CN102794179B - Catalyst for preparing formate from CO2 and preparation method thereof - Google Patents
Catalyst for preparing formate from CO2 and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of chemical industry production of formate from CO2, particularly a catalyst for preparing formate from CO2 and a preparation method thereof. The method for preparing the catalyst for preparing formate from CO2-containing synthetic gas, which is a spent contact mass generated in an organosilicon monomer methyl chlorosilane production process, comprises the following steps: washing the spent contact mass with an organic solvent, filtering, roasting, dissolving with acid, precipitating with alkali, filtering, drying and calcining. The invention solves the problem of high-value comprehensive utilization of solid residue spent contact mass in organosilicon synthesis industry. The prepared catalyst for preparing formate from CO2-containing synthetic gas has the advantages of low raw material cost and simple operational method, and can easily implement large-scale production; and the catalyst provided by the invention has higher formate synthesis activity, higher heat stability and better reproducibility, and is beneficial to controlling the product quality.
Description
Technical field
The present invention relates to synthesis gas formic acid esters chemical production field, relate to one particularly and utilize CO
2the catalyst of formic acid esters processed and preparation method.
Background technology
Producing synthesis gas from coal (CO, H
2and CO
2) to prepare high valuable chemicals be the important developing direction of coal chemical technology one.The production of synthesis gas and be applied in chemical industry and have consequence, can produce a series of chemicals by synthesis gas.Such as: synthesis gas produces ammonia and methyl alcohol, F-T synthesis produces liquid fuel, and oxo synthesis produces higher aliphatic aldehyde and alcohol etc.In addition, just under development still have the direct synthesizing glycol of synthesis gas, ethanol, acetic acid, BDO etc.Meanwhile, CO
2reduction of discharging and higher value application is also a focus of scientific research
Methylchlorosilane prepares the organic silicon monomer that organosilicon material is most important, consumption is maximum.Industrially mainly utilize this monomer of Rochow direct synthesis at present, namely in a fluidized bed reactor, silica flour and major catalyst copper powder, co-catalyst zinc powder are mixed to form active contact, along with constantly carrying out of reaction, the deposit on contact surface gets more and more, and contact activity is reduced, conversion ratio and selectively significantly to reduce, now waste catalyst need discharge reactor, adds new contact simultaneously and is beneficial to stable reaction and carries out.The gas solid separation system of fluid bed discharges the serious fine powder of surface contamination continuously, and this two parts waste residue becomes waste catalyst.These waste catalysts are made up of the zinc of porous silicon, copper, carbon and trace, and average grain diameter is comparatively thin, exposes and easily causes oxidation even to burn in atmosphere, and environmental pollution is serious, are also the hidden danger in safety in production simultaneously.Along with the production-scale continuous expansion of China's organic silicon monomer, the amount of waste catalyst constantly increases, and is China's silicone industry sustainable development problem demanding prompt solution to the reasonable disposal and utilization of waste catalyst always.
At present, large quantifier elimination has been carried out to the process of waste catalyst both at home and abroad.Patent US4758352 to reclaiming silicon from waste catalyst, copper is studied.Also waste catalyst can be carried out deep conversion is morning-night, SiCl
4, HSiCl
3, the product such as phenyl chlorosilane.For the ease of transport and process, by the process of waste catalyst deactivation, as patent US4892694 is processed into stable particle or bead.Although carried out large quantifier elimination to the process of waste catalyst, complex disposal process, secondary pollution is serious, and value-added content of product is lower.
Ester is the important Organic chemical products of a class, generally has fruital smell, therefore uses widely at perfume and essence industry.In addition, ester can be used as solvent, plasticizer and for a lot of industrial department, and can also be used in a large number producing polyester, also some is used as the raw material of organic synthesis.Ester production method is a lot, current industrial most widely used be direct esterification and transesterification.Direct esterification is reacted by Carboxylic acid and alcohol to generate ester and water, and reaction speed is comparatively slow, and only have in the presence of a catalyst, could obtain the reaction speed of industrial significance, conventional catalyst has sulfuric acid, hydrochloric acid, cationic ion-exchange resin etc.Transesterification is the course of reaction making ester and carboxylic acid, alcohol or another kind of ester react the ester needed for obtaining.Carry out in the liquid phase in the presence of a catalyst more than industrial, generally adopt base catalyst (as sodium alkoxide).
Formic acid esters is the ester that a class contains formic acid group (HCOO), belongs to the one of formates.Industrial general employing direct esterification reaction preparation.The industry preparation of such as butyl formate, hot reflux 24h is added with formic acid and butanols, take sulfuric acid as catalyst, cool rear saturated nacl aqueous solution, saturated sodium bicarbonate solution washing, then with saturated nacl aqueous solution washing, with anhydrous sodium sulfate drying, distillation, collect 106-107 DEG C of cut and namely obtain product, productive rate is 74%, and this method reaction time is long.Or obtain with formic acid, n-butanol and isopropyl formate azeotropic distillation.Study carefully in new Wuhan Research Institute and synthesize butyl formate with new catalyst, it is with heteropoly acid TiSiW
120
40/ TiO
2for catalyst, add formic acid and butanols, heating stirring and refluxing, keeps reflux temperature 94-98 DEG C, reacts after one hour and stops heating and stirring, pour out reactant liquor, first wash with a small amount of saturated common salt, then use saturated Na after cooling
2cO
3solution is washed, and adjust pH is 7-8, finally with saturated common salt washing, uses anhydrous Na
2cO
3drying, fractionation, collect the cut of 105-107 DEG C, productive rate is about 72%.Said method prepares butyl formate, and formic acid raw material is more expensive, complex process, and the sulfuric acid as catalyst is difficult to reclaim, seriously polluted and consume energy.
Summary of the invention
The present inventor is through carefully investigating certification, and the porous silicon contained in abandoned catalyst in direct synthesis methylchlorosilane can make catalyst carrier, and copper and zinc are active component, as CO
2catalyst in formic acid esters technique processed is with a wide range of applications, and not only realizes the high-valued comprehensive utilization of waste catalyst as organosilicon synthesis of solid residue, can also be CO
2formic acid esters processed provides the catalyst that cost is low, performance is good.
Therefore, the object of this invention is to provide one from CO
2the catalyst that formic acid esters processed is used.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst.
According to of the present invention from CO
2the preparation method of the catalyst that formic acid esters processed is used comprises the organic solvent cleaning of the waste catalyst produced in organic silicon monomer methylchlorosilane production process, filtration, acid dissolve, alkali precipitation, then filters, the step of dry, calcining.
According to method of the present invention, wherein, described calcining is in high temperature furnace and calcines in air, and the temperature of calcining step is l00 ~ 600 DEG C, and calcination time is 0.5 ~ 10h.
According to method of the present invention, wherein, described waste catalyst is that silicone industry utilizes that silicon is raw material, copper or the solid residue of its compound for producing in Catalyst Production organosilicon methyl chlorosilane monomer process, main containing silicon, one or more in copper and carbon etc., and one or more in the component such as the zinc of trace, iron, aluminium and tin.Waste catalyst granular size is 0.5-100 micron, and its pore structure size is 2 nanometer-10 microns, and wherein silicone content is 10-95% (weight ratio), copper content in 2-50% (weight ratio), carbon content 5-10% (weight ratio).
According to method of the present invention, wherein, the solid residue waste catalyst organic solvent produced in organosilicon compound probability is cleaned one time or multipass, dry in drying box after filtration, described organic solvent can be: one or more in ethanol, benzene, toluene, chloroform, acetone, oxolane, ether.Clean one time or roasting after multipass filtration, the condition of calcination steps is 100 ~ 900 DEG C of calcining 2 ~ 10h
According to method of the present invention, wherein, acid dissolve, alkali precipitate again, calcining step has carried out modifying and decorating to the waste catalyst after solvent clean process, what obtain containing one or more in the elements such as copper, carbon, zinc is silica-based composite porous, these method of modifying can change the pore structure, component, content etc. of regulation and control complex, and modified silica-based porous complex may be used for containing CO as catalyst
2the reaction of synthesis gas formic acid esters.
Such as, according to method of the present invention, wherein, be dissolved in acid solution by above-mentioned through the cleaned waste catalyst of organic solvent, after adding thermal agitation a period of time, add zinc salt, add precipitating reagent afterwards and regulate solution to arrive different pH value, metal after dissolving is precipitated again, finally obtains silicon/carbon/cupric oxide/zinc oxide porous complex, it can as containing CO
2the catalyst of synthesis gas formic acid esters.Described acid comprises hydrochloric acid, nitric acid, sulfuric acid etc., and described heating temperature range is 40-80 DEG C, and the reaction time is 2-10h, and described zinc salt comprises zinc nitrate, zinc chloride, zinc sulfate etc., and zinc salt addition is≤5g/mL.Described precipitating reagent is the one in NaOH, ammoniacal liquor, sodium carbonate etc., and described pH scope is 9-14, and the described time of precipitation reaction is again 2-10h.
Such as, according to method of the present invention, wherein, high temperature furnace roasting is in atmosphere placed in through the cleaned waste catalyst of organic solvent by above-mentioned, sintering temperature is at 100-900 DEG C, and roasting time is 0.5-10h, naturally cools to room temperature after roasting, obtain silicon/cupric oxide porous complex, afterwards, be dissolved in acid and stirred, added zinc salt and precipitating reagent precipitates again, finally obtain silicon/cupric oxide/zinc oxide porous complex, it can as containing CO
2synthesis gas formic acid esters in catalyst, in prepared catalyst, weight metal content copper is 1.0%-30.0%, and zinc is 0.1-10.0%.
Similarly, the invention provides one from CO
2the catalyst that formic acid esters processed is used, described catalyst with the waste catalyst produced in organic silicon monomer methylchlorosilane production process for raw material, through organic solvent cleaning, filtration, roasting, acid dissolve, alkali precipitation, and then filter, step that is dry, calcining obtains.
Formic acid esters involved in the present invention can comprise the formic acid esters such as Ethyl formate, propyl formate, isopropyl formate, butyl formate, formic acid-2-butyl ester, iso-butyl formate, t-butyl formate, amyl formate, hexyl formate.
Catalyst of the present invention is utilized from the catalytic mechanism of synthesis gas formic acid esters to be:
CO
2+1/2H
2+Cu＝HCOOCu--------------------------------(1)
HCOOCu+ROH＝HCOOR+CuOH----------------------(2)
CuOH+1/2H
2＝H
2O+Cu----------------------------------(3)
Net reaction: CO
2+ 2H
2+ ROH=CH
3oOR+H
2o--------(4)
CO
2be a kind of greenhouse gases, how to reduce discharging also higher value application is the focus of scientific research always, infers from above-mentioned mechanism, and in the reaction of synthesis gas formic acid esters, main component of its reaction is the CO in synthesis gas
2, therefore, this reaction can realize CO
2higher value application.
Catalyst prepared by the present invention, can complete the reaction of above-mentioned (4), can realize CO
2directly be converted to formic acid esters, catalyst raw material is the waste catalyst during organosilicon is produced, and CO
2one-step synthesis method butyl formate, achieves CO
2reduction of discharging and higher value application, save energy consumption.Catalyst activity and selectivity prepared by the present invention is higher, and technique is simple, and low cost of manufacture, has good industrial prospect.Meanwhile, the solid residue waste catalyst higher value application that can will produce in organosilicon compound probability process.
Organosilicon synthesis and CO
2formic acid esters processed is the field that two research directions are different.The present inventor breaks through the limitation of existing Research Thinking, considers state of development and the demand of two research fields on a macro scale, in conjunction with characteristic and the CO of organosilicon synthesis of solid residue
2the performance requirement of the catalyst in formic acid esters processed, such as utilize the loose structure of silicon materials in waste catalyst, the metallic element in waste catalyst such as copper, zinc are deposited in porous silica material after dissolving again uniformly again, achieve the high degree of dispersion of metallic particles, add the activity of metallic particles, CO
2be easy to reaction on metallic particles thus obtained formic acid esters.First the present invention finds and demonstrate abandoned catalyst in direct synthesis methylchlorosilane by experiment can as the catalyst in synthesis gas formic acid esters technique, technical solution of the present invention make use of the raw material of solid residue as catalyst of organosilicon compound probability, the twice laid of organosilicon compound probability is solved again, with CO while producing economic benefit
2the requirement of the high-performance and low-cost catalyst of formic acid esters processed, this all can exert far reaching influence to the development of two industries, therefore, the invention belongs to brand-new pioneer invention.
The invention has the advantages that:
1, the invention solves the high-valued problem of complex utilization of the solid residue waste catalyst of organosilicon compound probability;
2, the conduct that prepared by the present invention contains CO
2the catalyst of synthesis gas formic acid esters, low raw-material cost, method of operating is simple, is easy to large-scale production;
3, the catalyst that prepared by the present invention shows higher formic acid esters synthesizing activity and heat endurance.
4, the catalyst favorable reproducibility prepared of the present invention, is conducive to controlling product quality.
Accompanying drawing explanation
The XRD figure of catalyst prepared by Fig. 1 embodiment 1
The XRD figure of catalyst prepared by Fig. 2 embodiment 2
The XRD figure of catalyst prepared by Fig. 3 embodiment 3
The XRD figure of catalyst prepared by Fig. 4 embodiment 4
The XRD figure of catalyst prepared by Fig. 5 embodiment 5
The XRD figure of catalyst prepared by Fig. 6 embodiment 6
Detailed description of the invention
Following examples further illustrate the present invention, but the present invention is not limited to following examples.
The waste catalyst that following examples use for silicone industry utilize that silicon is raw material, copper or the solid residue of its compound for producing in Catalyst Production organosilicon methyl chlorosilane monomer process, namely elemental silicon and chloromethanes are under the effect of copper major catalyst and zinc co-catalyst, unreacted silicon and copper beaded catalyst powder completely in production chlorosilane monomer industrial process, and the porous complex that carbonaceous organic material pyrolysis in this process and the carbon distribution produced form.Embodiment 1-6 is the catalyst of the synthesis gas formic acid esters adopting different waste catalyst to prepare through modification.
Embodiment 1
Get the ether of abandoned catalyst in direct synthesis methylchlorosilane 5g 100mL, after ethanol respectively washes twice, after filtration in vacuum drying chamber in 100 DEG C of vacuum drying 2 hours, place it in 500mL beaker, add 100mL watery hydrochloric acid, thermal response 6h is added when 40 DEG C, slowly add sodium carbonate liquor, adjust ph is to 9, and 65 DEG C add thermal response 6h, washing, filter, in 100 DEG C of vacuum drying 6h, at 350 DEG C of calcining 2h.
X ' Pert PROMPD type the Multi-functional X ray diffractometer produced Dutch Panalytical company (PANalytical) by the catalyst material of above-mentioned preparation carries out XRD test.
The catalyst material of above-mentioned preparation is carried out ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, copper content is 3.0% (weight ratio, lower same), Zn-ef ficiency content is 0.1% (weight ratio, lower same).
Fig. 1 is the XRD figure of the catalyst that embodiment 1 obtains, wherein 2 θ=28.6 ° are the characteristic peak of Si, the acromion be made up of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, 2 θ=26.6 ° are the characteristic peaks of C, as can be seen here, with the method obtain catalyst be silicon/carbon/copper oxide catalyst.
Embodiment 2
Get the toluene of abandoned catalyst in direct synthesis methylchlorosilane 5g 100mL, after oxolane respectively washes twice, after filtration in vacuum drying chamber in 100 DEG C of vacuum drying 2 hours, be cooled to room temperature, place it in 500mL beaker, add 2gZn (N0
3)
2, add 100mL dust technology, add thermal response 4h, slowly add ammonia spirit when 60 DEG C, adjust ph is to 11, and 70 DEG C add thermal response 4h, washing, filters, in 100 DEG C of vacuum drying 6h, at 100 DEG C of calcining 10h..ICP test result display, copper content is 3.3%, and Zn-ef ficiency content is 4.3%.
Fig. 2 is the XRD figure of the catalyst that embodiment 2 obtains, wherein 2 θ=28.6 ° are the characteristic peak of Si, the acromion be made up of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, 2 θ=36.3 ° are the characteristic peaks of ZnO, as can be seen here, with the method obtain catalyst be silicon/cupric oxide/Zinc oxide catalytic.
Embodiment 3
Get the chloroform of abandoned catalyst in direct synthesis methylchlorosilane 5g 100mL, after acetone respectively washes twice, after filtration in vacuum drying chamber in 100 DEG C of vacuum drying 2 hours, put into Muffle furnace, in 600 DEG C of roasting 2h, be cooled to room temperature.Above-mentioned material is placed in 500mL beaker, adds 1gZn (NO
3)
2, add 100mL dilute sulfuric acid, 80 DEG C add thermal response 2h after, slowly add sodium hydroxide solution, regulate pH to 10,80 DEG C add thermal response 2h, washing, filter, in 100 DEG C of vacuum drying, 300 DEG C calcining 5h.ICP test result shows, and copper content is 2.3%, and Zn-ef ficiency content is 3.9%.
Fig. 3 is the XRD figure of the catalyst that embodiment 3 obtains, wherein 2 θ=28.6 ° are the characteristic peak of Si, the acromion be made up of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, 2 θ=36.3 ° are the characteristic peaks of ZnO, 2 θ=26.6 ° are the characteristic peaks of C, as can be seen here, with the method obtain catalyst be silicon/carbon/cupric oxide/Zinc oxide catalytic.
Embodiment 4
Get the toluene of abandoned catalyst in direct synthesis methylchlorosilane 5g 100mL, after ethanol respectively washes twice, after filtration in vacuum drying chamber in 100 DEG C of vacuum drying 2 hours, be cooled to room temperature, place it in 500mL beaker, add 5g Zn (NO
3)
2, add 100mL dust technology, add thermal response 8h, slowly add ammonia spirit when 50 DEG C, adjust ph is to 14, and 50 DEG C add thermal response 6h, washing, filters, in 100 DEG C of vacuum drying 6h, at 250 DEG C of calcining 8h.ICP test result shows, and copper content is 14.5%, and Zn-ef ficiency content is 10.0%.
Fig. 4 is the XRD figure of the catalyst that embodiment 4 obtains, wherein 2 θ=28.6 ° are the characteristic peak of Si, the acromion be made up of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, 2 θ=36.3 ° are the characteristic peaks of ZnO, 2 θ=26.6 ° are the characteristic peaks of C, as can be seen here, with the method obtain catalyst be silicon/carbon/cupric oxide/Zinc oxide catalytic.
Embodiment 5
Get the oxolane of abandoned catalyst in direct synthesis methylchlorosilane 5g 100mL, after ethanol respectively washes twice, after filtration in vacuum drying chamber in 100 DEG C of vacuum drying 2 hours, put into Muffle furnace, in 900 DEG C of roasting 0.5h, be cooled to room temperature, place it in 500mL beaker, add 3g Zn (NO
3)
2, add 100mL dust technology, add thermal response 3h, slowly add sodium carbonate liquor when 70 DEG C, adjust ph is to 11, and 70 DEG C add thermal response 2h, washing, filters, in 100 DEG C of vacuum drying 6h, at 350 DEG C of calcining 2h.ICP test result shows, and copper content is 23.8%, and Zn-ef ficiency content is 5.6%.
Fig. 5 is the XRD figure of the catalyst that embodiment 5 obtains, wherein 2 θ=28.6 ° are the characteristic peak of Si, the acromion be made up of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, 2 θ=36.3 ° are the characteristic peaks of ZnO, as can be seen here, with the method obtain catalyst be silicon/cupric oxide/Zinc oxide catalytic.
Embodiment 6
Get the toluene of abandoned catalyst in direct synthesis methylchlorosilane 5g 100mL, after acetone respectively washes twice, after filtration in vacuum drying chamber in 100 DEG C of vacuum drying 2 hours, put into Muffle furnace, in 600 DEG C of calcining 2h, be cooled to room temperature, place it in 500mL beaker, add 100mL dust technology, add thermal response 3h when 80 DEG C, slowly add sodium hydroxide solution, adjust ph is to 13,80 DEG C add thermal response 2h, washing, filter, in 100 DEG C of vacuum drying 6h, at 600 DEG C of calcining 0.5h.ICP test result shows, and copper content is 29.9%, and Zn-ef ficiency content is 0.3%.
Fig. 6 is the XRD figure of the catalyst that embodiment 6 obtains, and wherein 2 θ=28.6 ° be the characteristic peak of Si, and the acromion be made up of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, as can be seen here, is silicon/copper oxide catalyst with the catalyst of the method acquisition.
Evaluating catalyst
(1) butyl formate catalyst is catalyzed and synthesized
Take the catalyst of 3g embodiment 1,2,3 respectively, be placed in hyperbaric heating still, add 40mL butanols as solvent, use unstripped gas V
(CO): V
(CO2): V
(H2): V
(Ar)air 3 times in=33.8: 5.09: 3.09: 58.02 displacement stills, the blowing pressure 1.0MPa.After in still, air is got rid of, 5.0MPa is inflated in room temperature downhill reaction still, start afterwards to stir, stir speed (S.S.) 2000rpm, and temperature is risen to 170 DEG C, after 2h is carried out in reaction, stop stirring, cooling, detected to airbag by the gas collection in reactor, butyl formate catalyst activity test result is in table 1.
Butanols is changed to respectively ethanol, propyl alcohol, 1-amylalcohol and carries out catalytic evaluation to the catalyst of embodiment 4,5,6 respectively, the product of generation is respectively Ethyl formate, propyl formate, amyl formate, and catalytic activity test result is in table 1.
From ICP result, take waste catalyst as catalyst metals weight content copper prepared by raw material be 1.0%-30.0%, it is less that zinc is that 0.1-10.0%, XRD data show these metal component grain diameters, good dispersion degree.
As shown in Table 1, although be that catalyst activity constituent content prepared by raw material is different with waste catalyst, catalytic activity and selective all higher.Therefore take waste catalyst as raw material, after physical chemistry process, the catalyst of the synthesis gas formic acid esters of better performances can be obtained.
Table 1, catalyst activity result
Claims (8)
1. one kind utilizes CO
2the preparation method of formic acid esters used catalyst processed, is characterized in that, described method comprises the organic solvent cleaning of the waste catalyst produced in organic silicon monomer methylchlorosilane production process, filtration, acid dissolve, alkali precipitation, then filters, the step of dry, calcining;
Wherein, described acid dissolve and alkali precipitation are: be dissolved in acid solution through organic solvent cleaning, filtration, dried waste catalyst at 40-80 DEG C, after reaction 2-10h, add zinc salt and precipitating reagent, after regulating pH value of solution to 9-14,40-80 DEG C of reaction 2-10h, then filtration, drying;
Described calcining is in high temperature furnace and calcines in air, and the temperature of calcining step is 100 ~ 600 DEG C, and calcination time is 0.5 ~ 10h.
2. method according to claim 1, is characterized in that, described waste catalyst is that silicone industry utilizes that silicon is raw material, copper or the solid residue of its compound for producing in Catalyst Production organosilicon methyl chlorosilane monomer process; Described cleaning organic solvent used be selected from ethanol, benzene, toluene, chloroform, acetone, oxolane, ether one or more; Clean one time or filter after multipass, roasting after filtering, the condition of described calcination steps is 100 ~ 900 DEG C of roasting 2 ~ 10h.
3. method according to claim 1, is characterized in that, described acid solution is hydrochloric acid, nitric acid or sulfuric acid; Described zinc salt comprises zinc nitrate, zinc chloride or zinc sulfate, and zinc salt addition is≤5g/mL; Described precipitating reagent is NaOH, ammoniacal liquor or sodium carbonate.
4. method according to claim 1, is characterized in that, described formic acid esters is Ethyl formate, propyl formate, isopropyl formate, butyl formate, formic acid-2-butyl ester, iso-butyl formate, t-butyl formate, amyl formate or hexyl formate.
5. one kind from CO
2the catalyst that formic acid esters processed is used, is characterized in that, described catalyst, then filters through organic solvent cleaning, filtration, acid dissolve, alkali precipitation for raw material with the waste catalyst produced in organic silicon monomer methylchlorosilane production process, dry, calcining is obtained;
Wherein, described acid dissolve and alkali precipitation are: be dissolved in acid solution through organic solvent cleaning, filtration, dried waste catalyst at 40-80 DEG C, after reaction 2-10h, add zinc salt and precipitating reagent, after regulating pH value of solution to 9-14,40-80 DEG C of reaction 2-10h, then filtration, drying;
Described calcining is in high temperature furnace and calcines in air, and the temperature of calcining step is 100 ~ 600 DEG C, and calcination time is 0.5 ~ 10h.
6. catalyst according to claim 5, is characterized in that, described waste catalyst is that silicone industry utilizes that silicon is raw material, copper or the solid residue of its compound for producing in Catalyst Production organosilicon methyl chlorosilane monomer process; Described cleaning organic solvent used be selected from ethanol, benzene, toluene, chloroform, acetone, oxolane, ether one or more; Clean one time or filter after multipass, roasting after filtering, the condition of described calcination steps is 100 ~ 900 DEG C of roasting 2 ~ 10h.
7. catalyst according to claim 5, is characterized in that, described acid solution is hydrochloric acid, nitric acid or sulfuric acid; Described zinc salt comprises zinc nitrate, zinc chloride or zinc sulfate, and zinc salt addition is 0-5g/mL; Described precipitating reagent is NaOH, ammoniacal liquor or sodium carbonate.
8. catalyst according to claim 5, is characterized in that, described formic acid esters is Ethyl formate, propyl formate, isopropyl formate, butyl formate, formic acid-2-butyl ester, iso-butyl formate, t-butyl formate, amyl formate or hexyl formate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19618971A1 (en) * | 1996-05-10 | 1997-11-13 | Wacker Chemie Gmbh | Recovery of copper from residues from the Muller-Rochow process |
| CN101918132A (en) * | 2007-11-28 | 2010-12-15 | 雪佛龙美国公司 | Process for recovering base metals from used hydroprocessing catalyst |
| CN102020307A (en) * | 2010-10-15 | 2011-04-20 | 张家港凯纳信息技术有限公司 | Disposal method of organic silicon copper-containing waste catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19618971A1 (en) * | 1996-05-10 | 1997-11-13 | Wacker Chemie Gmbh | Recovery of copper from residues from the Muller-Rochow process |
| CN101918132A (en) * | 2007-11-28 | 2010-12-15 | 雪佛龙美国公司 | Process for recovering base metals from used hydroprocessing catalyst |
| CN102020307A (en) * | 2010-10-15 | 2011-04-20 | 张家港凯纳信息技术有限公司 | Disposal method of organic silicon copper-containing waste catalyst |
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