CN103709027A - Recovery method for aliphatic acid metal salt waste liquid - Google Patents
Recovery method for aliphatic acid metal salt waste liquid Download PDFInfo
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- CN103709027A CN103709027A CN201310648173.XA CN201310648173A CN103709027A CN 103709027 A CN103709027 A CN 103709027A CN 201310648173 A CN201310648173 A CN 201310648173A CN 103709027 A CN103709027 A CN 103709027A
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- waste liquid
- dilute sulphuric
- acid
- sulphuric acid
- recovery method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
Abstract
The invention discloses a recovery method for aliphatic acid metal salt waste liquid. The recovery method comprises the steps that: waste liquid and dilute sulphuric acid with a mass percentage concentration of 5%-35% are stirred at the temperature of 5-40 DEG C for complete reaction, and after standing, the mixture is separated into an organic phase and a water phase. The charging way of the waste liquid and the dilute sulphuric acid is simultaneous addition of the waste liquid and the dilute sulphuric acid or addition of the waste liquid into the dilute sulphuric acid. In the method, principles of preparation of weak acid from strong acid and dissolution in similar material are employed, dilute sulphuric acid is selected from a plurality of strong acids and parameters of dilute sulphuric acid concentration, charging way, stirring speed, reaction temperature and the like are optimized, thus aliphatic acid metal salts in the waste liquid are reacted with sulphuric acid to generate aliphatic acid and sulfate, after standing, stable layering is formed, the obtained organic phase and water phase can be utilized directly without treatment, and further recovery processing of the organic phase and the water phase can also be performed. Compared with existing recovery methods, the recovery method is advantaged by convenient and simple operation, low cost and environmental protection. The recovery rates of organic acids and metal salts are both above 95%.
Description
Technical field
The present invention relates to method for recovering waste liquid, especially a kind of recovery method of fatty acid metal bisulfate waste liquor.
Background technology
Lipid acid and metallic salt thereof are important organic chemistry products, are widely used for a plurality of fields of national economy such as medicine, dyestuff, agricultural chemicals, coating.The waste liquid that fatty acid metal bisulfate waste liquor forms from salt-making process, also has the waste liquid forming in the intermediates of product such as synthetic medicine, dyestuff, agricultural chemicals, coating and the process of catalyzer from lipid acid.
Fatty acid metal salt in process of production, except product, also often has a large amount of organic liquid wastes to produce; Fatty acid metal, in the intermediates of product such as synthetic medicine, dyestuff, agricultural chemicals, coating and the process of catalyzer, also often has the by products such as tar to generate.Tar is very strong to the destructiveness of catalyzer, fatty acid metal salt can be wrapped up and makes catalyst deactivation cause reaction to stop.In fatty acid metal bisulfate waste liquor, include organic inert solvent, fatty acid metal salt, also has the organic impuritys such as tar.At present, for the recovery process of fatty acid metal salt, be generally distillating recovering solvent, residue carries out environmental protection treatment, and these fatty acid metal salt that go out of use had both polluted environment, had caused again waste.
Summary of the invention
For above problem, the object of this invention is to provide a kind of technique simple and convenient, cost is low, the recovery method of the fatty acid metal bisulfate waste liquor that organic efficiency is high, particularly for the recovery method of the fatty acid metal bisulfate waste liquor of C8-C12, to overcome existing recovery method contaminate environment, highly energy-consuming, defect that the rate of recovery is low.
The present invention is by the following technical solutions:
A kind of recovery method of fatty acid metal bisulfate waste liquor, the dilute sulphuric acid that to comprise described waste liquid and mass percentage concentration be 5%-35% reacts completely at 5-40 ℃, after sufficient standing, be layered as organic phase and water, wherein, the feed way of described waste liquid and dilute sulphuric acid is that waste liquid and dilute sulphuric acid add simultaneously or waste liquid is added in dilute sulphuric acid.
Wherein, whether the waste liquid in above-mentioned recovery method and the reaction of dilute sulphuric acid be complete, can monitor by detecting pH value, when pH value approaches neutrality, reacts substantially complete.In addition,, in experiment or actual production, can determine reacting completely the time under a certain specific experiment condition by the preliminary experiment in early stage.
Wherein, after the sufficient standing in above-mentioned recovery method refers to reaction, liquid layered obviously and completely, is crossed and has standingly for a long time unnecessarily been extended the recovery process time, and cross the standing meeting of short period of time, makes reacted liquid layered also incomplete, affects recovering effect.
Wherein, in above-mentioned recovery method, after the reaction of the mass percentage concentration of dilute sulphuric acid when 5%-20%, layered effect is stable, and after layering, lower floor is transparent, and subsequent operations is convenient.In above-mentioned recovery method, the mass percentage concentration of dilute sulphuric acid is being greater than 20% while being less than or equal to 35%, stir speed (S.S.) is that the layered effect of 400rpm when following is stable, after layering, lower floor is transparent, subsequent operations is convenient, when stir speed (S.S.) is greater than 400rpm, although in most cases also can layering, yet after layering, lower floor is dope, and subsequent operations meeting is produced to certain impact.For example, when the mass percentage concentration of dilute sulphuric acid is 35%, stir speed (S.S.) has been carried out to a series of research find contriver, stir speed (S.S.) is when 200rpm, and layered effect is stable, and after layering, lower floor is transparent.
Preferably, during reaction, in waste liquid, the mol ratio of fatty acid radical and dilute sulphuric acid is 1.1-2:1.
Wherein, in above-mentioned recovery method, when temperature of reaction is 10 ℃-20 ℃, speed of response is suitable, subsequent hierarchy is clear.
Wherein, above-mentioned recovery method, obtain after organic phase and water, the organism such as lipid acid and inert organic solvents forms organic phase, and vitriol and water form water, and organic phase and water can directly reclaim use, simultaneously, when needed, also can reclaim respectively organic phase and water, the lipid acid in organic phase can adopt rectifying mode to reclaim; Vitriol in water can adopt distillation-crystallization mode to reclaim.
Wherein, the metal in above-mentioned fatty metal-salt comprises lithium, sodium, potassium, magnesium, zinc, copper, cobalt, manganese, cerium, vanadium etc. without limitation.
Above-mentioned recovery method is usually used in reclaiming C8-C12 fatty acid metal bisulfate waste liquor in industrial application.
The present invention is based on the principle of strong acid weak acid processed and similar compatibility, select suitable strong acid for recovery method, experiment is found, after dilute hydrochloric acid, rare nitric acid contact with spent catalyst, produces immediately volatile irritant gas, is unfavorable for carrying on of experiment.Analyzing reason may be that hydrochloric acid can volatilize HCl gas because strong acid weak acid processed is thermopositive reaction, and nitric acid can produce irritant gas NOx, and serious harm experimenter's is healthy.Therefore, the present invention selects dilute sulphuric acid from multiple strong acid, and to dilute sulphuric acid concentration, feed way, stir speed (S.S.), the parameters such as temperature of reaction are optimized, after making in waste liquid fatty acid metal salt with sulfuric acid reaction, generate lipid acid and vitriol, after standing, can stablize layering, the organism such as lipid acid and inert organic solvents forms organic phase, vitriol and water form water, the organic phase obtaining and water can not treated direct utilizations, also can further recycle organic phase and water, simultaneously, water in dilute sulphuric acid is as the solvent of vitriol, need not introduce in addition new solvent.More existing recovery method is compared, and recovery method of the present invention is easy to operate simply, cost is low, and technique is simple, and the rate of recovery of environmental protection, organic acid and metal-salt is all more than 95%.
Embodiment
Disclosed all features in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Disclosed arbitrary feature in this specification sheets (comprising any accessory claim, summary), unless narration especially all can be replaced by other equivalences or the alternative features with similar object.That is,, unless narration especially, each feature is an example in a series of equivalences or similar characteristics.
Embodiment 1
Take zinc neodecanoate spent catalyst (waste liquid) 200g, wherein containing neodecanoic acid root 34.74%, zinc 7.32%, containing high boiling point inert solvent 49.43%, other is organic impurity.The dilute sulphuric acid 248.4g that adds mass percentage concentration 10% stirs 40min at 20 ℃, stratification 80min.After separatory, organic phase is carried out to rectifying, obtain purity and be 99.45% neodecanoic acid 68.8g, the rate of recovery of neodecanoic acid is 97.90%.; Water distills, and obtaining purity is 97.45% zinc sulfate 50.2g, and the rate of recovery of zinc is 96.1%.
Embodiment 2
Take containing isocaprylic acid zinc waste liquid 200g, wherein containing isocaprylic acid root 12.68%, zinc 2.94%, containing high boiling point inert solvent 77.62%, other is organic impurity.The dilute sulphuric acid 76.8g that adds mass percentage concentration 15% stirs 40min at 10 ℃, stratification 80min.After layering, organic phase is carried out to rectifying, obtain purity and be 98.23% isocaprylic acid 25.2g, the rate of recovery of isocaprylic acid is 96.9%; Water distills, and obtaining purity is 97.57% zinc sulfate 20.3g, and the rate of recovery of zinc is 96.9%.
Embodiment 3
Take containing dodecylic acid waste liquor of sodium 200g, wherein containing dodecane acid group 23.79%, sodium 2.83%, containing high boiling point inert solvent 65.72%, other is organic impurity.Add 10% dilute sulphuric acid 134.2g, at 5 ℃, stir 40min, stratification 80min.After separatory, organic phase is carried out to rectifying, obtain purity and be 97.86% dodecylic acid 47.3g, the rate of recovery of dodecylic acid is 96.8%; Water distills, and obtaining purity is 96.89% sodium sulfate 34.9g, and the rate of recovery of sodium is 96.7%.
Embodiment 4 10% nitric acid and 10% sulfuric acid are for the effect assessment test of recovery method
Take zinc neodecanoate spent catalyst (waste liquid), adding respectively massfraction is that 10% dilute sulphuric acid (treatment group 1) and 10% rare nitric acid (treatment group 2) react with spent catalyst, and feeding quantity is: treatment group 1: in waste liquid, the mol ratio of fatty acid radical and dilute sulphuric acid is 1.1:1; Treatment group 2: in waste liquid, the mol ratio of fatty acid radical and rare nitric acid is 1.1:1; Feed way is that dilute sulphuric acid and waste liquid add in reactor simultaneously, rare nitric acid and waste liquid add in reactor simultaneously, stir the completely rear sufficient standing of 200rpm stirring reaction under 20 ℃ of conditions, after layering, respectively the organic phase for the treatment of group 1 and treatment group 2 is carried out to further rectification under vacuum recovery.Wherein, although treatment group 2 has volatile irritant gas to produce, experimenter, making on the basis of necessary protection, carries out this bench-scale testing in stink cupboard.
Result shows, treatment group 1(dilute sulphuric acid group) in the purity of the neodecanoic acid that reclaims to 99% left and right, the rate of recovery reaches 96.5%, and the rare nitric acid group for the treatment of group 2() in the highest 75% left and right that can only reach of purity of the neodecanoic acid that reclaims, the rate of recovery reaches 85%.In addition, research is found, treatment group 1(dilute sulphuric acid group) in the neodecanoic acid that reclaims sulphur content higher than the rare nitric acid group for the treatment of group 2(), but all maintain ppm level, on final impact all and little.
Embodiment 5 dilute sulphuric acid concentration are on reaction layered effect impact test
With the sulfuric acid of different concns, with zinc neodecanoate spent catalyst (waste liquid), react, feeding quantity is that in waste liquid, the mol ratio of fatty acid radical and dilute sulphuric acid is 1.1:1, feed way is that dilute sulphuric acid and waste liquid add in reactor simultaneously, under 20 ℃ of conditions, stir, the completely rear sufficient standing of 200rpm stirring reaction, each system layering situation is as shown in table 1.
The impact of table 1 sulfuric acid concentration on effect of extracting
As known from Table 1, under 20 ℃ of temperature, 200rpm agitation condition, react, the sulphuric acid soln layered effect of 10wt% and 35wt% is better, lower floor is transparent, and experimental result is stable, easy to operate, during 45% and 65% vitriolization waste liquid, system is not stratified, thereby cannot realize effective recovery.
The evaluation test to recovery method influential effect under different stirring efficiencies of embodiment 6 35% sulphuric acid solns
With the sulphuric acid soln of 35wt%, with zinc neodecanoate spent catalyst waste liquid, react, feeding quantity is that in waste liquid, the mol ratio of fatty acid radical and dilute sulphuric acid is 1.1:1, feed way is that dilute sulphuric acid and waste liquid add in reactor simultaneously, under 20 ℃ of conditions, stirs, and stir speed (S.S.) is respectively: 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, observe layering result, result is as shown in table 2.
The impact of table 2 sulfuric acid concentration on effect of extracting
From the result of table 2, can find, stir speed (S.S.) is when 200rpm, 300rpm, 400rpm, and system layering situation is better, lower floor is transparent water, and stir speed (S.S.) is when 500rpm, 600rpm, although system layering, but there is white dope in lower floor, impact operation.Visible, stir speed (S.S.) has a certain impact to the layering result of the sulfuric acid of 35wt%.Meanwhile, through inventor, repeatedly study discovery, when stir speed (S.S.) is 200rpm, the layered effect of the sulfuric acid of 35wt% is the most stable.
The test of the different feed way of embodiment 7 on the impact of recovery method layered effect
Choose waste liquid: zinc neodecanoate spent catalyst, dodecylic acid waste liquor of sodium, isocaprylic acid zinc waste liquid, zinc neodecanoate spent catalyst, 10% the sulfuric acid that adds mass percentage concentration, feeding quantity is that in waste liquid, the mol ratio of fatty acid radical and dilute sulphuric acid is 1.5:1, standing after reacting completely under the lower 20 ℃ of temperature condition of 200rpm agitation condition, wherein, feed way is respectively: waste liquid and dilute sulphuric acid are added in reactor and stirred simultaneously; Waste liquid is splashed in dilute sulphuric acid and stirred; Dilute sulphuric acid is splashed in waste liquid and is stirred, observe each waste liquid from dilute sulphuric acid the layering situation under different feed way.
From experimental result, observe known: waste liquid and dilute sulphuric acid are added while stirring reactor simultaneously, four kinds of waste liquids react completely with dilute sulphuric acid respectively and sufficient standing after layering, lower floor is transparent; Four kinds of waste liquids are splashed in dilute sulphuric acid and are stirred respectively, react completely and sufficient standing after, layering, lower floor is transparent; Dilute sulphuric acid is splashed into respectively in four kinds of waste liquids and is stirred, react completely and sufficient standing after, mixed solution emulsification, is difficult to layering.
Think that by analysis reason may be: the lipid acid generating in initial solution and a small amount of water generation emulsion, form emulsification seed, the dilute sulphuric acid that reaction adds cannot play demulsification, so whole system is milkiness state, emulsion is dark brown.
The test of embodiment 8 temperature of reaction on the impact of recovery method layered effect
Choose waste liquid: zinc neodecanoate spent catalyst, dodecylic acid waste liquor of sodium, isocaprylic acid zinc waste liquid, zinc neodecanoate spent catalyst, 10% the sulfuric acid that adds mass percentage concentration, feeding quantity is that in waste liquid, the mol ratio of fatty acid radical and dilute sulphuric acid is 1.5:1, feed way is for add waste liquid and dilute sulphuric acid in reactor and stir simultaneously, sufficient standing after reacting completely under condition of different temperatures under 200rpm agitation condition, temperature of reaction is set and is respectively 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, observe various waste liquids and the dilute sulphuric acid layered effect under differing temps.
From experimental result, observe known: under 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃ temperature condition, each waste liquid and dilute sulphuric acid react completely and sufficient standing after, normally layering, wherein the layering at 5 ℃, 10 ℃, 20 ℃ is all right, under 50 ℃, 60 ℃, 70 ℃, 80 ℃ temperature condition, each waste liquid and dilute sulphuric acid react completely and sufficient standing after, reaction solution becomes emulsion form, is difficult to layering.5 ℃ of reactions, carry out compared with slow-motion row, in the time of 10 ℃, 20 ℃, speed of response is medium, and in the time of 30 ℃, 40 ℃, 50 ℃, speed of response is very fast, and in the time of 60 ℃, 70 ℃, 80 ℃, reaction reaches the fastest.
Embodiment 9 different methods steps are tested recovering effect impact assessment
Choosing waste liquid is zinc neodecanoate spent catalyst, treatment group reclaims in accordance with the following methods: 10% the sulfuric acid that adds mass percentage concentration, feeding quantity is that in waste liquid, the mol ratio of fatty acid radical and dilute sulphuric acid is 1.5:1, feed way is for add waste liquid and dilute sulphuric acid in reactor and stir simultaneously, sufficient standing after reacting completely under 20 ℃ of conditions under 200rpm agitation condition, organic phase is carried out rectifying and is reclaimed neodecanoic acid.Control group reclaims in such a way: adopt twice vacuum distillation method, first steam the inert organic solvents in spent catalyst, then by the content of neodecanoic acid root in still liquid in molar ratio example dropwise add 10% sulfuric acid, add-on is identical with control group.After stirring, underpressure distillation first, except anhydrating, then steams neodecanoic acid.The neodecanoic acid amount summation that neodecanoic acid in the inert organic solvents steaming for the first time and for the second time underpressure distillation steam, is exactly the neodecanoic acid reclaiming, and obtains the neodecanoic acid rate of recovery after conversion.
Result: in treatment group, neodecanoic acid is almost all dissolved in upper organic phase, and zinc sulfate dissolves in lower floor's water completely, analyzes each component concentration, the neodecanoic acid rate of recovery reaches 97.99%, and in organic phase, neodecanoic acid can reach separated effect by simple distillation with inert organic solvents.And in control group, the neodecanoic acid rate of recovery only has 80.81%, for the second time after underpressure distillation, residue is the soup compound of thickness extremely, be difficult to analyze wherein component concentration, and twice underpressure distillation needs lot of energy.Analyze knownly, the separated easy handling of the inventive method of control group, consumes energy low, and the neodecanoic acid rate of recovery is high, and zinc can be recycled by the form of zinc sulfate, is obviously better than underpressure distillation.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination disclosing in this manual, and the arbitrary new method disclosing or step or any new combination of process.
Claims (10)
1. the recovery method of a fatty acid metal bisulfate waste liquor, it is characterized in that, the dilute sulphuric acid that is 5%-35% by described waste liquid and mass percentage concentration stirs and makes it to react completely at 5 ℃-40 ℃, after standing, be layered as organic phase and water, wherein, the feed way of described waste liquid and dilute sulphuric acid is that waste liquid and dilute sulphuric acid add simultaneously or waste liquid is added in dilute sulphuric acid.
2. the recovery method of a kind of fatty acid metal bisulfate waste liquor as claimed in claim 1, is characterized in that, the mass percentage concentration of described dilute sulphuric acid is 5%-20%.
3. the recovery method of a kind of fatty acid metal bisulfate waste liquor as claimed in claim 1, is characterized in that, the mass percentage concentration of described dilute sulphuric acid is being greater than 20% while being less than or equal to 35%, and described stir speed (S.S.) is below 400rpm.
4. the recovery method of a kind of fatty acid metal bisulfate waste liquor as claimed in claim 3, is characterized in that, when the mass percentage concentration of described dilute sulphuric acid is 35%, described stir speed (S.S.) is 200rpm.
5. the recovery method of a kind of fatty acid metal bisulfate waste liquor as described in arbitrary claim in claim 1-4, is characterized in that, in described waste liquid, the mol ratio of fatty acid radical and described dilute sulphuric acid is 1.1-2:1.
6. the recovery method of a kind of fatty acid metal bisulfate waste liquor as claimed in claim 1, is characterized in that, described temperature of reaction is 10 ℃-20 ℃.
7. the recovery method of a kind of fatty acid metal bisulfate waste liquor as claimed in claim 1, is characterized in that, organic phase and water are reclaimed respectively.
8. the recovery method of a kind of fatty acid metal bisulfate waste liquor as claimed in claim 7, is characterized in that, the way of recycling of described organic phase is rectifying mode.
9. the recovery method of a kind of fatty acid metal bisulfate waste liquor as claimed in claim 7, is characterized in that, the way of recycling of described water is distillation-crystallization mode.
10. the recovery method of a kind of fatty acid metal bisulfate waste liquor as claimed in claim 1, is characterized in that, described lipid acid is C8-C12 lipid acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104672079A (en) * | 2015-02-05 | 2015-06-03 | 河北工业大学 | Process for recovering sodium isooctoate from pharmaceutical waste liquor |
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| WO2013083236A1 (en) * | 2011-12-08 | 2013-06-13 | Oxea Gmbh | Process for recovering aliphatic monocarboxylic acids from distillation residues |
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| CN103130353A (en) * | 2011-11-25 | 2013-06-05 | 中国石油天然气股份有限公司 | High calcium organic wastewater treatment method |
| WO2013083236A1 (en) * | 2011-12-08 | 2013-06-13 | Oxea Gmbh | Process for recovering aliphatic monocarboxylic acids from distillation residues |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104672079A (en) * | 2015-02-05 | 2015-06-03 | 河北工业大学 | Process for recovering sodium isooctoate from pharmaceutical waste liquor |
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Application publication date: 20140409 |