CN100420508C - Microemulsion and its preparation process and use in treating industrial phenolic waste water - Google Patents
Microemulsion and its preparation process and use in treating industrial phenolic waste water Download PDFInfo
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- CN100420508C CN100420508C CNB2006100187742A CN200610018774A CN100420508C CN 100420508 C CN100420508 C CN 100420508C CN B2006100187742 A CNB2006100187742 A CN B2006100187742A CN 200610018774 A CN200610018774 A CN 200610018774A CN 100420508 C CN100420508 C CN 100420508C
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Abstract
The present invention relates to a microemulsion, a preparation method thereof and an application of the microemulsion in treating industrial sewage containing hydroxybenzene. The microemulsion comprises an oil phase and an inner water phase, wherein the oil phase is formed from two-(2-ethyl group hexyl) phosphate ester, dehydration sorbitol monooleate and coal oil according to the mass ratio of 1: 0.5 to 1.5: 4 to 6; the inner water phase is alkaline solution; the volumetric ratio of the oil phase to the inner water phase is 5: 2 to 3. When used for treating industrial sewage containing hydroxybenzene, the microemulsion has the advantages of good liquid film stability, high mass transfer speed, high separating efficiency, simple manufacturing process, recoverable solute, etc., and the microemulsion does not need to be strongly stirred and does not need a static electricity emulsion breaking device. The processing method has the advantages of low operation cost and good operating stability, and is particularly suitable for treating, recovering and using high-concentration sewage containing hydroxybenzene. The disadvantages of large initial investment, high operation cost, large area occupation and unsuitability for high-concentration sewage treatment existing in a biological method are overcome.
Description
Technical field:
The present invention is an improvement technology emulsion liquid film being removed the separating technology of phenol, is specifically related to a kind of microemulsion and preparation method and this microemulsion and contains purposes in the phenol industrial wastewater in processing.
Background technology:
Along with the develop rapidly of modern industry, a large amount of industrial wastewaters of the thing followed are more and more serious to the pollution of environment, especially phenol wastewater.Phenol belongs to the hypertoxic type material, is cell magma material, and low concentration phenol can make protein denaturation, and high concentration can make protein precipitation; Phenol has direct infringement to various cells, and skin and mucous membrane are had strong corrosiveness.Phenol wastewater often causes the pollution of rivers and lakes, makes aquatic organism mortalities such as fish, makes crop production reduction even withered.Because it is phenol wastewater is very harmful, therefore also many to the Study on Processing Methods of phenol wastewater.The main at present method that adopts has physico-chemical process, bioanalysis and chemical oxidization method.Comprise extraction, absorption method and liquid-film method in the physico-chemical process.Adopt active carbon adsorption that the phenol wastewater of high and low concentration is all had and remove effect preferably, but the reproduction ratio of active carbon difficulty.These class methods just concentrate after-combustion with the phenol organic matter and handle, and it are not thoroughly carried out harmless treatment.Granted publication day be on October 26th, 2005, Granted publication number for the patent of invention of CN1224579C discloses the method that a kind of CWO is handled high phenol wastewater, there is above-mentioned defective equally in this method.Along with researcher's the research that deepens continuously, people progressively adopt the emulsion liquid film method of removing to handle phenol waste water now.
The method that adopts emulsion liquid film to remove the solute that dissolves in the aqueous solution proposes and obtains patent (US3410794) by N.N.Li the earliest.This method is that the aqueous solution that needs are handled is contacted with a kind of emulsion, the foreign minister of emulsion (film phase) is not dissolved each other with the aqueous solution that needs to handle, but the solute that needs to remove can see through it, the interior reactant that this solute can be changed into impermeable material that contains mutually of emulsion.Emulsion is when the processed aqueous solution contacts, and the foreign minister that the solute penetration that needs to remove is crossed emulsion enters interior phase, changes into impervious material and stays mutually interior with the reactant effect.To not contain the emulsion separation of the water and the enrichment solute of this solute then, the emulsion of enrichment solute reclaims solute behind breakdown of emulsion, and emulsion recycles.Advantages such as that this method has is efficient, energy-conservation, selectivity is good, applied widely, the solute that can remove comprise organic and inorganic compound, ionic and nonionic compound, acidity and alkali compounds etc.But, most of emulsion liquid films of being developed so far, be difficult to possess simultaneously the film separation process the key propertys such as high osmosis, high selectivity, high stability that should possess.At present, the technical barriers such as poor stability, easy swelling and breakdown of emulsion difficulty of emulsion liquid film in separation process solves as yet fully, thereby hindered the process of industrialization of Emulsion Liquid Membrane Separation Technique.
For many years, many researchers have invented microemulsion in order to overcome the above-mentioned shortcoming of emulsion liquid film, the application of microemulsion is expanded rapidly in recent years, has been penetrated into fields such as fine chemistry industry, material science, biotechnology, oil exploitation, environmental science, analytical chemistry at present.Compare with common emulsion, microemulsion is a thermodynamic stable system, and phase droplet can not cause the film leakage because of coalescent in it, thereby makes liquid film more stable; The particle diameter of micro emulsion is little, and specific area is big, this means that the micro emulsion liquid film has mass transfer rate faster; The formation of microemulsion and breakdown of emulsion are all than being easier to.Therefore invent a kind of possess simultaneously the film separation process high osmosis, high selectivity, the microemulsion of high stability that should possess be many researchers' research topic always.The inventor is through concentrating on studies, and preferred several microemulsion prescriptions by micro emulsion liquid film Research on Phenol Wastewater Treatment, have solved the liquid film instability that exists in the emulsion liquid film separation process, easy deficiency such as swelling and breakdown of emulsion difficulty preferably.
Summary of the invention:
Technical problem to be solved by this invention is the defective at prior art, and a kind of microemulsion is provided, and it has solved the problem of the liquid film instability that exists in the existing emulsion liquid film separation process, easy swelling and breakdown of emulsion difficulty effectively.
The present invention also provides this preparation of microemulsion method and this microemulsion to contain purposes in the phenol industrial wastewater in processing.
Technical scheme of the present invention is achieved in that it is mixed by oil phase and interior water, wherein oil phase is made up of by mass ratio 1: 0.5～1.5: 4～6 two-(2-ethylhexyl) phosphates, sorbitan monooleate, kerosene, interior water is an alkaline solution, and the volume ratio of oil phase and interior water is 5: 2～3.
Wherein said alkaline solution is that mass concentration is 4～10% NaOH, KOH, Na
2CO
3, K
2CO
3Solution.
Preparation method of the present invention may further comprise the steps:
Two-(2-ethylhexyl) phosphates, sorbitan monooleate, kerosene mixed in mass ratio 1: 0.5～1.5: 4～6 ratios be prepared into oil phase, under stirring at a slow speed, the interior aqueous alkaline solution of slow adding 4～10%, wherein the volume ratio of oil phase and interior water is 5: 2～3, when system gradually becomes transparent and homogeneous liquid by muddiness, promptly obtain microemulsion.
Microemulsion of the present invention is used for handling and contains the phenol industrial wastewater and have good effect, it carries out according to following steps: a, phenol wastewater enter the top of adverse current turntable extracting tower after wherein suspension, mechanical admixture are removed in coagulation, precipitation, filtration, carry out the counter current contacting extraction with microemulsion, the control speed of agitator is 200～300r/min, the volume ratio of emulsion and waste water is 1: 3～1: 10, and the time of staying of water in tower is 5～20min; B, the waste water after handling go out to enter waste water tank by tower bottom flow, and is up to standard after regulate that the pH value is directly discharged or recycling; The emulsion of c, enrichment phenol is flowed out by cat head and enters the emulsion defecator, tells oil phase and interior water after HCl back extraction three times, oil reuse behind system breast again mutually, and interior water is used to reclaim phenol or phenol sodium.
The present invention is an improvement technology emulsion liquid film being removed the separating technology of phenol.Liquid-film method removes the used emulsion of phenol and is generally Water-In-Oil (W/O) type, and interior water reagent is the NaOH aqueous solution, and outer water is a phenol wastewater, and the foreign minister of emulsion (film phase) is not dissolved each other with outer water.Phenol wastewater fully contacts by a certain percentage with emulsion, because phenol has big solubility in mutually at film, the alternative liquid film that sees through enters interior water, and generate phenol sodium with NaOH reaction, and phenol sodium is insoluble to the film phase, turn back to outer aqueous phase mutually again so it can not see through film, like this phenol in the waste water continually the ground warp liquid film enter the interior phase of film, finally the form enrichment with phenol sodium is got up in liquid film; Will be except that the emulsion separation of water behind the phenol and enrichment phenol, the emulsion of enrichment phenol reclaims phenol sodium behind breakdown of emulsion, and emulsion recycles.
The present invention is the improvement of above-mentioned emulsion liquid film separating technology:
(1) prescription of emulsion and preparation method thereof difference.
The used microemulsion of the present invention (is called for short P with two-(2-ethylhexyl) phosphates
204) be that flowing carrier, sorbitan monooleate (being called for short Span80) they are that membrane solvent, NaOH are interior water for surfactant, kerosene.Two-(2-ethylhexyl) phosphates are extractants of a kind of function admirable, in the presence of NaOH, two-(2-ethylhexyl) phosphates are generated diisooctyl phosphoric acid sodium by saponification, and diisooctyl phosphoric acid sodium has the double action of surfactant and carrier concurrently, is easy to form Water-In-Oil w/o type microemulsion.Sorbitan monooleate belongs to non-ionic surface active agent, adopts this surfactant to make the emulsion Phenol-Containing Wastewater Treatment respectively, all has to remove the phenol effect preferably, all has the shortcoming that condensate film stability is poor, swelling ratio is higher but remove in the phenol process.Research also finds, when using this surfactant separately, is difficult to form stable microemulsion liquid, but they and two-(2-ethylhexyl) phosphates all have compatibility preferably.Select suitable proportioning, can not only make stable microemulsion liquid, and remove phenol efficient and obviously improve.
The microemulsion that microemulsion preparation method of the present invention makes is the transparent system of Thermodynamically stable, and long-term storage is not stratified.And common emulsion is dispersion, and opaque, the easy layering of long-term storage.
(2) adopt the microemulsion embrane method to remove phenol, micro emulsion liquid film breakdown of emulsion automatically in separation process, interior water all returns outer water, and oil phase does not lose substantially, does not have obvious swelling and leakage, and third phase does not appear, oil phase can be made newborn reuse again after the HCl back extraction.And liquid film swelling and leakage easily take place in separation process in emulsion liquid film, and breakdown of emulsion often needs the high-voltage electrostatic demulsifying device.
Agents useful for same of the present invention is all inexpensive to be easy to get, and solvent does not lose substantially.Compare with emulsion liquid membrane, it is fast that micro emulsion liquid film Phenol-Containing Wastewater Treatment has separating rate, and good stability removes phenol rate height, does not have obvious swelling and leakage, and breakdown of emulsion does not need advantages such as strong stirring and high-voltage electrostatic demulsifying device automatically.Compare with traditional phenol method (solvent method and biochemical process) that removes, the microemulsion embrane method is removed phenol, and to have equipment simple, small investment, and advantage such as operating cost is low, and is easy and simple to handle, applied widely is particularly suitable for the improvement and the recovery of high density pollution thing.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
(1) two-(2-ethylhexyl) phosphate, sorbitan monooleate, kerosene, NaOH preparation of microemulsion
Two-(2-ethylhexyl) phosphates, sorbitan monooleate, kerosene are mixed in 1: 1.5: 5 ratio of mass ratio, under normal temperature, magnetic agitation, to wherein slowly dripping mass concentration is 5%NaOH solution, when the volume ratio that drops to oil phase and interior water is 5: 2, system gradually becomes transparent and homogeneous liquid by muddiness, promptly gets water in oil microemulsion.
(2) extraction of phenol in the waste water
A, phenol wastewater enter the top of adverse current turntable extracting tower after wherein suspension, mechanical admixture are removed in coagulation, precipitation, filtration, carry out the counter current contacting extraction with microemulsion, rotating speed, ratio of milk and water and the water time of staying in tower of control rotating disc column; B, the waste water after handling go out to enter waste water tank by tower bottom flow, and carry out sample analysis, and is up to standard after regulate that the pH value is directly discharged or recycling.If it is not up to standard that one-level is handled, then adopt two stage treatment; The emulsion of c, enrichment phenol is flowed out by cat head and enters the emulsion defecator, tells oil phase and interior water after HCl back extraction three times, oil phase reuse behind system breast again, and interior water is used to reclaim phenol or phenol sodium.
Experimental result is as follows: as the rotating speed 300r/min of rotating disc column, wastewater flow is 10L/h, and the volume ratio of emulsion and waste water is 1: 5, and the pH value of outer water is 5 o'clock, selects P for use
204, Span80, kerosene, NaOH microemulsion film system concentration of treatment be the coking phenol containing waste water of 1150mg/L, moves 210min continuously, one-level is handled, and removes the phenol rate all greater than 97%, two stage treatment goes out saliva and contains the phenol amount less than 0.02mg/L.Adopt identical experiment condition, will reclaim oil phase and reuse 5 times after breast is made in the HCl back extraction again, one-level is removed the phenol rate and is followed successively by 97.37%, 96.79%, 95.23%, 93.56%, 91.28%.
Embodiment 2
(1) two-(2-ethylhexyl) phosphate, sorbitan monooleate, kerosene,
The NaOH preparation of microemulsion
Two-(2-ethylhexyl) phosphates, sorbitan monooleate, kerosene are mixed in 1: 0.5: 4 ratio of mass ratio, under normal temperature, magnetic agitation, to wherein slowly dripping mass concentration is 4%KOH solution, when the volume ratio that drops to oil phase and interior water is 5: 2.5, system gradually becomes transparent and homogeneous liquid by muddiness, promptly gets water in oil microemulsion.
(2) in the waste water extraction of phenol with embodiment 1
Embodiment 3
(1) two-(2-ethylhexyl) phosphate, sorbitan monooleate, kerosene,
The NaOH preparation of microemulsion
Two-(2-ethylhexyl) phosphates, sorbitan monooleate, kerosene are mixed in 1: 1: 6 ratio of mass ratio, under normal temperature, magnetic agitation, are 10%Na to wherein slowly dripping mass concentration
2CO
3Solution, when the volume ratio that drops to oil phase and interior water was 5: 3, system gradually became transparent and homogeneous liquid by muddiness, promptly got water in oil microemulsion.
(2) in the waste water extraction of phenol with embodiment 1
Claims (4)
1. microemulsion, it is mixed by oil phase and interior water, wherein oil phase is made up of by mass ratio 1: 0.5～1.5: 4～6 two-(2-ethylhexyl) phosphates, sorbitan monooleate, kerosene, and interior water is an alkaline solution, and the volume ratio of oil phase and interior water is 5: 2～3.
2. according to a kind of microemulsion of claim 1, wherein said alkaline solution is that mass concentration is 4～10% NaOH, KOH, Na
2CO
3Or K
2CO
3Solution.
3. preparation of microemulsion method, it may further comprise the steps:
Two-(2-ethylhexyl) phosphates, sorbitan monooleate, kerosene mixed in mass ratio 1: 0.5～1.5: 4～6 ratios be prepared into oil phase, under stirring at a slow speed, slowly the adding mass concentration is 4～10% interior aqueous alkaline solution, wherein the volume ratio of oil phase and interior water is 5: 2～3, when system gradually becomes transparent and homogeneous liquid by muddiness, promptly obtain microemulsion.
4. the purposes of a kind of microemulsion of claim 1, it is characterized in that: described microemulsion is used for handling and contains the phenol industrial wastewater, it carries out according to following steps: a, phenol wastewater enter the top of adverse current turntable extracting tower after wherein suspension, mechanical admixture are removed in coagulation, precipitation, filtration, carry out the counter current contacting extraction with microemulsion, the control speed of agitator is 200～300r/min, the volume ratio of emulsion and waste water is 1: 3～1: 10, and the time of staying of water in tower is 5～20min; B, the waste water after handling go out to enter waste water tank by tower bottom flow, and is up to standard after regulate that the pH value is directly discharged or recycling; The emulsion of c, enrichment phenol is flowed out by cat head and enters the emulsion defecator, tells oil phase and interior water after HCl back extraction three times, oil reuse behind system breast again mutually, and interior water is used to reclaim phenol or phenol sodium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DK177307B1 (en) * | 2010-12-17 | 2012-11-12 | Aquaporin As | A liquid membrane |
| CN103173616A (en) * | 2011-12-23 | 2013-06-26 | 北京石油化工学院 | Method for extracting and separating copper and cobalt in waste lithium ion battery leach solution with microemulsion |
| CN102698622B (en) * | 2012-06-20 | 2014-10-29 | 山东大学 | Micro-emulsion for forming nano-emulsion in situ and preparation method of micro-emulsion |
| CN104944496A (en) * | 2015-06-24 | 2015-09-30 | 华东理工大学 | Phenol removing method for sodium sulfate waste water of coal tar processing |
| CN106422785A (en) * | 2016-08-04 | 2017-02-22 | 天津商业大学 | Method of refining wood vinegar based on emulsion liquid membrane |
| CN112479323A (en) * | 2020-11-23 | 2021-03-12 | 上海安赐环保科技股份有限公司 | Emulsion for treating phenolic wastewater, preparation method thereof and wastewater treatment method |
| CN115418503B (en) * | 2022-08-23 | 2023-08-01 | 成都先进金属材料产业技术研究院股份有限公司 | Method for selectively extracting scandium from leaching solution based on microemulsion |
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