH

Abstract

Process for degrading organic substances in an aqueous composition comprising a step (a) wherein, in a liquid reaction medium, said aqueous composition is reacted with at least one composition comprising hydroxide ions (OH⁻) and hypochlorite in a molar ratio between hydroxide and hypochlorite higher than or equal to 0.001 and lower than 1.5, in order to oxidize said organic substances.

Claims

1. A process for degrading an organic substance in an aqueous composition, said method comprising:

(a) reacting, in a liquid reaction medium, said aqueous composition with at least one composition comprising hydroxide ions (OH⁻

) and hypochlorite in a molar ratio between hydroxide and hypochlorite higher than or equal to 0.001 and lower than 1.5, in order to oxidize said organic substance,

wherein said reacting is carried out at a first pH value controlled and maintained at a value of 6-9.

2. The process according to claim 1 wherein the reaction of in (a) is carried out in at least one of the following conditions:

i. a pH controlled and maintained in a range which lowest limit is higher than or equal to 7 and which highest limit is lower than or equal to 9,

ii. a temperature higher than or equal to 10°

C. and lower than or equal to 200°

C.,

iii. a pressure higher than or equal to 1 bar (absolute) and lower than or equal to 11 bar,

iv. when (a) of the process is carried out in a discontinuous mode, a duration higher than or equal to 0.05 h and lower than or equal to 8 h,

v. when (a) of the process is carried out in a continuous mode, a residence time higher than or equal to 0.05 h and lower than or equal to 8 h.

3. The process according to claim 1 wherein (a) is carried out in a continuous mode, and wherein the reaction of (a) is carried out in at least two consecutive reaction zones, at least one of which is operated under mixed regime and at least one other of which is operated under plug flow regime.

4. The process according to claim 1 wherein the aqueous composition originates from a process for manufacturing an epoxide, or from a process for manufacturing a chlorinated organic compound, or from both processes.

5. The process according to claim 1, comprising reacting, in a liquid reaction medium, said aqueous composition with at least one composition comprising hydroxide ions (OH⁻

) and hypochlorite in a molar ratio between hydroxide and hypochlorite higher than or equal to 0.05 and lower than 1.2, in order to oxidize said organic substance.

6. The process according to claim 1, comprising reacting, in a liquid reaction medium, said aqueous composition with at least one composition comprising hydroxide ions (OH⁻

) and hypochlorite in a molar ratio between hydroxide and hypochlorite higher than or equal to 0.75 and lower than 1.0, in order to oxidize said organic substance.

7. The process according to claim 1 wherein the aqueous composition comprises at least one salt, and wherein said method further comprises (b1) subjecting at least part of the reaction medium of (a) to an operation selected from the group consisting of cooling, evaporative crystallization, and any combination thereof, in order to precipitate at least part of the salt, followed by recovering at least part of the precipitated salt and at least part of the water present in the aqueous composition.

8. The process according to claim 7, further comprising (b2) subjecting at least part of the reaction medium of (a) to an acidification operation in order to bring the pH to a second value lower than said first pH value and further oxidizing the organic substance.

9. The process according to claim 8, wherein (b1) is carried out on the reaction medium obtained at the end of (b2).

10. The process according to claim 8 wherein at least one of (a), (b1) and (b2) is carried out in a continuous mode.

11. The process according to claim 8, comprising reacting, in a liquid reaction medium, said aqueous composition with at least one composition comprising hydroxide ions (OH⁻

) and hypochlorite in a molar ratio between hydroxide and hypochlorite higher than or equal to 0.05 and lower than 1.2, in order to oxidize said organic substance.

12. The process according to claim 8, comprising reacting, in a liquid reaction medium, said aqueous composition with at least one composition comprising hydroxide ions (OH⁻

) and hypochlorite in a molar ratio between hydroxide and hypochlorite higher than or equal to 0.75 and lower than 1.0, in order to oxidize said organic substance.

13. The process according to claim 1, further comprising (b2) subjecting at least part of the reaction medium of (a) to an acidification operation in order to bring the pH to a second value lower than said first pH value and further oxidizing the organic substance.

14. The process according to claim 13, wherein at least one compound selected from the group consisting of chlorine, hypochlorite, chlorate, chlorine dioxide, dichlorine monoxide, and any mixture thereof, is added to the reaction medium of (b2).

15. The process according to claim 14, wherein the compound is chlorine and the partial pressure of chlorine during (b2) is higher than or equal to 0.001 bar and lower than or equal to 10 bar.

16. The process according to claim 13, wherein during or after (b2) a treatment with UV-visible light is carried out on the reaction medium.

17. The process according to claim 16, wherein the UV-visible light has a wavelength higher than or equal to 100 nm and lower than or equal to 400 nm, wherein the UV-visible light is emitted by a source and wherein a ratio between the electrical energy consumed by the source in watt-hour Wh and the volume of the treated part of the reaction medium of (a) in liters is 1-100 Wh/liter.

18. The process according to claim 13, wherein during or after (b2) a treatment by electrolysis is carried out on the reaction medium.

19. The process according to claim 18, wherein the treatment by electrolysis is carried out in an anodic compartment of a divided electrolysis cell, wherein the anodic current density is higher than or equal to 1 A/m2 of anode and lower than or equal to 25000 A/m² of anode and wherein the ratio between the surface of the anode and the volume of the part of the treated reaction medium from step (a) is higher than or equal to 0.001 cm⁻

1 and lower than or equal to 1 cm<sup>−

1</sup>.

20. The process according to claim 13 wherein (b2) is carried out in at least one of the following conditions:

i. a pH controlled and maintained in a range which lowest limit is higher than or equal to 0.01 and which highest limit is lower than 6,

ii. a temperature higher than or equal to 10°

C. and lower than or equal to 200°

C., a pressure higher than or equal to 1 bar (absolute) and lower than or equal to 11 bar,

iii. when (b2) of the process is carried out in a discontinuous mode, a duration higher than or equal to 0.05 h and lower than or equal to 8 h,

iv. when (b2) of the process is carried out in a continuous mode, a residence time higher than or equal to 0.05 h and lower than or equal to 8 h.