CN104961187A - Method for treating wastewater with organic solvents - Google Patents
Method for treating wastewater with organic solvents Download PDFInfo
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- CN104961187A CN104961187A CN201510335384.7A CN201510335384A CN104961187A CN 104961187 A CN104961187 A CN 104961187A CN 201510335384 A CN201510335384 A CN 201510335384A CN 104961187 A CN104961187 A CN 104961187A
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- molecular sieve
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Abstract
The invention discloses a method for treating wastewater with organic solvents. The method includes steps of (1), adsorbing and treating the wastewater by the aid of adsorption columns; (2), cleaning the adsorption columns with molecular sieves by the aid of regeneration solvents (dichloromethane or methanol); (3), treating the adsorption columns with the molecular sieves by the aid of hydrogen peroxide or ozone and oxidizing the organic solvents which remain in the molecular sieves; (4), directly heating the columns with the molecular sieves by the aid of water vapor and displacing oxidized residual products by the aid of steam; (5), carrying out the steps (1), (2), (3) and (4) repeatedly. Adsorption materials of the adsorption columns are the water increasing molecular sieves, silica-alumina ratios of the molecular sieves are higher than 300, and the specific surface areas of the molecular sieves are larger than 500m<2>/g. The oxidized residual products remain in molecular sieve pores. The method has the advantages that discharge requirements of national regulation can be met by the wastewater, the organic solvents in the wastewater can be recycled, and accordingly resources can be recycled.
Description
Technical field
The present invention relates to field of waste water treatment, specifically containing organic solvent method of wastewater treatment.
Background technology
Extraction process separating metal generally uses in liquid method is smelted.Conventional extraction agent comprises P507(formal name used at school: 2-ethylhexyl phosphoric acid 2-(ethyl hexyl) ester, molecular formula: (C
8h
17) 2HPO
3) and extraction agent P204(formal name used at school: di-(2-ethylhexyl)phosphoric acid ester, molecular formula: (C
8h
17o) 2PO
2h).Under normal circumstances, extraction agent in use needs to add thinner, as kerosene, solvent wet goods organic solvent etc., to reduce to extract organic viscosity.
Utilize the waste water containing thinner and extraction agent that can produce some amount when extraction agent separation of rare earth elements and non-ferrous metal, under normal circumstances, these Phosphorus From Wastewater content are at 30mg/L, solvent is at 150 mg/L, in waste water, COD value and phosphorus content all exceed the discharge value of national national regulation, so the organic solvent in rational technology removing waste water and phosphorus must be taked, to meet the emission request of national regulation.
Traditional treatment process is: extraction wastewater first utilizes lime slurry neutralization sedimentation, then utilizes ozone to carry out catalytic oxidation treatment.Although the method only consumes electricity, the lime, on a small quantity coagulating agent, flocculation agent etc. of some amount, catalytic ozonation cost is high, so the method application prospect is dim.Afterwards, have research this present and utilize insoluble rare earth compound, such as, rare earth carbonate, alkali formula rare earth carbonate, rare-earth hydroxide, rare earth oxide, as sorbent material or filtering layer process extraction wastewater.But, because the agent of sorbent material specific surface only has 20m
2/ below g, so, sorbent material to extraction wastewater COD decline with phosphorous decline contribute very little.
Similar with hydrometallurgy, various filtering membrane, such as membrane for water treatment, blood penetration film, battery diaphragm etc., manufacturing processed in also produce containing the waste water of organic solvent.Mainly contain micro-film forming material in the waste water that film manufacture produces, be dissolved into the organic solvent of mould material and make film form the pore former in hole.The COD value of waste water that film manufacture produces considerably beyond the discharge value of national regulation, so, discharge again after also having to pass through process.
Summary of the invention
The object of the invention is to for above-mentioned Problems existing and deficiency, provide a kind of waste water that not only can make to reach the emission request of national regulation, meanwhile, organic solvent can also be reclaimed from waste water, realize resource circulation utilization.
Above-mentioned purpose of the present invention is achieved by following steps:
(1) waste water is carried out adsorption treatment by adsorption column, adsorption column sorbing material be silica alumina ratio more than 300, specific surface area is more than 500m
2the hydrophobicity molecular sieve of/g;
(2) regenerated solvent (methylene dichloride or methyl alcohol) is utilized to clean molecular sieve adsorption post;
(3) utilize hydrogen peroxide or ozonize molecular sieve adsorption post, make the oxidation in organic solvent remained in molecular sieve;
(4) utilize water vapor direct heating molecular sieve column, utilize steam to displace and remain in the bottom product after being oxidized in molecular sieve pores;
(5) (1), (2), (3), (4) are repeated.
For the method for wastewater treatment produced in Metal smelting process, point following steps:
(1) waste water is carried out adsorption treatment by adsorption column, adsorption column sorbing material is that silica alumina ratio is greater than 500, and specific surface area is 540m
2the hydrophobicity molecular sieve of/g, it is about 0.1mg/L that waste water carries out oil-contg after adsorption treatment through adsorption column, and phosphorus content is about 0.3mg/L;
(2) utilize methanol loop to flow through molecular sieve column, after for some time, absorption solvent oil over a molecular sieve is all taken away by methyl alcohol, and phosphorus substantially all retains over a molecular sieve;
(3) molecular sieve column utilizing hydrogen peroxide dipping phosphorous, after half an hour, oxidized by the organophosphorus of molecular sieve adsorption;
(4) utilize water vapor purging molecular sieve, the residuals remained in molecular sieve pores cements out by water vapor;
(5) (1), (2), (3), (4) are repeated.
For the method for wastewater treatment produced in filtering membrane manufacturing processed, point following steps:
(1) waste water is carried out adsorption treatment by adsorption column, in adsorption column, sorbing material is Hydrophobic Zeolite, and molecular sieve silica alumina ratio is greater than 300, the about 560m of surface-area
2/ g.Containing N,N-DIMETHYLACETAMIDE, the waste water of the film-forming base material PVC granule of Liquid Macrogol and trace is after sorbing material, N,N-DIMETHYLACETAMIDE, the film-forming base material PVC granule of Liquid Macrogol and trace is by molecular sieve adsorption, and in waste water, COD content meets public pipe network wastewater discharge standard;
(2) methylene dichloride is utilized to be circulated through molecular sieve column, after for some time, absorption all N,N-DIMETHYLACETAMIDEs, most of Liquid Macrogol and PVC granule are over a molecular sieve taken away by methylene dichloride, and Micro Amount of Polyethylene Glycol 300, PVC granule is residual over a molecular sieve;
(3) utilize hydrogen peroxide dipping to contain Micro Amount of Polyethylene Glycol 300, PVC granule molecular sieve column, after half an hour, all organic substances remained on molecular sieve adsorption post are oxidized;
(4) utilize water vapor purging molecular sieve, the residuals after the oxidation remained in molecular sieve pores cements out by water vapor;
(5) (1), (2), (3), (4) are repeated.
The present invention adopts above-mentioned design, and waste water not only can be made to reach the emission request of national regulation, meanwhile, can also reclaim organic solvent, realize resource circulation utilization from waste water.
Embodiment
The present invention is containing organic solvent method of wastewater treatment.
Embodiment < mono->:
For the method for wastewater treatment produced in Metal smelting process, point following steps:
(1) waste water is carried out adsorption treatment by adsorption column, adsorption column sorbing material is that silica alumina ratio is greater than 500, and specific surface area is 540m
2the hydrophobicity molecular sieve of/g, it is about 0.1mg/L that waste water carries out oil-contg after adsorption treatment through adsorption column, and phosphorus content is about 0.3mg/L;
(2) utilize methanol loop to flow through molecular sieve column, after half an hour, absorption solvent oil over a molecular sieve is all taken away by methyl alcohol, and phosphorus substantially all retains over a molecular sieve;
(3) molecular sieve column utilizing hydrogen peroxide dipping phosphorous, after half an hour, oxidized by the organophosphorus of molecular sieve adsorption;
(4) utilize water vapor purging molecular sieve, the residuals remained in molecular sieve pores cements out by water vapor;
(5) (1), (2), (3), (4) are repeated.
The mixed solvent containing solvent oil and methyl alcohol can be produced in above-mentioned treating processes simultaneously, because solvent oil boiling point is at about 200 DEG C, and methyl alcohol boiling point only has 64.5 DEG C, so solvent oil just can be separated through distilling to process with methyl alcohol, after separating treatment, methyl alcohol is reused as regenerated solvent, and recovered solvent oil uses as extraction thinner further across after rectification and purification process.
In the invention that utility model patent CN202881027U announces: total phosphorus is merely able to drop to 0.33mg/L from 0.90mg/L, and in design of the present invention, total phosphorus can drop to 0.3mg/L from 24.mg/L, and dephosphorization efficiency by using increases substantially
Embodiment < bis->:
For the method for wastewater treatment produced in filtering membrane manufacturing processed, point following steps:
(1) waste water is carried out adsorption treatment by adsorption column, in adsorption column, sorbing material is Hydrophobic Zeolite, and molecular sieve silica alumina ratio is greater than 300, the about 560m of surface-area
2/ g.Containing N,N-DIMETHYLACETAMIDE, the waste water of the film-forming base material PVC granule of Liquid Macrogol and trace is after sorbing material, N,N-DIMETHYLACETAMIDE, the film-forming base material PVC granule of Liquid Macrogol and trace is by molecular sieve adsorption, and in waste water, COD content meets public pipe network wastewater discharge standard;
(2) methylene dichloride is utilized to be circulated through molecular sieve column, after half an hour, absorption all N,N-DIMETHYLACETAMIDEs, most of Liquid Macrogol and PVC granule are over a molecular sieve taken away by methylene dichloride, and Micro Amount of Polyethylene Glycol 300, PVC granule are residual over a molecular sieve;
(3) utilize hydrogen peroxide dipping to contain Micro Amount of Polyethylene Glycol 300, PVC granule molecular sieve column, after half an hour, all organic substances remained on molecular sieve adsorption post are oxidized;
(4) utilize water vapor purging molecular sieve, the residuals after the oxidation remained in molecular sieve pores cements out by water vapor;
(5) (1), (2), (3), (4) are repeated.
The mixed solvent containing methylene dichloride and Liquid Macrogol, N,N-DIMETHYLACETAMIDE can be produced in above-mentioned treating processes simultaneously.Due to N,N-DIMETHYLACETAMIDE boiling point 166 DEG C, Liquid Macrogol boiling point is more than 250 DEG C, and methylene dichloride boiling point only has 39.8 DEG C, just methylene dichloride can be isolated so distill to process containing the mixed solvent process of methylene dichloride and Liquid Macrogol, N,N-DIMETHYLACETAMIDE, methylene dichloride is reused as regenerated solvent, and the bottom materials of distillation process is further across pure N,N-DIMETHYLACETAMIDE of can purifying after rectification and purification process, realize thus reclaiming N,N-DIMETHYLACETAMIDE in the waste water produced from filtering membrane manufacturing processed.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (3)
1., containing organic solvent method of wastewater treatment, it is characterized in that: point following steps:
(1) waste water is carried out adsorption treatment by adsorption column, adsorption column sorbing material be silica alumina ratio more than 300, specific surface area is more than 500m
2the hydrophobicity molecular sieve of/g;
(2) regenerated solvent (methylene dichloride or methyl alcohol) is utilized to clean molecular sieve adsorption post;
(3) utilize hydrogen peroxide or ozonize molecular sieve adsorption post, make the oxidation in organic solvent remained in molecular sieve;
(4) utilize water vapor direct heating molecular sieve column, utilize steam to displace and remain in the bottom product after being oxidized in molecular sieve pores;
(5) (1), (2), (3), (4) are repeated.
2. method of wastewater treatment according to claim 1, is characterized in that: point following steps:
(1) waste water is carried out adsorption treatment by adsorption column, adsorption column sorbing material is that silica alumina ratio is greater than 500, and specific surface area is 540m
2the hydrophobicity molecular sieve of/g, it is about 0.1mg/L that waste water carries out oil-contg after adsorption treatment through adsorption column, and phosphorus content is about 0.3mg/L;
(2) utilize methanol loop to flow through molecular sieve column, after for some time, absorption solvent oil over a molecular sieve is all taken away by methyl alcohol, and phosphorus substantially all retains over a molecular sieve;
(3) molecular sieve column utilizing hydrogen peroxide dipping phosphorous, after half an hour, oxidized by the organophosphorus of molecular sieve adsorption;
(4) utilize water vapor purging molecular sieve, the residuals remained in molecular sieve pores cements out by water vapor;
(5) (1), (2), (3), (4) are repeated.
3. method of wastewater treatment according to claim 1, is characterized in that: point following steps:
(1) waste water is carried out adsorption treatment by adsorption column, in adsorption column, sorbing material is Hydrophobic Zeolite, and molecular sieve silica alumina ratio is greater than 300, and surface-area is about 560m
2/ g, containing N,N-DIMETHYLACETAMIDE, the waste water of the film-forming base material PVC granule of Liquid Macrogol and trace is after sorbing material, N,N-DIMETHYLACETAMIDE, the film-forming base material PVC granule of Liquid Macrogol and trace is by molecular sieve adsorption, and in waste water, COD content meets public pipe network wastewater discharge standard;
(2) methylene dichloride is utilized to be circulated through molecular sieve column, after for some time, absorption all N,N-DIMETHYLACETAMIDEs, most of Liquid Macrogol and PVC granule are over a molecular sieve taken away by methylene dichloride, and Micro Amount of Polyethylene Glycol 300 and PVC granule remain over a molecular sieve;
(3) utilize hydrogen peroxide dipping molecular sieve column, after half an hour, all organic substances remained on molecular sieve adsorption post are oxidized;
(4) utilize water vapor purging molecular sieve, the residuals after the oxidation remained in molecular sieve pores cements out by water vapor;
(5) (1), (2), (3), (4) are repeated.
Priority Applications (1)
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|---|---|---|---|
| CN201510335384.7A CN104961187A (en) | 2015-06-17 | 2015-06-17 | Method for treating wastewater with organic solvents |
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|---|---|---|---|
| CN201510335384.7A CN104961187A (en) | 2015-06-17 | 2015-06-17 | Method for treating wastewater with organic solvents |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106241932A (en) * | 2016-07-31 | 2016-12-21 | 武汉理工大学 | A kind of method drawing organic solvent from water body |
| CN114195309A (en) * | 2021-12-09 | 2022-03-18 | 郭思捷 | Deep coal chemical wastewater treatment fluidization equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05220319A (en) * | 1991-10-04 | 1993-08-31 | Boc Group Plc:The | Device for removing hydrocarbon impurity from gas |
| CN101480623A (en) * | 2009-02-24 | 2009-07-15 | 江苏扬农化工集团有限公司 | Method for regenerating titanium-silicon molecular sieve catalyst |
| CN101703869A (en) * | 2009-10-28 | 2010-05-12 | 马军 | New method and device for recovering organic solvent from waste gas |
| CN101759246A (en) * | 2010-01-15 | 2010-06-30 | 马军 | Method for treatment of waste water containing organic solvents and treatment device |
-
2015
- 2015-06-17 CN CN201510335384.7A patent/CN104961187A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05220319A (en) * | 1991-10-04 | 1993-08-31 | Boc Group Plc:The | Device for removing hydrocarbon impurity from gas |
| CN101480623A (en) * | 2009-02-24 | 2009-07-15 | 江苏扬农化工集团有限公司 | Method for regenerating titanium-silicon molecular sieve catalyst |
| CN101703869A (en) * | 2009-10-28 | 2010-05-12 | 马军 | New method and device for recovering organic solvent from waste gas |
| CN101759246A (en) * | 2010-01-15 | 2010-06-30 | 马军 | Method for treatment of waste water containing organic solvents and treatment device |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106241932A (en) * | 2016-07-31 | 2016-12-21 | 武汉理工大学 | A kind of method drawing organic solvent from water body |
| CN106241932B (en) * | 2016-07-31 | 2019-10-25 | 武汉理工大学 | A method of drawing organic solvent from water body |
| CN114195309A (en) * | 2021-12-09 | 2022-03-18 | 郭思捷 | Deep coal chemical wastewater treatment fluidization equipment |
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Application publication date: 20151007 |