CN102794179A - Catalyst for preparing formate from CO2 and preparation method thereof - Google Patents
Catalyst for preparing formate from CO2 and preparation method thereof Download PDFInfo
- Publication number
- CN102794179A CN102794179A CN2011101411394A CN201110141139A CN102794179A CN 102794179 A CN102794179 A CN 102794179A CN 2011101411394 A CN2011101411394 A CN 2011101411394A CN 201110141139 A CN201110141139 A CN 201110141139A CN 102794179 A CN102794179 A CN 102794179A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- formate
- calcining
- acid
- formic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
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 synthesis gas system of the present invention relates to formic acid esters chemical industry production field relates to a kind of CO of utilization particularly
2The catalyst and the preparation method of system formic acid esters.
Background technology
Producing synthesis gas from coal (CO, H
2And CO
2) preparation high added value chemicals is important developing direction of coal chemical technology.The production of synthesis gas and be applied in and have consequence in the chemical industry can be produced a series of chemicals by synthesis gas.For example: synthesis gas is produced ammonia and methyl alcohol, the synthetic liquid fuel of producing of Fischer-Tropsch, and oxo synthesis is produced senior fatty aldehyde and alcohol etc.In addition, just under development still have the direct synthesizing glycol of synthesis gas, ethanol, acetic acid, 1, a 4-butanediol etc.Simultaneously, CO
2A reduction of discharging and higher value application focus also being scientific research
Methylchlorosilane is the preparation organic silicon monomer that organosilicon material is most important, consumption is maximum.Mainly utilize the Rochow direct method to synthesize this monomer in the industry at present, promptly in fluidized-bed reactor, silica flour and major catalyst copper powder, co-catalyst zinc powder mix the active contact of formation; Along with constantly carrying out of reaction; The deposit on contact surface is more and more, makes the active reduction of contact, and conversion ratio and selectivity reduce significantly; This moment, waste catalyst need be discharged reactor, added new contact simultaneously and was 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 thinner, is exposed to be prone in the air cause oxidation even burning, and environmental pollution is serious, also are simultaneously the hidden danger in the safety in production.Along with the production-scale continuous expansion of China's organic silicon monomer, the amount of waste catalyst constantly increases, to the reasonable processing of waste catalyst with to utilize be China's organosilicon industry sustainable development problem demanding prompt solution always.
At present, a large amount of research has been carried out in the processing of waste catalyst both at home and abroad.Patent US4758352 to from waste catalyst, reclaim silicon, copper is studied.Also can waste catalyst be carried out the degree of depth and be converted into morning-night, SiCl
4, HSiCl
3, product such as phenyl chlorosilane.For the ease of transportation and processing, the waste catalyst deactivation is handled, be processed into stable particle or bead like patent US4892694.Although a large amount of research has been carried out in the processing to waste catalyst, complex disposal process, secondary pollution is serious, and value-added content of product is lower.
Ester is one type of important organic chemical industry's product, generally has the fruital smell, therefore uses widely at perfume and essence industry.In addition, ester can be used as solvent, plasticizer and is used for a lot of industrial departments, can also be used for producing polyester in a large number, and also some is as the raw material of organic synthesis.The ester production method is a lot, and what present industrial application was the widest is direct esterification and transesterification.Direct esterification is that reaction generates ester and water with alcohol by carboxylic acid, and reaction speed is slower, only in the presence of catalyst, could obtain the reaction speed of industrial significance, and catalyst commonly used has sulfuric acid, hydrochloric acid, cationic ion-exchange resin etc.Transesterification is to make ester and carboxylic acid, alcohol or the reaction of another kind of ester obtain the course of reaction of required ester.Industrial how in the presence of catalyst, in liquid phase, carrying out generally adopted base catalyst (like sodium alkoxide).
Formic acid esters is one type of ester that contains formic acid group (HCOO), belongs to a kind of of formates.Industrial general employing direct esterification prepared in reaction.For example the industrial preparation of butyl formate with formic acid and butanols reflux 24h, is a catalyst with sulfuric acid; Anhydrous sodium sulfate drying with the saturated nacl aqueous solution washing, is used again with saturated nacl aqueous solution, saturated sodium bicarbonate solution washing in the cooling back; Distillation; Collect 106-107 ℃ of cut and promptly get product, productive rate is 74%, and this method reaction time is long.Perhaps get with formic acid, n-butanol and isopropyl formate azeotropic distillation.Study carefully with the synthetic butyl formate of new catalyst in new Wuhan Research Institute, it is with heteropoly acid TiSiW
120
40/ TiO
2Be catalyst, add formic acid and butanols, heated and stirred refluxes, and keeps 94-98 ℃ of reflux temperature, reacts to stop heating and stirring after one hour, pours out reactant liquor after the cooling, with a small amount of saturated common salt washing, uses saturated Na then earlier
2CO
3Solution is washed, and adjust pH is 7-8, with the saturated common salt washing, uses anhydrous Na at last
2CO
3Drying, 105-107 ℃ cut is collected in fractionation, and productive rate is about 72%.The method for preparing butyl formate, the formic acid raw material is more expensive, and complex process is difficult to reclaim as the sulfuric acid of catalyst, seriously polluted and power consumption.
Summary of the invention
Inventor of the present invention is through careful investigation authentication, and the porous silicon that contains in the organosilicon waste catalyst can be made catalyst carrier, and copper and zinc are active component, as CO
2Catalyst in the system formic acid esters technology 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
2The system formic acid esters provides the catalyst that cost is low, performance is good.
Therefore, the purpose of this invention is to provide a kind of from CO
2The used catalyst of system formic acid esters.
A purpose more of the present invention provides above-mentioned Preparation of catalysts method.
According to of the present invention from CO
2System formic acid esters used Preparation of catalysts method comprises that the organic solvent of the waste catalyst that produces in the organic silicon monomer methylchlorosilane production process cleans, filters, acid dissolving, alkali precipitation, filters then, the step of dry, calcining.
According to the method for the invention, wherein, described calcining in high temperature furnace with calcine in the air, the temperature of calcining step is l00~600 ℃, calcination time is 0.5~10h.
According to the method for the invention; Wherein, Said waste catalyst is that organosilicon industrial utilization silicon is that raw material, copper or its compound are the solid residue that produces in the Catalyst Production organosilicon methylchlorosilane monomer process; Mainly contain silicon, one or more in copper and the carbon etc., and the trace components such as zinc, iron, aluminium and tin in one or more.The waste catalyst granular size is the 0.5-100 micron, and its pore structure size is in 2 nanometers-10 micron, and wherein silicone content is 10-95% (weight ratio), and copper content is in 2-50% (weight ratio), carbon content 5-10% (weight ratio).
According to the method for the invention; Wherein, The solid residue waste catalyst that produces in the organosilicon compound probability is cleaned one time or multipass with organic solvent; It is dry in drying box to filter the back, and said organic solvent can be: one or more in ethanol, benzene, toluene, chloroform, acetone, oxolane, the ether.Clean one time or multipass filtration back roasting, the condition of calcination steps is 100~900 ℃ of calcining 2~10h
According to the method for the invention; Wherein, Acid dissolving, alkali precipitate again, calcining step has carried out modifying and decorating to the waste catalyst after handling through solvent clean; Obtain containing one or more silica-based composite porous in the elements such as copper, carbon, zinc, these method of modifying can change the pore structure, component, content of regulation and control complex etc., and the silica-based porous complex after the modification can be used to contain CO as catalyst
2The reaction of synthesis gas system formic acid esters.
For example, according to the method for the invention, wherein; Be dissolved in acid solution with above-mentioned through the cleaned waste catalyst of organic solvent, heated and stirred adds zinc salt after a period of time; Add precipitating reagent and regulator solution afterwards to different pH values; Metal after the dissolving is precipitated again, obtain silicon/carbon/cupric oxide/zinc oxide porous complex at last, it can be used as and contains CO
2The catalyst of synthesis gas system formic acid esters.Said acid comprises hydrochloric acid, nitric acid, sulfuric acid etc., and said heating-up temperature scope is 40-80 ℃, and the reaction time is 2-10h, and said zinc salt comprises zinc nitrate, zinc chloride, zinc sulfate etc., and the zinc salt addition is≤5g/mL.Described precipitating reagent is a kind of in NaOH, ammoniacal liquor, the sodium carbonate etc., and said pH scope is 9-14, and the said time of precipitation reaction again is 2-10h.
For example, according to the method for the invention, wherein, place high temperature furnace in the air roasting through the cleaned waste catalyst of organic solvent with above-mentioned; Sintering temperature is at 100-900 ℃, and roasting time is 0.5-10h, naturally cools to room temperature after the roasting; Obtain silicon/cupric oxide porous complex, afterwards, it is dissolved in acid stirs; Add zinc salt and precipitating reagent and precipitate again, obtain silicon/cupric oxide/zinc oxide porous complex at last, it can be used as and contains CO
2Synthesis gas system formic acid esters in catalyst, weight metal content copper is 1.0%-30.0% in the prepared catalyst, zinc is 0.1-10.0%.
Likewise, the invention provides a kind of from CO
2System formic acid esters used catalyst, said catalyst is a raw material with the waste catalyst that produces in the organic silicon monomer methylchlorosilane production process, through organic solvent cleaning, filtration, roasting, acid dissolving, alkali precipitation, and then filter, step dry, calcining makes.
Formic acid esters involved in the present invention can comprise 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.
Utilize catalyst of the present invention to be from the catalytic mechanism of synthesis gas system formic acid esters:
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 reduce discharging and higher value application is the focus of scientific research always, infer that from above-mentioned mechanism in the reaction of synthesis gas system formic acid esters, the main component of its reaction is the CO in the synthesis gas
2, therefore, this reaction can realize CO
2Higher value application.
The catalyst of the present invention's preparation can be accomplished the reaction of above-mentioned (4), can realize CO
2Directly convert formic acid esters into, the catalyst raw material is the waste catalyst during organosilicon is produced, and CO
2One-step method is synthesized butyl formate, has realized CO
2Reduction of discharging and higher value application, save energy consumption.The catalyst activity and the selectivity of the present invention's preparation are higher, and technology is simple, and low cost of manufacture has the good industrial prospect.Simultaneously, can be with the solid residue waste catalyst higher value application that produces in the organosilicon compound probability process.
Synthetic and the CO of organosilicon
2The system formic acid esters is two fields that research direction is different.Inventor of the present invention breaks through the limitation of existing research thinking, considers the state of development and the demand of two research fields, in conjunction with the characteristic and the CO of organosilicon synthesis of solid residue macroscopically
2The performance requirement of the catalyst in the system formic acid esters; For example utilize the loose structure of silicon materials in the waste catalyst, the metallic element in the waste catalyst for example is deposited in the porous silica material after copper, the zinc dissolving more again uniformly, realized the high degree of dispersion of metallic particles; Increased the activity of metallic particles, CO
2Thereby be easy on metallic particles, react and make formic acid esters.The present invention at first find and through experimental verification the organosilicon waste catalyst can be used as the catalyst in the synthesis gas system formic acid esters technology; Technical scheme of the present invention has been utilized the raw material of the solid residue of organosilicon compound probability as catalyst; The twice laid that has solved the organosilicon compound probability again when producing economic benefit is with CO
2The requirement of the high-performance and low-cost catalyst of system formic acid esters, this development to two industries all can exert far reaching influence, and 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 of the present invention's preparation contains CO
2The catalyst of synthesis gas system formic acid esters, cost of material is cheap, method of operating is simple, is easy to large-scale production;
3, the catalyst of the present invention's preparation shows higher formic acid esters synthesizing activity and heat endurance.
4, the catalyst favorable reproducibility of the present invention's preparation helps controlling product quality.
Description of drawings
The XRD figure of the catalyst of Fig. 1 embodiment 1 preparation
The XRD figure of the catalyst of Fig. 2 embodiment 2 preparations
The XRD figure of the catalyst of Fig. 3 embodiment 3 preparations
The XRD figure of the catalyst of Fig. 4 embodiment 4 preparations
The XRD figure of the catalyst of Fig. 5 embodiment 5 preparations
The XRD figure of the catalyst of Fig. 6 embodiment 6 preparations
The specific embodiment
Following examples further specify the present invention, but the present invention is not limited to following examples.
The employed waste catalyst of following examples is that organosilicon industrial utilization silicon is that raw material, copper or its compound are the solid residue that produces in the Catalyst Production organosilicon methylchlorosilane monomer process; Be that elemental silicon and chloromethanes are under the effect of copper major catalyst and zinc co-catalyst; Produce in the chlorosilane monomer industrial process unreacted silicon and copper beaded catalyst powder completely, and the carbonaceous organic material pyrolysis in this process and porous complex that the carbon distribution that produces is formed.Embodiment 1-6 is for adopting the catalyst of different waste catalysts through the synthesis gas system formic acid esters of modification Processing of Preparation.
Embodiment 1
After getting organosilicon waste catalyst 5g and respectively washing twice with ether, the ethanol of 100mL, filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours, place it in the 500mL beaker; Add 100mL watery hydrochloric acid, reacting by heating 6h in the time of 40 ℃ slowly adds sodium carbonate liquor; Regulate pH value to 9,65 ℃ of reacting by heating 6h, washing; Filter, in 100 ℃ of vacuum drying 6h, at 350 ℃ of calcining 2h.
The catalyst material of above-mentioned preparation is carried out the XRD test on the X ' Pert PROMPD type multi-functional X-ray diffractometer that Dutch Panalytical company (PANalytical) produces.
The catalyst material of above-mentioned preparation is carried out the ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, copper content is 3.0% (weight ratio, down together), and the zinc constituent content is 0.1% (weight ratio, down together).
The XRD figure of the catalyst that Fig. 1 obtains for embodiment 1; Wherein 2 θ=28.6 ° are the characteristic peak of Si; By 2 θ=35.5 ° and 2 θ=38.7 a ° acromion of forming is the characteristic peak of CuO; 2 θ=26.6 ° are the characteristic peaks of C, this shows, the catalyst that uses the method to obtain is silicon/carbon/copper oxide catalyst.
Embodiment 2
After getting organosilicon waste catalyst 5g and respectively washing twice with toluene, the oxolane of 100mL, filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours, be cooled to room temperature, place it in the 500mL beaker, add 2gZn (N0
3)
2, adding the rare nitric acid of 100mL, reacting by heating 4h in the time of 60 ℃ slowly adds ammonia spirit, regulates pH value to 11,70 ℃ of reacting by heating 4h, washing is filtered, in 100 ℃ of vacuum drying 6h, at 100 ℃ of calcining 10h..ICP test result shows, copper content is 3.3%, and the zinc constituent content is 4.3%.
The XRD figure of the catalyst that Fig. 2 obtains for embodiment 2; Wherein 2 θ=28.6 ° are the characteristic peak of Si; By 2 θ=35.5 ° and 2 θ=38.7 a ° acromion of forming is the characteristic peak of CuO; 2 θ=36.3 ° are the characteristic peaks of ZnO, this shows, the catalyst that uses the method to obtain is silicon/cupric oxide/Zinc oxide catalytic.
Embodiment 3
After getting organosilicon waste catalyst 5g and respectively washing twice with chloroform, the acetone of 100mL, filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours, put into Muffle furnace, in 600 ℃ of roasting 2h, be cooled to room temperature.Above-mentioned material is placed in the 500mL beaker, adds 1gZn (NO
3)
2, add the 100mL dilute sulfuric acid, behind 80 ℃ of reacting by heating 2h, slowly add sodium hydroxide solution, regulate pH to 10,80 ℃ of reacting by heating 2h, washing is filtered, in 100 ℃ of vacuum drying, at 300 ℃ of calcining 5h.The ICP test result shows that copper content is 2.3%, and the zinc constituent content is 3.9%.
The XRD figure of the catalyst that Fig. 3 obtains for embodiment 3; Wherein 2 θ=28.6 ° are the characteristic peak of Si; By 2 θ=35.5 ° and 2 θ=38.7 a ° acromion of forming is the characteristic peak of CuO, and 2 θ=36.3 ° are the characteristic peaks of ZnO, and 2 θ=26.6 ° are the characteristic peaks of C; This shows that the catalyst that uses the method to obtain is silicon/carbon/cupric oxide/Zinc oxide catalytic.
Embodiment 4
After getting organosilicon waste catalyst 5g and respectively washing twice with toluene, the ethanol of 100mL, filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours, be cooled to room temperature, place it in the 500mL beaker, add 5g Zn (NO
3)
2, adding the rare nitric acid of 100mL, reacting by heating 8h in the time of 50 ℃ slowly adds ammonia spirit, regulates pH value to 14,50 ℃ of reacting by heating 6h, washing is filtered, in 100 ℃ of vacuum drying 6h, at 250 ℃ of calcining 8h.The ICP test result shows that copper content is 14.5%, and the zinc constituent content is 10.0%.
The XRD figure of the catalyst that Fig. 4 obtains for embodiment 4; Wherein 2 θ=28.6 ° are the characteristic peak of Si; By 2 θ=35.5 ° and 2 θ=38.7 a ° acromion of forming is the characteristic peak of CuO, and 2 θ=36.3 ° are the characteristic peaks of ZnO, and 2 θ=26.6 ° are the characteristic peaks of C; This shows that the catalyst that uses the method to obtain is silicon/carbon/cupric oxide/Zinc oxide catalytic.
Embodiment 5
After getting organosilicon waste catalyst 5g and respectively washing twice with oxolane, the ethanol of 100mL, filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours, put into Muffle furnace; In 900 ℃ of roasting 0.5h; Be cooled to room temperature, place it in the 500mL beaker, add 3g Zn (NO
3)
2, adding the rare nitric acid of 100mL, reacting by heating 3h in the time of 70 ℃ slowly adds sodium carbonate liquor, regulates pH value to 11,70 ℃ of reacting by heating 2h, washing is filtered, in 100 ℃ of vacuum drying 6h, at 350 ℃ of calcining 2h.The ICP test result shows that copper content is 23.8%, and the zinc constituent content is 5.6%.
The XRD figure of the catalyst that Fig. 5 obtains for embodiment 5; Wherein 2 θ=28.6 ° are the characteristic peak of Si; By 2 θ=35.5 ° and 2 θ=38.7 a ° acromion of forming is the characteristic peak of CuO; 2 θ=36.3 ° are the characteristic peaks of ZnO, this shows, the catalyst that uses the method to obtain is silicon/cupric oxide/Zinc oxide catalytic.
Embodiment 6
After getting organosilicon waste catalyst 5g and respectively washing twice with toluene, the acetone of 100mL, filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours, put into Muffle furnace, in 600 ℃ of calcining 2h; Be cooled to room temperature, place it in the 500mL beaker, add the rare nitric acid of 100mL, reacting by heating 3h in the time of 80 ℃; Slowly add sodium hydroxide solution, regulate pH value to 13,80 ℃ of reacting by heating 2h, washing; Filter, in 100 ℃ of vacuum drying 6h, at 600 ℃ of calcining 0.5h.The ICP test result shows that copper content is 29.9%, and the zinc constituent content is 0.3%.
The XRD figure of the catalyst that Fig. 6 obtains for embodiment 6, wherein 2 θ=28.6 ° are the characteristic peak of Si, are the characteristic peaks of CuO by 2 θ=35.5 ° and 2 θ=38.7 a ° acromion of forming, and this shows that the catalyst that uses the method to obtain is silicon/copper oxide catalyst.
Evaluating catalyst
(1) the synthetic butyl formate catalyst of catalysis
Take by weighing the catalyst of 3g embodiment 1,2,3 respectively, place the high pressure heating kettle, add the 40mL butanols, use unstripped gas V as solvent
(CO): V
(CO2): V
(H2): V
(Ar)=33.8: air is 3 times in 5.09: 3.09: 58.02 displacement stills, the blowing pressure 1.0MPa.After air is got rid of in the still, be inflated to 5.0MPa in the room temperature downhill reaction still, begin afterwards to stir; Stir speed (S.S.) 2000rpm, and temperature risen to 170 ℃, after 2h is carried out in reaction; Stop to stir; Cooling is collected airbag with the gas in the agitated reactor and is detected, and butyl formate catalyst activity test result is seen table 1.
Butanols is changed to ethanol, propyl alcohol, 1-amylalcohol respectively respectively the catalyst of embodiment 4,5,6 is carried out catalytic evaluation, the product of generation is respectively Ethyl formate, propyl formate, and amyl formate, the catalytic activity test result is seen table 1.
Can be known by ICP result, be that the catalyst metals weight content copper of feedstock production is 1.0%-30.0% with the waste catalyst, and zinc is 0.1-10.0%, and the XRD data show that these metal component grain diameters are less, good dispersion degree.
Can know that by table 1 though be that the catalyst activity constituent content of feedstock production is different with the waste catalyst, catalytic activity and selectivity are all than higher.Therefore be raw material with the waste catalyst, after physical chemistry is handled, can obtain the catalyst of the synthesis gas system formic acid esters of better performances.
Table 1, catalyst activity result
Claims (12)
1. one kind is utilized CO
2The preparation method of system formic acid esters catalyst system therefor is characterized in that, said method comprises that the organic solvent of the waste catalyst that produces in the organic silicon monomer methylchlorosilane production process cleans, filters, acid dissolving, alkali precipitation, filters then, the step of dry, calcining.
2. method according to claim 1 is characterized in that, said waste catalyst is that organosilicon industrial utilization silicon is that raw material, copper or its compound are the solid residue that produces in the Catalyst Production organosilicon methylchlorosilane monomer process; The used organic solvent of said cleaning is to be selected from ethanol, benzene, toluene, chloroform, acetone, oxolane, the ether one or more; Clean one time or multipass filtration back roasting, the condition of said calcination steps is 100~900 ℃ of calcining 2~10h.
3. method according to claim 1; It is characterized in that said acid dissolving and alkali precipitation are: be dissolved in acid solution through organic solvent cleaning, filtration, dried waste catalyst at 40-80 ℃, behind the reaction 2-10h; Add zinc salt and precipitating reagent; Regulator solution pH is to 9-14, behind the 40-80 ℃ of reaction 2-10h, filters then, drying.
4. method according to claim 1 is characterized in that, described calcining is in high temperature furnace and calcines in the air that the temperature of calcining step is 100~600 ℃, and calcination time is 0.5~10h.
5. method according to claim 3 is characterized in that, said acid solution is hydrochloric acid, nitric acid or sulfuric acid; Said zinc salt comprises zinc nitrate, zinc chloride or zinc sulfate, and the zinc salt addition is≤5g/mL; Described precipitating reagent is NaOH, ammoniacal liquor or sodium carbonate.
6. method according to claim 1 is characterized in that, said 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.
7. one kind from CO
2System formic acid esters used catalyst is characterized in that said catalyst is a raw material with the waste catalyst that produces in the organic silicon monomer methylchlorosilane production process, through organic solvent clean, filter, acid dissolving, alkali precipitation, filter then, dry, calcining makes.
8. catalyst according to claim 7 is characterized in that, said waste catalyst is that organosilicon industrial utilization silicon is raw material, copper or is the solid residue that produces in the Catalyst Production organosilicon methylchlorosilane monomer process with compound; The used organic solvent of said cleaning is to be selected from ethanol, benzene, toluene, chloroform, acetone, oxolane, the ether one or more; Clean one time or multipass filtration back roasting, the condition of said calcination steps is 100~900 ℃ of calcining 2~10h.
9. catalyst according to claim 7; It is characterized in that said acid dissolving and alkali precipitation are: be dissolved in acid solution through organic solvent cleaning, filtration, dried waste catalyst at 40-80 ℃, behind the reaction 2-10h; Add zinc salt and precipitating reagent; Regulator solution pH is to 9-14, behind the 40-80 ℃ of reaction 2-10h, filters then, drying.
10. catalyst according to claim 7 is characterized in that, described calcining is in high temperature furnace and calcines in the air that the temperature of calcining step is 100~600 ℃, and calcination time is 0.5~10h.
11. catalyst according to claim 9 is characterized in that, said acid solution is hydrochloric acid, nitric acid or sulfuric acid; Said zinc salt comprises zinc nitrate, zinc chloride or zinc sulfate, and the zinc salt addition is 0-5g/mL; Described precipitating reagent is NaOH, ammoniacal liquor or sodium carbonate.
12. catalyst according to claim 7 is characterized in that, said 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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110141139.4A CN102794179B (en) | 2011-05-27 | 2011-05-27 | Catalyst for preparing formate from CO2 and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110141139.4A CN102794179B (en) | 2011-05-27 | 2011-05-27 | Catalyst for preparing formate from CO2 and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102794179A true CN102794179A (en) | 2012-11-28 |
CN102794179B CN102794179B (en) | 2015-04-01 |
Family
ID=47193630
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201110141139.4A Active CN102794179B (en) | 2011-05-27 | 2011-05-27 | Catalyst for preparing formate from CO2 and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102794179B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104549304A (en) * | 2014-11-26 | 2015-04-29 | 中国科学院过程工程研究所 | Catalyst for hydrogenating octenal gas phase to prepare octanol and preparation method of catalyst |
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 |
-
2011
- 2011-05-27 CN CN201110141139.4A patent/CN102794179B/en active Active
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 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104549304A (en) * | 2014-11-26 | 2015-04-29 | 中国科学院过程工程研究所 | Catalyst for hydrogenating octenal gas phase to prepare octanol and preparation method of catalyst |
CN104549304B (en) * | 2014-11-26 | 2017-06-06 | 中国科学院过程工程研究所 | A kind of catalyst of octenal gas phase hydrogenation octanol and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN102794179B (en) | 2015-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109794276B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
CN1241164A (en) | Method of hydrocarbon reforming and catalyst and catalyst precursor therefor | |
CN105195156A (en) | Preparation method and application of high-dispersity copper-based catalyst | |
CN101934233B (en) | Preparation method of catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas | |
CN103922931B (en) | A kind of method of a step catalytically synthesizing glycol ether acetate | |
CN104557562A (en) | Method for producing N,N,N',N'- tetramethylethylenediamine by virtue of direct catalytic amination of dimethylethanolamine | |
CN104837799A (en) | Catalytic conversion of bio-mass derivable aliphatic alcohols to valuable alkenes or oxygenates | |
CN112517012A (en) | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation | |
CN111170829B (en) | Preparation method of hexamethyl indanol | |
CN112047803B (en) | Method for synthesizing difluoromethane by gas phase catalysis | |
CN103551154B (en) | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst | |
CN110240197B (en) | Ultrathin nanosheet self-assembled multilayer BiOCl microsphere and application thereof in photocatalytic coupling of benzylamine to imine | |
CN110354882B (en) | BiVO4@ZnIn2S4/g-C3N4Visible light response photocatalyst and preparation method thereof | |
CN110327959B (en) | BiVO4@CdIn2S4/g-C3N4Visible light response photocatalyst and preparation method thereof | |
CN102794179B (en) | Catalyst for preparing formate from CO2 and preparation method thereof | |
CN102773102B (en) | Catalyst for low-temperature synthesis of methanol and preparation method | |
CN113797939B (en) | ZnZrO (zinc ZrO-rich alloy) x /MoS 2 Composite catalyst, preparation and application thereof | |
CN113559862B (en) | Atomic-grade auxiliary-modified CuO composite mesomorphic catalyst and preparation method thereof | |
CN109772419B (en) | Preparation method for constructing carbon nitride-based ultrathin nanosheet composite material in confined space | |
JP2016073964A (en) | Heterogeneous catalyst for production of 3-hydroxypropionic acid from allyl alcohol, and method for production of 3-hydroxypropionic acid from allyl alcohol using the same | |
CN101851154B (en) | Improved method for producing 2-alkylene alicyclic ketone | |
CN110354883B (en) | BiVO4@CuIn2S4/g-C3N4Visible light response photocatalyst and preparation method thereof | |
CN110038609B (en) | Dehydration catalyst and application thereof in preparation of organic carboxylic anhydride | |
CN113398912A (en) | Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate | |
CN112121805A (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |