CN101041497A - Treatment method for chromium-containing industrial sewage - Google Patents
Treatment method for chromium-containing industrial sewage Download PDFInfo
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- CN101041497A CN101041497A CN 200710010270 CN200710010270A CN101041497A CN 101041497 A CN101041497 A CN 101041497A CN 200710010270 CN200710010270 CN 200710010270 CN 200710010270 A CN200710010270 A CN 200710010270A CN 101041497 A CN101041497 A CN 101041497A
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- microcapsule
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Abstract
The invention discloses a handling method of chrome industrial wastewater belonging to tertiry treatment and multi-purpose use domain, which comprises the following steps: (1) preparing polyamide microcapsule include soda solution through interfacial polycondensation reaction; setting ploy single succinyl imines as disperser; (2) proceeding functionalization pretreating of polyamide microcapsule; using skellysolve C -carbon tetrachloride solution of tributyl phosphate (TBP) to soak microcapsule with finite time; (3) enriching hexavalent chromium of industrial waste water through functionalization microcapsule; making microcapsule possess function of enriching hexavalent chromium. This invention avoids hexavalent chromium ion transfer to trivalent chromium and retrieving use hexavalent chromium.
Description
Technical field
This invention relates to a kind of treatment process of trade effluent.Especially relate to direct processing of a kind of use microcapsulary and contain Cr
6+The treatment process of ion trade effluent.
Background technology
In metallurgy, plating, metal finishing, leather processing and/or other industry, extensively exist the sexavalent chrome that environment is produced severe contamination, chromate waste water is discharged in the environment and can not degrades, can only change form or be transferred, dilute, accumulate, chromic processing more complicated of while, thus very big to environmental hazard.Developed at present and practical application the method for multiple processing waste water containing chrome, wherein using more widely, the processing waste water containing chrome method is the redox precipitation method, promptly make reductive agent with ferrous sulfate, with sulfuric acid the pH value of solution value is transferred between 2～3 earlier, add the ferrous sulfate solid again, making hexavalent chrome reduction is trivalent chromium, wherein the weight ratio of ferrous sulfate and hexavalent chromium is 40～50: 1, adding sodium hydroxide then is adjusted to the pH value of waste liquid between 8～9, after entering settling tank and carrying out precipitate and separate, discharge of wastewater, mud focuses on after treatment.The chromate waste water that aforesaid method is handled needs earlier Cr
6+Ion is converted into Cr
3+Although ion is Cr
6+Ion reaches emission standard, but total chrome content is still not up to standard, still can not reach emission standard.The method of above-mentioned processing waste water containing chrome exists a large amount of alkali of consumption and a large amount of ferrous sulfate simultaneously, and forms more mud, causes secondary pollution easily.
In order directly to handle the Cr that contains of industrial generation
6+Ionic waste water makes chromate waste water reach national specified discharge standard, i.e. Pai Fang Cr
6+Ion content is less than 0.5mg/l (" integrated wastewater discharge standard " GB9878-1996), and we have invented direct processing of functionalization microcapsulary and have contained Cr
6+Ion trade effluent technology.Use this method to handle industrial wastewater containing chromium, do not need Cr
6+Ion is converted into Cr
3+Ion, the industrial wastewater containing chromium after the processing can reach emission standard, and can not produce secondary pollution.
Functionalization microcapsule of the present invention are handled industrial wastewater containing chromium and are mainly used in the following industry, as the industrial chromium-containing waste water of generations such as metal finishing industry, multicolor printing, chemical industry and pharmaceutical industry.
Summary of the invention
One of purpose of this invention just provide a kind of rapidly and efficiently, simple, direct processing contains Cr
6+The method of ion trade effluent.
Functionalization microcapsule of the present invention are directly handled and are contained Cr
6+The ion trade effluent has following characteristics: prepare the microcapsule that include sodium carbonate solution earlier, control the intensity of microcapsule by the wall thickness of regulating microcapsule; Then microcapsule are carried out surface-functionalized processing, be about to microcapsule and soak certain hour at the normal heptane-carbon tetrachloride solution of tributyl phosphate (TBP); Cr in the direct enrichment trade effluent of function of surface microcapsules
6+Ion is to the Cr of enrichment
6+Ion recyclable utilization or focus on after chemical separation.
Now part science and engineering industry chromate waste water technology division of the present invention is as follows.
1. the preparation of polymeric amide microcapsule
Known emulsion process or electrodispersion method, preferably emulsion process are adopted in the preparation that includes the polymeric amide microcapsule of sodium carbonate solution.One of monomer is chloroform-carbon tetrachloride solution of sebacoyl chloride 2%～5% (v/v), sebacoyl chloride is between 1.5%～2.5% (v/v) in the concentration of chloroform-carbon tetrachloride solution, and the density of the ratio control solution by regulating chloroform and tetracol phenixin is between 0.9～1.1; Two of monomer is the aqueous sodium carbonate that contains polyamine, the concentration of polyamine is between 4%～6%, be the intensity and the thickness of control microcapsule wall, the polyamine that can select comprises the composite of hexanediamine, quadrol, diethylenetriamine, tetraethylenepentamine or any two kinds of materials.
The dispersion agent that emulsion process prepares the polymeric amide microcapsule can be the tensio-active agent of water-in-oil-type, wherein first-selected is poly-mono butonediimide, be commonly referred to blue 113B, poly-mono butonediimide is oil-soluble tensio-active agent, usually be mixed with 1: 1 kerosin before the use, the working concentration of the poly-mono butonediimide of tensio-active agent is between 0.5%～1% (v/v).Poly-mono butonediimide has following chemical structural formula:
The concentration of contained sodium carbonate solution is between 10%～20% (m/m) in the polymeric amide microcapsule, and after the microcapsule preparation was finished, with materials such as the chloroform of removing surface of microcapsule and tetracol phenixin, sherwood oil can be repeatedly used with petroleum ether microcapsule 1～2 time.Processing contains Cr
6+Generally between 200～300 μ m, the capsule wall thickness is generally between 20～40 μ m for the microcapsule particle diameter of ion waste water.
The interfacial polycondensation chemical equation of preparation polymeric amide microcapsule is as follows:
nNH
2-(CH
2)
6-NH
2+nClCO-(CH
2)
8-COCl→[-NH-(CH
2)
6-NH-CO-(CH
2)
8-CO-]
n+HCl
2. the functionalization preconditioning technique of polymeric amide microcapsule
The key character that contains the direct treatment technology of sexavalent chrome trade effluent of the present invention is the pre-treatment of polymeric amide microcapsule.Its method is: will include the normal heptane-carbon tetrachloride solution immersion certain hour of the polymeric amide microcapsule of sodium carbonate solution with tributyl phosphate (TBP), the purpose of immersion is to make microcapsule have reverse osmosis and active transmission Gr
6+Ionic function, tributyl phosphate (TBP) in the concentration of normal heptane-carbon tetrachloride solution between 8%～12% (v/v), the soak time of microcapsule usually between 5～6h effect best.
The polymeric amide microcapsule are had the function of active transportation after tributyl phosphate (TBP) modification, promptly have biomembranous characteristic, the microcapsule with this characteristic can be efficiently, the Cr in the enrichment trade effluent apace
6+Ion.
3. the functionalization microcapsule are to chromic enrichment in the trade effluent
Under normal temperature, normal pressure, the pH value of regulating trade effluent with sulfuric acid is regulated water quality to industrial wastewater containing chromium by the oil removal equalizing tank simultaneously between 4～5, and removal is oily; And then the microcapsule after the above-mentioned surface-functionalized processing are fixed in the purification tank for liquid waste Cr in can direct enrichment chromate waste water
6+Ion.According to Cr in the waste water
6+Ionic content is adjusted the duration of contact of microcapsule and waste water, and be controlled between 5～20min general duration of contact, the Cr in the waste water after handling like this
6+Ion content promptly meets national specified discharge standard.To monitor the color and the Cr of waste water in the industrial wastewater containing chromium treating processes at any time
6+Ion content and pH value, colourless, the Cr of waste water
6+Ionic concn is less than getting final product waste discharge between 0.5mg/L, pH=6～7.The high chromium concentration that is enriched in the microcapsule is recycled.
The action principle of functionalization microcapsule processing waste water containing chrome is the complexing action of dichromate ion and tributyl phosphate.Cr in the solution
2O
7 2-Complex reaction takes place in the tributyl phosphate on ion and the microcapsule wall (TBP), reacts available following chemical equation and represents:
The salt yellow soda ash of bag is weakly alkaline in the microcapsule, with H
2Cr
2O
7The nTBP reaction generates chromate ion CrO
4 2-, the TBP that discharges simultaneously turns back on the microcapsule wall.Because have only H
2Cr
2O
7Can with TBP complexing, and CrO
4 2-Ion can not with the TBP complexing.
Embodiment
The present invention also can be explained with reference to following embodiment, is not to define or limit the present invention by any way.
Embodiment 1
1. the diethylenetriamine of selecting 10% quadrol+5% is as water-soluble monomer, chloroform-the carbon tetrachloride solution of 5% (v/v) sebacoyl chloride is as oil-soluble monomer, include the microcapsule of sodium carbonate solution by the interfacial polycondensation prepared in reaction, the concentration of sodium carbonate solution is 10% (w/v); 2. tributyl phosphate (TBP) normal heptane-carbon tetrachloride solution with 10% after microcapsule being washed with sherwood oil soaks 6h; 3. the pH value of regulating chromate waste water with sulfuric acid is regulated water quality to industrial wastewater containing chromium by the oil removal equalizing tank simultaneously between 4～6, and removal is oily; 4. will be fixed in the chromate waste water treating pond through the microcapsule after tributyl phosphate (TBP) is handled, microcapsule and chromate waste water volume ratio are 1: 6, and waste water and microcapsule are controlled between 4.5～18min duration of contact; 5. monitor color and Cr in the waste water
6+Ion content and pH value, colourless, the Cr of waste water
6+Ionic concn is less than getting final product waste discharge between 5mg/L, pH=6～7; 6. the high chromium concentration that is enriched in the microcapsule is recycled.
Following table has been listed Cr in the waste water
6+The relation of ionic concn and duration of contact:
| Test piece number (Test pc No.) | Cr in the waste water 6+Ionic concn mg/L | Reach required min duration of contact of emission standard | Handle back Cr 6+Concentration mg/L | Handle back pH |
| 1 2 3 4 | 50 250 500 1000 | 4.5 8 12 18 | 0.13 0.24 0.11 0.38 | 6～7 6～7 6～7 6～7 |
Embodiment 2
1. select 10% diethylenetriamine as water-soluble monomer, the chloroform-carbon tetrachloride solution of 5% (v/v) sebacoyl chloride prepares the microcapsule that include sodium carbonate solution as oil-soluble monomer by electrical dispersion, and the concentration of sodium carbonate solution is 15% (w/v); 2. tributyl phosphate (TBP) normal heptane-carbon tetrachloride solution with 10% after microcapsule being washed with sherwood oil soaks 6h; 3. the pH value of regulating chromate waste water with sulfuric acid is regulated water quality to industrial wastewater containing chromium by the oil removal equalizing tank simultaneously between 4～6, and removal is oily; 4. will be fixed in the chromate waste water treating pond by microcapsule after tributyl phosphate (TBP) is handled, microcapsule and chromate waste water volume ratio are 1: 10, Cr in the waste water
6+Ionic concn is 500mg/L, and makes microcapsule contact 12min with this waste water; 5. monitor Cr in the waste water
6+Ion content and pH value, the Cr in the processed waste water
6+Ionic concn is between 0.11mg/L, pH=6～7, allow compliance with emission standards; 6. the high chromium concentration that is enriched in the microcapsule is recycled.
Such scheme and embodiment only play illustration, and those skilled in the art can make many changes or improvement to the present invention, but do not break away from the protection domain of essence of the present invention and claim.
Claims (7)
1. the treatment process of an industrial wastewater containing chromium, comprise that (1) includes the preparation of sodium carbonate solution polymeric amide microcapsule, (2) the functionalization pre-treatment of polymeric amide microcapsule, (3) sexavalent chrome in the functionalization microcapsule enrichment trade effluent, it is characterized in that, the microcapsule of handling with tributyl phosphate (TBP) can be efficiently, fast, the sexavalent chrome in the enrichment waste water directly, do not need earlier sexavalent chrome to be converted into trivalent chromium, the waste water after the processing reaches national specified discharge standard.
2. according to the method for the described functionalization microcapsule of claim 1 processing waste water containing chrome, the dispersion agent that emulsion process prepares the polymeric amide microcapsule is poly-mono butonediimide, be called for short blue 113B, usually will be mixed with it kerosin of 1: 1 before poly-mono butonediimide uses, the working concentration of the poly-mono butonediimide of tensio-active agent is between 0.5%～1% (v/v).
3. according to the described industrial chromium-containing waste water treatment process of claim 1, it is characterized in that with normal heptane-carbon tetrachloride solution immersion polymeric amide microcapsule certain hour of tributyl phosphate (TBP), the soak time of microcapsule is between 5～6h.
4. according to the described industrial chromium-containing waste water treatment process of claim 1, it is characterized in that, tributyl phosphate (TBP) in the concentration of normal heptane-carbon tetrachloride solution between 8%～12% (v/v).
5. according to the described industrial chromium-containing waste water treatment process of claim 1, it is characterized in that, under normal temperature, normal pressure, be adjusted between 4～5 with the pH value of sulfuric acid with industrial wastewater containing chromium.
6. according to the described industrial wastewater containing chromium treatment process of claim 1, it is characterized in that, the microcapsule after the above-mentioned surface-functionalized processing are fixed in the purification tank for liquid waste, get final product the Cr in the direct enrichment chromate waste water
6+Ion.
7. according to the described industrial wastewater containing chromium treatment process of claim 1, it is characterized in that, according to Cr in the trade effluent
6+Ionic content is adjusted the duration of contact of microcapsule and waste water, and be controlled between 5～20min general duration of contact.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710010270 CN101041497A (en) | 2007-02-01 | 2007-02-01 | Treatment method for chromium-containing industrial sewage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710010270 CN101041497A (en) | 2007-02-01 | 2007-02-01 | Treatment method for chromium-containing industrial sewage |
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|---|---|
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Family
ID=38807325
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293041A (en) * | 2018-09-25 | 2019-02-01 | 成都兴蓉环保科技股份有限公司 | The combination treatment method of discarded sodium dichromate and emulsion |
| CN112691498A (en) * | 2020-12-14 | 2021-04-23 | 辽宁师范大学 | Processing apparatus that multiple exhaust-gas treatment technology coupling was used jointly |
-
2007
- 2007-02-01 CN CN 200710010270 patent/CN101041497A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293041A (en) * | 2018-09-25 | 2019-02-01 | 成都兴蓉环保科技股份有限公司 | The combination treatment method of discarded sodium dichromate and emulsion |
| CN109293041B (en) * | 2018-09-25 | 2021-05-18 | 成都兴蓉环保科技股份有限公司 | Combined treatment method of waste sodium dichromate and emulsion |
| CN112691498A (en) * | 2020-12-14 | 2021-04-23 | 辽宁师范大学 | Processing apparatus that multiple exhaust-gas treatment technology coupling was used jointly |
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Open date: 20070926 |