CN101532089B - Method for recycling wolfram from oxidation reaction solution containing wolfram catalyst - Google Patents
Method for recycling wolfram from oxidation reaction solution containing wolfram catalyst Download PDFInfo
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- CN101532089B CN101532089B CN2009100647449A CN200910064744A CN101532089B CN 101532089 B CN101532089 B CN 101532089B CN 2009100647449 A CN2009100647449 A CN 2009100647449A CN 200910064744 A CN200910064744 A CN 200910064744A CN 101532089 B CN101532089 B CN 101532089B
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- tungsten
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- oxidation reaction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recycling wolfram from oxidation reaction solution containing wolfram catalyst. The method comprises the steps as follows: organic oxidation reaction solution containing the wolfram catalyst is added with alkaline matter for processing and heightening pH value; then acidic material is added to lower the pH value reversely; the wolfram is separated out in the form of wolframic acid under the condition that reaction solution is acidic; and finally the wolfram can be recycled by separating the wolframic acid from the reaction solution. The method has simple operation steps, reduces the operation cost during the process of recycling the wolfram and improving the recovery coefficient of the wolfram.
Description
Technical field
The present invention relates to a kind of method that from the oxidation reaction solution of tungsten-containing catalyst, reclaims tungsten.
Background technology
Tungsten-containing catalyst relies on its excellent catalytic performance, has been widely used in the multiple oxidizing reaction system.But because involving great expense of tungsten just needs to adopt the circulating reaction mode of production if will carry out large-scale production.Adopt tungstenic liquid catalyst system to react, not only its transformation efficiency and selectivity are all higher, and its condition is gentle, but maximum problem react exactly finish after, catalyzer is dissolved in the reaction mother liquor, catalyst recovery is very difficult.Along with the reaction mother liquor circulating reaction several times after, catalyst loss and by product accumulation are quite serious, and product yield constantly reduces, and the by product yield improves bigger, influenced production efficiency and product quality greatly, what make circulating reaction proceeds to lose basically value.Adopt tungstenic solid-carried catalyst reaction system, product yield is lower than tungstenic liquid catalyst system, and post catalyst reaction is solid-state, catalyzer can be separated with reaction mother liquor by simple filtration, is convenient to the recycling of catalyzer.But in each reaction, all there is the loss that can not ignore in the active ingredient of solid-carried catalyst, the overwhelming majority that runs off enters in the reaction solution, after very limited several circulation, the remaining tungstenic amount of active ingredients of solid-carried catalyst can't satisfy reaction and normally carry out, can cause product yield to reduce significantly equally, the by product yield increases substantially, and has a strong impact on production efficiency and product quality.In order to control production cost preferably; realize that tungsten-containing catalyst is used for the mass-producing economic production of oxidizing reaction, simultaneously also for the tungsten resource of saves valuable, avoids the tungsten contamination environment that discharges; reach economical environment-protective production, just must carry out recycling tungsten catalyst.
At present, the method for research recovery tungsten from the oxidation system of tungsten-containing catalyst is less.Some bibliographical information adopt ion exchange resin to reclaim the method for tungsten in ammonium para-tungstate crystal mother solution or other waste liquids, the technology of this method is longer, the slow and elutriant of wash-out consumes more, elutriant needs further processing just can obtain the more purified tungsten product that contains.Japanese Patent (WO 2006-JP319091 20060920.) has been reported and fed a kind of gas (air or nitrogen etc.) precipitation wolframic acid in the organic reaction liquid of tungsten-containing catalyst, and then isolate the method that wolframic acid reclaims tungsten, under 80 ℃ of heated and stirred, nitrogen is blown into 8h in this reaction solution, separates out yellow wolframic acid precipitation.Though the rate of recovery of this patent is very high, in fact except consuming a large amount of nitrogen, its rate of recovery is not high, also exists the yellow wolframic acid of separating out too thin most of attached to the weakness that is difficult on the wall taking out.Other tungsten tradition recovery method is not owing to consider to exist in the solution organic influence, and the tungsten catalyst that also is not suitable for organic oxidizing reaction reclaims.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of method that from the oxidation reaction solution of tungsten-containing catalyst, reclaims tungsten, simple to operate, reduce the running cost of tungsten removal process and improve tungsten recovery rate.
For achieving the above object, the present invention by the following technical solutions:
Method of the present invention will comprise the steps: to add alkaline matter for processing at least with heightening pH value in the organic oxidizing reaction liquid of tungsten-containing catalyst; And then add acidic substance and oppositely turn down the pH value, be that tungsten is separated out with the wolframic acid form at reaction solution; Be recyclable tungsten the last again wolframic acid of separating out the separation with reaction solution.The oxidizing reaction of the tungsten-containing catalyst described in the present invention is meant the oxidizing reaction that organifying compound and oxygenant carry out in the presence of tungsten-containing catalyst.The tungsten raw material of the used tungsten-containing catalyst of the present invention can be oxide compound, the tungstenic of tungsten metal, tungsten boride, carbide, tungsten sulfide, tungsten salt, wolframic acid, heteropoly acid containing tungsten, tungstenic peroxide heteropolyacid, tungstenic superoxide, contain one or more of tungsten complex etc.; Oxygenant can be one or more of oxygen, air, ozone, peroxide thing, super-oxide etc.The oxidizing reaction system of tungsten-containing catalyst of the present invention can adopt the liquid catalyst reaction system also can adopt the solid-carried catalyst reaction system, if adopt the solid-carried catalyst reaction system, after the reaction solid-carried catalyst is separated by simple filtration, and then reclaim the tungsten that is lost in the reaction solution.The reaction solution of tungsten-containing catalyst of the present invention is meant the reaction solution of oxidizing reaction system behind separated product of tungsten-containing catalyst, and this reaction solution is that the mixed system of the homogeneous aqueous solution or organic phase and water is all passable.
Further, before the step of described adding alkaline matter heightening pH value, tungsten concentration is preferably in more than the 1mg/mL in the reaction solution.Add alkaline matter and adjust the pH value in reaction mother liquor, purpose is to destroy the tungsten catalyst structure, and tungsten is existed with the acid group form.Adding acidic substance again is that tungsten is separated out with wolframic acid with the acid purpose of reaction mother liquor furnishing, behind the adding acidic substance, suitably after the ageing cooling wolframic acid of separating out is isolated from system.To add alkaline matter can be inorganic base substance in institute, for example NaOH, KOH, ammoniacal liquor, strong base-weak acid salt etc., and strong base-weak acid salt is the salt of highly basic and weak acid reaction, molten water shows alkalescence, as yellow soda ash; But this step had better not be used the material of alkaline including earth metal; Also can be organic basic material, for example organic amine, pyridines etc.It can be the mineral acid material that institute adds acidic substance, for example hydrochloric acid, sulfuric acid, nitric acid etc.; Also can be the organic acidity material, carboxylic-acid etc. for example.
In addition, in the method for the invention, at the acid-reaction liquid of isolating wolframic acid after concentrating to a certain degree, with the solids constituent separated out from, can also be with of a part of recycle of remaining acid-reaction liquid as the acidic substance described in described the inventive method.
Beneficial effect of the present invention:
The rate of recovery height of tungsten when adopting the inventive method to reclaim tungsten in the oxidizing reaction system of tungsten-containing catalyst, technological process is simple and conditional request is very low, so running cost is lower.The inventive method all obtains reclaiming not only with the tungsten that discharges in the oxidizing reaction system of tungsten-containing catalyst in the waste liquid, makes the loss of metal values reduce to zero, has saved valuable tungsten resource, has solved the pollution of the loss of tungsten to environment; And in treating processes, having reduced sour use, the material that is produced can fully utilize, and has the double benefit of economy and environmental protection.It is higher that the inventive method obtains wolframic acid purity, needing aftertreatment to prepare catalyzer again hardly reacts, the wolframic acid Separation and Recovery tungsten of promptly separating out from reaction solution is very easy, separate and adopt simple filtering to get final product, but wolframic acid dilute acid wash, for example rare nitric acid etc. can prepare tungsten catalyst after the drying again.In addition, isolate the acid-reaction mother liquor of wolframic acid, contain a small amount of undecomposed tungsten, after concentrating to a certain degree, with the solids constituent separated out from, remaining acid-reaction liquid can be used as the acidic substance recycle, reacts with initiate acidic substance one.And wherein isolated solid is roughly organic reaction product (comprising target product and by product) and inorganic salt, by the organic solvent extraction organism, separates with inorganic salt, and organism and inorganic salt can be used in other respects.So not only avoid the loss of tungsten, saved sour use, fully utilized other materials, and reduced the material environmental pollution caused by discharge, met economy, environmental protection treatment requirement.In a word, adopt the whole technology tungsten recovery rate of the inventive method higher, simple to operate, convenient post-treatment, working cost is low, and product is easy to comprehensive utilization, and environmental pollution is little, has the industrial applications prospect.
Other advantages of the present invention, target and feature will be set forth to a certain extent in the following description, and to a certain extent, based on being conspicuous to those skilled in the art, perhaps can obtain instruction from the practice of the present invention to investigating hereinafter.Target of the present invention and other advantages can be passed through following specification sheets, and claims are realized and obtained.
Embodiment
With embodiment the present invention is described further below.
Embodiment 1
Reclaim tungsten the reaction system of present embodiment hydrogen peroxide oxidation tetrahydrobenzene synthesizing adipic acid under the catalyst effect of tungstenic.The reaction of hydrogen peroxide oxidation tetrahydrobenzene synthesizing adipic acid is finished after cooling, with product crystal filtering separation from system of separating out, get above-mentioned reaction solution then, after adding NaOH adjustment reaction solution pH is 7 left and right sides agitation as appropriate, add concentrated nitric acid, separate out a large amount of precipitations, cooled and filtered, with rare nitric acid washing precipitation, drying.In order to obtain rate of recovery numerical value accurately, with the yellow solid roasting, learn it all is tungstic oxide with the x-ray powder diffraction analysis, the rate of recovery that calculates W elements after weighing is 83.3%.
Embodiment 2
Reaction system is with embodiment 1, and the reaction of hydrogen peroxide oxidation tetrahydrobenzene synthesizing adipic acid is finished after cooling, with product crystal filtering separation from system of separating out.Get above-mentioned reaction solution then, adding ammoniacal liquor adjustment reaction solution pH is about 9, after the agitation as appropriate, adds concentrated hydrochloric acid, separates out a large amount of precipitations, and cooled and filtered is used the dilute hydrochloric acid washing precipitation, drying.With the yellow solid roasting, learn it all is tungstic oxide with the x-ray powder diffraction analysis, the rate of recovery that calculates W elements after weighing is 85.4%.
Embodiment 3
Reaction system is with embodiment 1, and the reaction of hydrogen peroxide oxidation tetrahydrobenzene synthesizing adipic acid is finished after cooling, with product crystal filtering separation from system of separating out.Get above-mentioned reaction solution then, adding KOH adjustment reaction solution pH is about 10, after the agitation as appropriate, adds the vitriol oil, separates out a large amount of precipitations, and cooled and filtered is with dilute sulphuric acid washing precipitation, drying.With the yellow solid roasting, learn it all is tungstic oxide with the x-ray powder diffraction analysis, the rate of recovery that calculates W elements after weighing is 95.7%.
Embodiment 4
Reaction system is with embodiment 1, and the reaction of hydrogen peroxide oxidation tetrahydrobenzene synthesizing adipic acid is finished after cooling, with the product crystal filtering separation of separating out.Get above-mentioned reaction solution then, adding triethylamine adjustment reaction solution pH is about 5, after the agitation as appropriate, add acetate, separate out a large amount of precipitations, cooled and filtered, use the acetic acid,diluted washing precipitation, drying is with the yellow solid roasting, learn it all is tungstic oxide with the x-ray powder diffraction analysis, the rate of recovery that calculates W elements after weighing is 85.7%.
Embodiment 5
Reaction system is with embodiment 1, and the reaction of hydrogen peroxide oxidation tetrahydrobenzene synthesizing adipic acid is finished after cooling, with the product crystal filtering separation of separating out.Get above-mentioned reaction solution then, adding triethylamine adjustment reaction solution pH is about 6, after the agitation as appropriate, adds concentrated nitric acid, separates out a large amount of precipitations, and cooled and filtered is with rare nitric acid washing precipitation, drying.With the yellow solid roasting, learn it all is tungstic oxide with the x-ray powder diffraction analysis, the rate of recovery that calculates W elements after weighing is 99.5%.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, other modifications that those of ordinary skills make technical scheme of the present invention or be equal to replacement, only otherwise break away from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of the claim scope of the present invention.
Claims (7)
1. a method that reclaims tungsten from the oxidation reaction solution of tungsten-containing catalyst is characterized in that comprising the steps: adding alkaline matter and improves the pH value in the organic oxidizing reaction liquid of tungsten-containing catalyst, and the tungsten raw material of tungsten-containing catalyst is the tungstenic superoxide; And then add acidic substance and oppositely turn down the pH value, be that tungsten is separated out with the wolframic acid form at reaction solution; Be recyclable tungsten the last again wolframic acid of separating out the separation with reaction solution.
2. the method that reclaims tungsten from the oxidation reaction solution of tungsten-containing catalyst according to claim 1, it is characterized in that: before the step of described adding alkaline matter heightening pH value, tungsten concentration is preferably in more than the 1mg/mL in the reaction solution.
3. the method that reclaims tungsten from the oxidation reaction solution of tungsten-containing catalyst according to claim 1 and 2 is characterized in that: described alkaline matter adopts inorganic base substance or organic basic material; Described acidic substance adopt mineral acid material or organic acidity material.
4. the method that reclaims tungsten from the oxidation reaction solution of tungsten-containing catalyst according to claim 3 is characterized in that: described inorganic base substance adopts one or more in NaOH, KOH, ammoniacal liquor, the strong base-weak acid salt.
5. the method that reclaims tungsten from the oxidation reaction solution of tungsten-containing catalyst according to claim 3 is characterized in that: described organic basic material adopts organic amine or pyridines material.
6. the method that reclaims tungsten from the oxidation reaction solution of tungsten-containing catalyst according to claim 3 is characterized in that: described mineral acid material adopts one or more in hydrochloric acid, sulfuric acid, the nitric acid.
7. the method that reclaims tungsten from the oxidation reaction solution of tungsten-containing catalyst according to claim 3 is characterized in that: described organic acidity material adopts the carboxylic-acid substance.
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| CN2009100647449A CN101532089B (en) | 2009-04-28 | 2009-04-28 | Method for recycling wolfram from oxidation reaction solution containing wolfram catalyst |
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| CN2009100647449A CN101532089B (en) | 2009-04-28 | 2009-04-28 | Method for recycling wolfram from oxidation reaction solution containing wolfram catalyst |
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| CN101532089B true CN101532089B (en) | 2011-08-03 |
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| CN107649182B (en) * | 2017-09-07 | 2019-11-19 | 中国石油大学(华东) | The circulation utilization method of oil-soluble tungsten base slurry bed system hydrocracking catalyst |
| CN107469837B (en) * | 2017-09-07 | 2019-10-29 | 中国石油大学(华东) | Autovulcanization oil-soluble NiMo catalyst and its preparation method and application |
| CN107649152B (en) * | 2017-09-07 | 2020-01-07 | 中国石油大学(华东) | Self-vulcanized oil-soluble NiW catalyst precursor and preparation method and application thereof |
| CN114752771B (en) * | 2022-05-05 | 2023-07-28 | 崇义章源钨业股份有限公司 | Method for recovering W from XRF detection sample |
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