CN103626254A - Method for removing cyanides in cyaniding wastewater by use of emulsion liquid membrane technology - Google Patents
Method for removing cyanides in cyaniding wastewater by use of emulsion liquid membrane technology Download PDFInfo
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- CN103626254A CN103626254A CN201310552613.1A CN201310552613A CN103626254A CN 103626254 A CN103626254 A CN 103626254A CN 201310552613 A CN201310552613 A CN 201310552613A CN 103626254 A CN103626254 A CN 103626254A
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Abstract
The invention discloses a method for removing cyanides in cyaniding wastewater by use of an emulsion liquid membrane technology, which comprises the steps of dissolving a surfactant into a membrane solvent, and adding a carrier, a membrane auxiliary and sodium hydroxide internal-phase liquid; mixing, and preparing a white water-in-oil type emulsion liquid membrane by an emulsion maker; performing a mixing reaction between the emulsion liquid membrane and the cyaniding wastewater; then demulsifying, and enriching and recycling the cyanides. By imitating the characteristic of active transmission of a biological membrane, the method disclosed by the invention has the characteristics of good selectivity, high separation efficiency, great enrichment multiple, low energy consumption, simplicity in operation and short treatment period; the cyanides can be recycled, and engineering application is easy to implement; moreover, due to the advantage of repeated utilization of the membrane, the removal rate can exceed 95%, and efficient treatment and resource recycling of cyanides can be realized.
Description
Technical field
The invention belongs to environmental chemical engineering field, particularly a kind of method of utilizing liquid membrane emulsion technology to remove prussiate in cyanide wastewater.
Background technology
Prussiate is a kind of highly toxic substance, and its wide material sources the industry such as are smelted, agriculture, medical and can be produced a large amount of cyanide wastewaters in plating, ore dressing, rare precious metal.Cyanide wastewater has caused serious harm to human body and ecology, and the method for the processing cyanide wastewater of developing both at home and abroad at present is roughly divided into destroys or reclaim two large classes to prussiate.In destroy method, except traditional alkaline chlorination process, active carbon adsorption, Ozonation, ferrate oxidation method, photocatalytic oxidation, biological process etc. have been developed again; Absorption method is except traditional coagulation complex-precipitation method and acidifying volatilization-alkali absorb method, and scholars have researched and developed again membrane processing method, ion exchange method, solvent extraction, zinc sulfate method, electrolytic process etc.Aforesaid method has certain effect to the processing of prussiate, but still has in some aspects deficiency.Destroy method direct convenience, but cause the wasting of resources; Absorption method can be recycled resource within the specific limits, but exists cost high, processes the problems such as degree of depth deficiency.So, for cyanide wastewater, need practicable method, reduce the prussiate in cyanide wastewater on the one hand, reduce its pollution to environment, to reclaim resource useful in waste water on the other hand, thereby realize the innoxious and resource utilization of such waste water.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of method of utilizing liquid membrane emulsion technology to remove prussiate in cyanide wastewater, the characteristic of mimic biology film active transmission, have the advantages that selectivity is good, separation efficiency is high, enrichment times is large, energy consumption is low, easy and simple to handle, treatment cycle is short, prussiate recoverable, be easy to through engineering approaches application, and the film reusable advantage of being on good terms, clearance can reach more than 95%, can realize and processing and resource recycling prussiate is efficient.
To achieve these goals, the technical solution used in the present invention is:
Utilize liquid membrane emulsion technology to remove a method for prussiate in cyanide wastewater, surfactant dissolves, in membrane solvent, and added to phase liquid in carrier, film auxiliary agent and sodium hydroxide, after mixing, utilize system breast machine-processed Liquid Paraffin water-in type emulsion liquid film; By emulsion liquid film and cyanide wastewater hybrid reaction, then breakdown of emulsion utilizes prussiate enriching and recovering.
Described tensio-active agent is Span-80, and membrane solvent is kerosene, and carrier is tri-n-octyl amine (TOA), and film auxiliary agent is whiteruss, and in described sodium hydroxide, phase liquid is the sodium hydroxide solution of concentration 2%-3%.
In described tensio-active agent, sodium hydroxide, the proportioning of phase liquid, membrane solvent, carrier and film auxiliary agent is that volume ratio is (1～4): (90～136): (90～96): (1～5): 1.
Described emulsion liquid film and cyanide wastewater hybrid reaction are carried out at normal temperatures, and whey duration of contact is 5min～20min, and mechanical stirring rotating speed is 230r/min～270r/min, and whey volume ratio is 1:3～21, and oily internal ratio is 1:1.
The process of described breakdown of emulsion is: by hybrid reaction products therefrom stratification, then upper oil phase is utilized Ultrasonic Cleaners to carry out breakdown of emulsion 30min～60min, proceeded to the interior phase liquid that stratification after separating funnel obtains liquid film oil phase and enrichment sodium cyanide.
Wherein, can utilize breakdown of emulsion gained liquid film oil phase, use the newborn machine of system again to make emulsion liquid film to recycle.
Compared with prior art, the invention has the beneficial effects as follows:
1, emulsion liquid film of the present invention belongs to water-in-oil-type, and the specific surface area of emulsion droplets is large, and enrichment times is large, and extraction completes with the step of stripping, and selectivity is good, and its clearance can reach more than 95%, has prussiate recyclable, the advantage that water can reuse.
2, the present invention adopts low-speed machinery to stir contact recovery of cyanide, fast convenient, and the enrichment cycle is short, and processing capacity is larger.
3, the film that the present invention adopts is on good terms and is repeatedly reused.
4, the present invention adopts ultrasonic dehydration, carries out at normal temperatures, and effect is better, is convenient to subsequent disposal.
5, the present invention is that 644.46mg/L, 483.35mg/L, 322.23mg/L have good effect to different concns waste water.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and Examples, describe embodiments of the present invention in detail.
Embodiment mono-
As shown in Figure 1, the preparation of the emulsion of this embodiment is that phase liquid in TOA, whiteruss, Span-80, kerosene, sodium hydroxide is mixed standby with volume ratio 2:1:2:95:100,2:1:3:94:100,2:1:4:93:100 respectively.Mixed solution, under high shearing mixing emulsor, is mixed to 10min and obtains emulsion liquid film under rotating speed 2300r/min.By cyanide wastewater pH regulator, be 4, by emulsion liquid film and cyanide wastewater by volume 1:7 mix, mechanical stirring contact 15min under 250r/min rotating speed.By the standing phase-splitting at normal temperatures of above-mentioned mixed solution, obtain liquid film and process rear water.The standing water that obtains enrichment sodium cyanide after liquid film phase and interior water mechanical stirring breakdown of emulsion, prussiate is recycled.After treatment, Cyanide in Waste Water compound clearance is respectively 91.27%, 93.45%, 95.64%.
Embodiment bis-
As shown in Figure 1, the preparation of the emulsion of this embodiment is that phase liquid in TOA, whiteruss, Span-80, kerosene, sodium hydroxide is mixed standby with volume ratio 2:1:4:93:100 respectively.Mixed solution, under high shearing mixing emulsor, is mixed to 10min and obtains emulsion liquid film under rotating speed 2300r/min.For starting point concentration, be the cyanide wastewater waste water of 644.46mg/L, 483.35mg/L, 322.23mg/L, wastewater pH be adjusted to 4, by emulsion liquid film and cyanide wastewater by volume 1:7 mix, mechanical stirring contact 15min under 250r/min rotating speed.By the standing phase-splitting at normal temperatures of above-mentioned mixed solution, obtain liquid film and process rear water.The standing water that obtains enrichment sodium cyanide after liquid film phase and interior water mechanical stirring breakdown of emulsion, prussiate is recycled.After treatment, Cyanide in Waste Water compound clearance is respectively 86.92%, 95.35%, 97.06%.
Embodiment tri-
As shown in Figure 1, the preparation of the emulsion of this embodiment is that phase liquid in TOA, whiteruss, Span-80, kerosene, sodium hydroxide is mixed standby with volume ratio 2:1:4:93:100 respectively.Mixed solution, under high shearing mixing emulsor, is mixed to 10min and obtains emulsion liquid film under rotating speed 2300r/min.Wastewater pH is adjusted to 4, by emulsion liquid film and cyanide wastewater by volume 1:7 mix, mechanical stirring contact 15min under 250r/min rotating speed.By the standing phase-splitting at normal temperatures of above-mentioned mixed solution, obtain liquid film and process rear water.The standing water that obtains enrichment sodium cyanide after liquid film phase and interior water mechanical stirring breakdown of emulsion, prussiate is recycled, and the oil phase of gained is repeatedly reused.Repeatedly the emulsion of recycling continues cyanide wastewater to process, and after treatment, Cyanide in Waste Water compound clearance is respectively 91.27%, 93.45%, 90.40%.
Claims (6)
1. a method of utilizing liquid membrane emulsion technology to remove prussiate in cyanide wastewater, it is characterized in that, surfactant dissolves, in membrane solvent, and is added to phase liquid in carrier, film auxiliary agent and sodium hydroxide, after mixing, utilize system breast machine-processed Liquid Paraffin water-in type emulsion liquid film; By emulsion liquid film and cyanide wastewater hybrid reaction, then breakdown of emulsion utilizes prussiate enriching and recovering.
2. the method for utilizing liquid membrane emulsion technology to remove prussiate in cyanide wastewater according to claim 1, it is characterized in that, described tensio-active agent is Span-80, membrane solvent is kerosene, carrier is tri-n-octyl amine (TOA), film auxiliary agent is whiteruss, and in described sodium hydroxide, phase liquid is the sodium hydroxide solution of concentration 2%-3%.
3. the method for utilizing liquid membrane emulsion technology to remove prussiate in cyanide wastewater according to claim 1 and 2, it is characterized in that, in described tensio-active agent, sodium hydroxide, the proportioning of phase liquid, membrane solvent, carrier and film auxiliary agent is that volume ratio is (1～4): (90～136): (90～96): (1～5): 1.
4. the method for utilizing liquid membrane emulsion technology to remove prussiate in cyanide wastewater according to claim 1, it is characterized in that, described emulsion liquid film and cyanide wastewater hybrid reaction are carried out at normal temperatures, whey duration of contact is 5min～20min, mechanical stirring rotating speed is 230r/min～270r/min, whey volume ratio is 1:3～21, and oily internal ratio is 1:1.
5. the method for utilizing liquid membrane emulsion technology to remove prussiate in cyanide wastewater according to claim 1, it is characterized in that, the process of described breakdown of emulsion is: by hybrid reaction products therefrom stratification, then upper oil phase is utilized Ultrasonic Cleaners to carry out breakdown of emulsion 30min～60min, proceeded to the interior phase liquid that stratification after separating funnel obtains liquid film oil phase and enrichment sodium cyanide.
6. the method for utilizing liquid membrane emulsion technology to remove prussiate in cyanide wastewater according to claim 5, is characterized in that, utilizes breakdown of emulsion gained liquid film oil phase, uses the newborn machine of system again to make emulsion liquid film to recycle.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609495A (en) * | 2015-01-27 | 2015-05-13 | 东北大学 | Method for recycling copper and cyanide in cyanide-containing wastewater by using emulsion liquid membrane |
| WO2015169125A1 (en) * | 2014-05-07 | 2015-11-12 | 华北理工大学 | Method for removing dust in gas fumes |
| CN105347422A (en) * | 2015-11-16 | 2016-02-24 | 西安建筑科技大学 | Method for removing cyanide in cyanogen-containing waste water by ionic liquid supported liquid membrane technology |
| CN110791649A (en) * | 2018-08-01 | 2020-02-14 | 南开大学 | Method for preparing nano material from metal in electronic waste |
| CN113372240A (en) * | 2021-07-02 | 2021-09-10 | 湖北金玉兰医药科技有限公司 | Green preparation process of ethyl 2, 3-dicyanopropionate |
| CN113881847A (en) * | 2020-07-03 | 2022-01-04 | 南开大学 | Method for recovering silver from waste circuit board |
| CN114181388A (en) * | 2021-11-30 | 2022-03-15 | 河北圣雪大成制药有限责任公司 | Method for extracting polylysine from fermentation liquor |
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| CN101628767A (en) * | 2009-08-14 | 2010-01-20 | 山东科信生物化学有限公司 | Waste water integrated treatment method of paraquat produced by cyanamideprocess |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628767A (en) * | 2009-08-14 | 2010-01-20 | 山东科信生物化学有限公司 | Waste water integrated treatment method of paraquat produced by cyanamideprocess |
Non-Patent Citations (1)
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| 缪福度等: "乳化液膜法处理含氰废水", 《水处理技术》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015169125A1 (en) * | 2014-05-07 | 2015-11-12 | 华北理工大学 | Method for removing dust in gas fumes |
| CN104609495A (en) * | 2015-01-27 | 2015-05-13 | 东北大学 | Method for recycling copper and cyanide in cyanide-containing wastewater by using emulsion liquid membrane |
| CN104609495B (en) * | 2015-01-27 | 2017-02-01 | 东北大学 | Method for recycling copper and cyanide in cyanide-containing wastewater by using emulsion liquid membrane |
| CN105347422A (en) * | 2015-11-16 | 2016-02-24 | 西安建筑科技大学 | Method for removing cyanide in cyanogen-containing waste water by ionic liquid supported liquid membrane technology |
| CN110791649A (en) * | 2018-08-01 | 2020-02-14 | 南开大学 | Method for preparing nano material from metal in electronic waste |
| CN113881847A (en) * | 2020-07-03 | 2022-01-04 | 南开大学 | Method for recovering silver from waste circuit board |
| CN113372240A (en) * | 2021-07-02 | 2021-09-10 | 湖北金玉兰医药科技有限公司 | Green preparation process of ethyl 2, 3-dicyanopropionate |
| CN114181388A (en) * | 2021-11-30 | 2022-03-15 | 河北圣雪大成制药有限责任公司 | Method for extracting polylysine from fermentation liquor |
| CN114181388B (en) * | 2021-11-30 | 2023-12-01 | 河北圣雪大成制药有限责任公司 | Method for extracting polylysine from fermentation liquor |
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