CN1317054C - Liquid membrane emulsion and its usage - Google Patents
Liquid membrane emulsion and its usage Download PDFInfo
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- CN1317054C CN1317054C CNB2004100610920A CN200410061092A CN1317054C CN 1317054 C CN1317054 C CN 1317054C CN B2004100610920 A CNB2004100610920 A CN B2004100610920A CN 200410061092 A CN200410061092 A CN 200410061092A CN 1317054 C CN1317054 C CN 1317054C
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- heavy metal
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- liquid film
- emulsion
- metal ion
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Abstract
The present invention relates to a liquid membrane emulsion and a purpose thereof. The liquid membrane emulsion is a mixture, and comprises reagent solution, kerosine and an emulsifying agent, wherein the reagent solution is the ligand solution of a coordination compound and/or the salt compound solution of the acid radical of a precipitate, wherein the ligand solution and heavy metal ions can form an overall stability constant which is greater than 10<15>, and the salt compound solution and heavy metal ions can form a solubility product constant which is smaller than 10<-12>. the concentration of the reagent solution is from 0.01 M to 0.2M. the liquid membrane emulsion is applied to a regeneration method after the heavy metal is adsorbed by mineral absorbing material. The liquid membrane emulsion and the purpose thereof enable the mineral material to be desorbed and regenerated after the mineral material absorbs heavy metal ions.
Description
Technical field
The present invention relates to liquid film extractive technique field, liquid film emulsion of particularly in liquid-film method, using and uses thereof.
Background technology
It is to develop emerging extraction and separation technology very rapidly over past ten years that liquid film separates, and is called for short the ELM technology.Because liquid Membrane Separation Technique has advantages such as efficient, quick, easy, energy-conservation, at present, this technology is extensive studies in space flight, oil, metallurgy, environmental protection, medicine, biology, desalinization, chemical and electronics industry, and many fields are by the laboratory production that moves towards the industrialization.As: " Guangxi chemical industry " the 23rd rolled up 1994 the 1st articles " liquid-film method is put forward the rare earth Study on Conditions " on the phase 44-48 page or leaf, discloses liquid Membrane Separation Technique and using aspect the extraction rare earth.
In addition, along with developing rapidly of industry and concentrating of urban population, the pollutant of people's discharging in producing and living, especially the sewage that contains some heavy metal ion, eliminate by the degraded of biology because heavy metal ion can not be polluted as organic matter, the water environment of depending on for existence to the mankind has caused serious threat.For this reason, the scientific worker of various countries has taked by every means as air supporting method, the precipitation method, electrochemical process, electroosmose process, centrifugal exchange process, vacuum distillation method etc.But these methods, or need to introduce other materials, or the preliminary treatment complexity; Or complex operation, being difficult for grasping, especially disposal cost costliness is brought difficulty to implementing, and is difficult to remove simultaneously contents of many kinds of heavy metal ion.
In order effectively to eliminate the heavy metal ion in the sewage, people utilize the Interfacial Adsorption effect of mineral material at present, adopt the method for absorption to handle the waste water that contains heavy metal ion, the research of this respect is carried out quite a lot ofly at home and abroad, as: Chinese patent publication number CN1194238A, disclosed " method that the industrial wastewater heavy metal is removed " etc., although these methods have obtained water treatment effect preferably, but the mineral material that has adsorbed heavy metal ion can cause secondary pollution as the processing of not regenerating.
Now, mineral material both domestic and external regeneration is main adopts methods such as chemical reagent such as acid, alkali, salt or heat-flash, magnetic field, microwave to regenerate, and these methods or regeneration effect are not good, or mineral structure is changed, and mineral material can't be repeatedly used.
Summary of the invention
Technical problem to be solved by this invention is: a kind of liquid film emulsion and uses thereof is provided, and this liquid film emulsion and uses thereof can make desorb after the mineral material Adsorption of Heavy Metal Ions, regeneration.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of liquid film emulsion, it is a mixture, it comprises reagent solution, kerosene, department's basis, thickener; Its weight proportion is:
100 parts of reagent solutions, kerosene 50-100 part, take charge of this 4-5 part, thickener 0.5-2 part;
Above-mentioned reagent solution is:
Energy and heavy metal ion form accumulation stability constant ratio greater than 10
15The ligand solution of complex
Or/and
Have and to form solubility product constant less than 10 with heavy metal ion
-12The compound solution of sedimentary acid group;
Reagent solution concentration is 0.01-0.2M (mol/L).
In the such scheme, energy and heavy metal ion form the accumulation stability constant greater than 10
15The ligand solution of complex be one or both combination in ammoniacal liquor, the EDTA sodium salt solution.
In the such scheme, have and to form solubility product constant less than 10 with heavy metal ion
-12The compound solution of sedimentary acid group be Na
2S, Na
2CO
3, Na
3PO
4The combination of one or more in the solution.
In the such scheme, take charge of this employing SPAN-80.
In the such scheme, thickener is Henkel KGaA DSX2000.
Application in the renovation process of above-mentioned liquid film emulsion behind mineral adsorbing material absorption heavy metal.
The raw material that liquid film emulsion of the present invention, the reagent solution of liquid film (interior water) adopt is: 0.01-0.2M (can and heavy metal ion form accumulation stability constant ratio greater than 10
15The part of complex or/and have and can form solubility product constant less than 10 with heavy metal ion
-12The compound of sedimentary acid group) solution; Oil phase adopts kerosene; Emulsifying agent employing department originally.
Energy and heavy metal ion form the accumulation stability constant greater than 10
15The ligand solution of complex be that ammoniacal liquor (forms the accumulation stability constant greater than 10 with heavy metal ion
15), the EDTA sodium salt (forms the accumulation stability constant greater than 10 with heavy metal ion
15) one or both combination in the solution.
Have and to form solubility product constant less than 10 with heavy metal ion
-12The compound solution of sedimentary acid group be Na
2S (forms solubility product constant greater than 10 with heavy metal ion
-12), Na
2CO
3(form solubility product constant greater than 10 with heavy metal ion
-12), Na
3PO
4(forming solubility product constant with heavy metal ion is greater than 10
-12) one or more combination in the solution.
Take charge of this employing SPAN-80.
In order to form stable liquid film and to make bubble be not easy to break, also be added with thickener in the liquid film emulsion of the present invention and make membrane stabilizer, coating thickener adopts Henkel KGaA DSX2000.
Adopt the mineral material after heavy metal is adsorbed in liquid film emulsion regeneration of the present invention, its operation principle is: utilize interior phase material in the liquid film to have with the Johnson ﹠ Johnson of heavy metal ion and become active force, in the liquid film separation process, oil phase adopts kerosene, because the mineral material of Adsorption of Heavy Metal Ions still exists absorption and desorb balance in water, because the warm-up movement of self can be passed liquid film, enter interior water in the aqueous phase heavy metal ion.Since the part of heavy metal ion and aqueous phase generate the very big complex of accumulation stability constant or and the anion acid group of aqueous phase generate the very little sediment of solubility product constant, thereby in solid-liquid film contact process, realize the destructive contact of the nothing of mineral material structure, carry out heavy metal ion from the mineral material interface to liquid film in the transfer of phase, realize desorb and regeneration after the mineral material Adsorption of Heavy Metal Ions.
Description of drawings
Fig. 1 is the fundamental diagram of the embodiment of the invention
The specific embodiment
The method of preparing liquid film emulsion of the present invention is: add reagent solution, SPAN-80, aviation kerosine, the DSX2000 of 0.01-0.2M, adopting rotating speed is to make emulsion in 2000-3000 rev/min the high speed dispersor to get final product.The weight such as the table 1 of each component.
Table 1
| Example example 1 | Example example 2 | Example example 3 | Example example 4 | Example example 5 | Example example 6 | Example example 7 | ||
| Reagent solution | Ammoniacal liquor (0.1M) | 100g | 50g | 25g | ||||
| EDTA sodium salt (0.01M) | 100kg | 25g | ||||||
| Na 2S(0.01M) | 100g | 50g | ||||||
| Na 2CO 3(0.05M) | 100g | 25g | ||||||
| Na 3PO 4(0.2M) | 100g | 25g | ||||||
| Aviation kerosine | 60g | 100kg | 60g | 80g | 100g | 50g | 100g | |
| SPAN-80 | 3g | 5kg | 3g | 4g | 5g | 2.5g | 5g | |
| DSX2000 | 1.2g | 2kg | 1.2g | 1.6g | 2g | 0.5g | 2g | |
Application in the renovation process of liquid film emulsion of the present invention behind mineral adsorbing material absorption heavy metal:
1, gets the absorption heavy metal Cu
2+Zeolite (water content 40%-60%) 150g, its mesolite is to Cu by analysis
2+Adsorption capacity be 3mg/g.It is dropped in the embodiment of the invention 1 liquid film emulsion, adopt 80 rev/mins rotating speed to stir 30 minutes.
Standing demix 5 minutes.The upper strata emulsion is poured out in another beaker, with the mineral material 110-120 ℃ oven dry of bottom.Through atomic absorption analysis, the Cu of zeolite
2+Content be 0.03mg/g, reach again the standard of utilizing.
To emulsion breaking, obtain two-phase with static.The day-coal oil phase is poured in another beaker, and water is a blue solution, obtains blue colored crystal through 110-120 ℃ of oven dry.
2, with mineral material the waste water that contains heavy metal is handled and the method for mineral material regeneration:
(1) contains the wastewater treatment of heavy metal: will contain heavy metal Cu
2+Waste water is useful on mineral material---the zeolite 150kg of heavy metal in the absorption waste water by adsorption tank in the adsorption tank, whether the absorption that detects mineral material has reached degree of saturation;
(2) the mineral material regenerative agent is handled: (its mesolite is to Cu by analysis when the absorption of mineral material reaches when saturated
2+Adsorption capacity be 3mg/g), drain the water in the recovery pond, the water content of the mineral material in this moment recovery pond is 40%-60%, adds the embodiment of the invention 2 liquid film emulsion 100kg, stirs 30 minutes.
(3) standing demix is 5 minutes.The upper strata emulsion is entered other container, with the mineral material 110-120 ℃ oven dry of bottom, pond.Through atomic absorption analysis, the Cu of zeolite
2+Content be 0.03mg/g, the mineral material after promptly obtaining regenerating.
(4) with static to emulsion breaking, obtain two-phase.The day-coal oil phase is poured out utilization again, and water is a blue solution, obtains blue colored crystal through 110-120 ℃ of oven dry.
3, get the absorption heavy metal Cr
3+Zeolite (water content 40%-60%) 150g, its mesolite is to Cr by analysis
3Adsorption capacity be 2.5mg/g.It is dropped in the embodiment of the invention 3 liquid film emulsions, adopt 80 rev/mins rotating speed to stir 20-40 minute.
Standing demix 5 minutes.The upper strata emulsion is poured out in another beaker, with the mineral material 110-120 ℃ oven dry of bottom.Through atomic absorption analysis, the Cr of zeolite
3Content be 0.018mg/g.
To emulsion breaking, obtain two-phase with static.The day-coal oil phase is poured in another beaker, and water is a black suspension, obtains black powder through 110-120 ℃ of oven dry.
4, get the absorption heavy metal Pb
2+Rectorite (water content 40%-60%) 150g, by analysis wherein rectorite to Pb
2+Adsorption capacity be 4.7mg/g.It is dropped in the embodiment of the invention 4 liquid film emulsions, adopt 80 rev/mins rotating speed to stir 20-40 minute.
Standing demix 5 minutes.The upper strata emulsion is poured out in another beaker, with the mineral material 110-120 ℃ oven dry of bottom.Through atomic absorption analysis, the Pb of rectorite
2+Content be 0.016mg/g.
To emulsion breaking, obtain two-phase with static.The day-coal oil phase is poured in another beaker, and water is a black suspension, obtains black powder through 110-120 ℃ of oven dry.
5, get the absorption heavy metal Ni
2+Bentonite (water content 40%-60%) 150g, its mesolite is to Ni by analysis
2+Adsorption capacity be 3.3mg/g.It is dropped in the embodiment of the invention 5 liquid film emulsions, adopt 80 rev/mins rotating speed to stir 20-40 minute.
Standing demix 5 minutes.The upper strata emulsion is poured out in another beaker, with the mineral material 110-120 ℃ oven dry of bottom.Through atomic absorption analysis, bentonitic Ni
2+Content be 0.020mg/g.
To emulsion breaking, obtain two-phase with static.The day-coal oil phase is poured in another beaker, and water is blue suspension, obtains blue powder through 110-120 ℃ of oven dry.
6, get the absorption heavy metal Cu
2+Zeolite (water content 40%-60%) 150g, its mesolite is to Cu by analysis
2+Adsorption capacity be 3mg/g.It is dropped in the embodiment of the invention 6 liquid film emulsions, adopt 80 rev/mins rotating speed to stir 30 minutes.
Standing demix 5 minutes.The upper strata emulsion is poured out in another beaker, with the mineral material 110-120 ℃ oven dry of bottom.Through atomic absorption analysis, the Cu of zeolite
2+Content be 0.022mg/g.
To emulsion breaking, obtain two-phase with static.The day-coal oil phase is poured in another beaker, and water is blue suspension, obtains blue powder through 110-120 ℃ of oven dry.
7, get the absorption heavy metal Cu
2+Zeolite (water content 40%-60%) 150g, its mesolite is to Cu by analysis
2+Adsorption capacity be 3mg/g.It is dropped in the embodiment of the invention 7 liquid film emulsions, adopt 80 rev/mins rotating speed to stir 30 minutes.
Standing demix 5 minutes.The upper strata emulsion is poured out in another beaker, with the mineral material 110-120 ℃ oven dry of bottom.Through atomic absorption analysis, the Cu of zeolite
2+Content be 0.025mg/g.
To emulsion breaking, obtain two-phase with static.The day-coal oil phase is poured in another beaker, and water is blue suspension, obtains blue powder through 110-120 ℃ of oven dry.
Operation principle such as the Fig. 1 of mineral material behind the liquid film emulsion regeneration absorption heavy metal of the present invention.
Claims (6)
1, a kind of liquid film emulsion is characterized in that: it is a mixture, and it comprises reagent solution, kerosene, department's basis, thickener; The weight proportion of each component is:
100 parts of reagent solutions, kerosene 50-100 part, take charge of this 4-5 part, thickener 0.5-2 part;
Above-mentioned reagent solution is:
Energy and heavy metal ion form the accumulation stability constant greater than 10
15The ligand solution of complex
Or/and
Have and to form solubility product constant less than 10 with heavy metal ion
-12The salt compound solution of sedimentary acid group;
Reagent solution concentration is 0.01-0.2M.
2, liquid film emulsion as claimed in claim 1 is characterized in that: energy and heavy metal ion form the accumulation stability constant greater than 10
15The ligand solution of complex be one or both combination in ammoniacal liquor, the EDTA sodium salt solution.
3, liquid film emulsion as claimed in claim 1 is characterized in that: have and can form solubility product constant less than 10 with heavy metal ion
-12The compound solution of sedimentary acid group be Na
2S, Na
2CO
3, Na
3PO
4The combination of one or more in the solution.
4, liquid film emulsion as claimed in claim 1 is characterized in that: take charge of this employing SPAN-80.
5, liquid film emulsion as claimed in claim 1 is characterized in that: thickener is DSX2000.
6, the application in the renovation process of liquid film emulsion as claimed in claim 1 behind mineral adsorbing material absorption heavy metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100610920A CN1317054C (en) | 2004-11-11 | 2004-11-11 | Liquid membrane emulsion and its usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100610920A CN1317054C (en) | 2004-11-11 | 2004-11-11 | Liquid membrane emulsion and its usage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1631496A CN1631496A (en) | 2005-06-29 |
| CN1317054C true CN1317054C (en) | 2007-05-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100610920A Expired - Fee Related CN1317054C (en) | 2004-11-11 | 2004-11-11 | Liquid membrane emulsion and its usage |
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| Country | Link |
|---|---|
| CN (1) | CN1317054C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262795B (en) * | 2021-12-27 | 2023-03-14 | 南开大学 | Water-in-oil type emulsion and preparation method and application thereof |
| CN114933325A (en) * | 2022-05-31 | 2022-08-23 | 南开大学 | Method for preparing nano copper oxide by using waste mobile phone circuit board containing copper element as raw material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070229A (en) * | 1991-08-30 | 1993-03-24 | 中国科学院大连化学物理研究所 | A kind of emulsion liquid membrane is carried gold and is reclaimed sodium cyanide technology |
| WO2001089670A1 (en) * | 2000-05-23 | 2001-11-29 | National University Of Singapore | Method for metal recovery from aqueous solutions |
-
2004
- 2004-11-11 CN CNB2004100610920A patent/CN1317054C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070229A (en) * | 1991-08-30 | 1993-03-24 | 中国科学院大连化学物理研究所 | A kind of emulsion liquid membrane is carried gold and is reclaimed sodium cyanide technology |
| WO2001089670A1 (en) * | 2000-05-23 | 2001-11-29 | National University Of Singapore | Method for metal recovery from aqueous solutions |
Non-Patent Citations (5)
| Title |
|---|
| 2 乳状液膜法迁移及分离的研究，无机化，第14期 1998 * |
| 2 乳状液膜法迁移及分离的研究，无机化，第14期 1998;乳状液膜法迁移及分离钯(II) 王靖芳，无机化学学报，第12卷第2期 1998;乳状液膜法迁移及分离钯(II)的研究 王靖芳，无机化学学报，第14卷第2期 1998;液膜处理过程中粘度的变化 曾平，膜科学与技术，第13卷第3期 1993 * |
| 乳状液膜法迁移及分离钯(II) 王靖芳，无机化学学报，第12卷第2期 1998 * |
| 乳状液膜法迁移及分离钯(II)的研究 王靖芳，无机化学学报，第14卷第2期 1998 * |
| 液膜处理过程中粘度的变化 曾平，膜科学与技术，第13卷第3期 1993 * |
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|---|---|
| CN1631496A (en) | 2005-06-29 |
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