CN102773102A - Catalyst for low-temperature synthesis of methanol and preparation method - Google Patents
Catalyst for low-temperature synthesis of methanol and preparation method Download PDFInfo
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Abstract
The invention relates to the production field of low-temperature synthesis of methanol, and particularly relates to a catalyst for low-temperature synthesis of methanol and a preparation method. The method includes the steps of: crushing and screening waste contacts generated from direct method production of methyl chlorosilane, and then using an organic solvent for cleaning. The method also can further include the following steps of: subjecting the cleaned waste contacts to one or more of an oxidation treatment, a reduction treatment and a heat treatment, thus obtaining the catalyst for low-temperature preparation of methanol from synthesis gas. The method provided in the invention solves the high value comprehensive utilization problem of solid residual waste contacts in the organosilicon synthesis industry. The prepared catalyst has the advantages of low raw material cost, simple operation method, as well as easy large-scale production, and shows higher methanol synthesis activity and thermal stability.
Description
Technical field
The present invention relates to the low-temp synthesis of methanol production field, particularly, the present invention relates to a kind of catalyst and preparation method of low-temp synthesis of methanol.
Background technology
Organosilicon material has the dual performance of inorganic material and organic material simultaneously, and high-and low-temperature resistance, electric insulation, excellent specific property such as weather-proof, corrosion-resistant, nonpoisonous and tasteless are widely used in fields such as electronics, automobile, oil, chemical industry, building, Aero-Space.Methylchlorosilane be the preparation organosilicon material most important, also be the maximum organic silicon monomer of consumption, be the basis and the pillar of whole organosilicon industry.
In the whole bag of tricks of synthesizing methyl-chloro-silane, direct method is simple because of technology, yield is high, without solvent, dangerous little and be convenient to realize that continuous mass production becomes unique industrialized production method.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, this part need to be discharged reactor, added new contact simultaneously and was beneficial to stable reaction and carries out, in addition; 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 to be main with silicon, copper, carbon, and contain the waste residue of components such as a small amount of tin, zinc, and the waste catalyst average grain diameter is thinner; And contain highly active copper; Be exposed in the air and can cause oxidation even burning, environmental pollution is serious, also is simultaneously the hidden danger in the safety in production.Along with the production-scale continuous expansion of 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, and in waste catalyst, adds 70 ℃-80 ℃ hydrochloric acid, forms suspension; Continuous then aerating oxygen, the temperature of beginning oxidation is 51 ℃, slowly is warming up to 69 ℃; Regulate pH value to 6 with highly basic, feed SO continuously
2, adding 15% sodium hydroxide solution adjusting pH value to 9, sediment is dry under 120 ℃, obtains cupric oxide; Can also waste catalyst be carried out the degree of depth and be converted into morning-night, SiCl
4, HSiCl
3, product such as phenyl chlorosilane, US2811853 packs the 120g particle diameter in the fluid bed into less than the waste catalyst of 50 μ m, at 120-140 ℃ of heating 70h down, reacts with the 460g monochloro methane down at 320 ℃ then, obtains the 232g mix monomer, consists of 82%M
2, 13.3%M
1, 3.5%M
3, 1.2%CH
3HSiCl
2For 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, therefore, seeks the method that a kind of simple, cleaning, product can also higher value applications, is very necessary and reality.
Methyl alcohol is a kind of important basic Organic Chemicals, also is a kind of vehicle fuel that has a high potential and fuel-cell fuel simultaneously, and the research of synthesizing methanol and exploration come into one's own in the world always.Be applied to industrialized methanol synthesis catalyst and mainly contain two big types, the catalyst based and copper-based catalysts of zinc chrome, zinc chrome base (ZnO/Cr
2O
3) catalyst is a kind of high pressure solid catalyst, because its activity is low, selectivity is low, the rectifying difficulty, and chromium is to toxic elements in human body, and such catalyst progressively is eliminated at present.Copper-based catalysts is a kind of low-temp low-pressure methanol synthesis catalyst, and its key component is CuO/ZnO/Al
2O
3(Cu/Zn/Al), low (in) operating temperature of platen press copper-based catalysts is 210 ℃～300 ℃, pressure is 5MPa～10MPa, and is more much lower than traditional synthesis technique temperature, favourable to the methyl alcohol molecular balance.It is active high, and selectivity is high, but heat-resisting quantity is poor, to sulfur sensitive, is that the synthetic main catalyst that uses of methyl alcohol is gone up in industry at present.
The method of present existing industrial synthesizing methanol has reached quite high level; Have to be overcome and breakthrough but still exist 3 big shortcomings: (1) is owing to receive the restriction of thermodynamical equilibrium under the reaction temperature; Conversion per pass is low; Methanol concentration seldom can surpass 7% in synthetic tower outlet product, therefore has to use repeatedly circulation, and this has just increased the investment and the synthesis gas cost of synthesis gas manufacturing process greatly.(2) method such as ICI requires must contain 5% CO in the unstripped gas
2Thereby, produced harmful impurity-water, meet the requirement of fuel and downstream chemical products in order to make methanol product, have to carry out the very high methanol-water of energy consumption and separate.(3) the purified synthesis gas cost of conventional method such as ICI is very high.
In order to overcome above-mentioned 3 big shortcomings; Since the seventies, carried out a large amount of improvement research abroad; Long term studies result shows must fundamentally change catalyst system; Develop the catalyst system of have low temperature (90-180 ℃), high activity, high selectivity, no problems of excessive heat, make production process operation under, Here it is low-temperature liquid phase synthesis of methanol greater than 90% high conversion per pass and high selectivity state.
Low-temp synthesis of methanol has overcome the shortcoming of conventional method; Possesses a series of advantage; For example: conversion per pass is high, do not need circulation, thick product composition is good, do not generate water, higher alcohol and carbonyls, thereby obtains pure level absolute ethyl alcohol especially easily, and separating energy consumption is reduced significantly.The synthetic method of low-temp methanol liquid phase comes into one's own just day by day.
At present, domestic and international catalyst to low-temp synthesis of methanol has carried out a large amount of research.With U.S. Amoco company and Brookhaven National Laboratory is representative; It has developed nickel catalyst, and result of study shows that the activated centre of system is made up of homogeneous catalyst, and reaction system is very active; The selectivity of methyl alcohol can only have a spot of methyl formate and dimethyl ether accessory substance greater than 95%.The Machionna of SNAM company etc. has carried out number of research projects on copper-based catalysts, result of study shows that its activity and selectivity can reach suitable with nickel system.Cu/SiO
2And Cu/Al
2O
3Catalyst is very active, but is prone to seriously poisoned by CO, when modifying Cu/Al
2O
3The time can obtain activity higher, be difficult for fouled catalyst.Tsubaki etc. have prepared the Cu/ZnO catalyst, are solvent with the alcoholic solvent, synthesizing methanol under the low-temp low-pressure (Catalysis Communications 2001,2,213-217), its reaction mechanism mechanism of reaction is following:
CO+H
2O＝CO
2+H
2
CO
2+1/2H
2+Cu＝HCOOCu
HCOOCu+ROH＝HCOOR+CuOH
HCOOR+2H
2＝ROH+CH
3OH
CuOH+1/2H
2＝H
2O+Cu
Overall reaction is: CO+2H
2=CH
3OH
React when carrying out, at first CO and H
2The O reaction generates CO
2And H
2, afterwards, CO
2With H
2Be reflected on the copper catalyst surface and generated copper formate, copper formate and alcoholic solvent carry out nucleophilic addition elimination reaction then, generate formic acid esters, and last formic acid esters is reduced to methyl alcohol by reactive hydrogen on the copper, and used ROH is the liquid phase alcoholic solvent in the process.
The catalyst of method for preparing; Its cost is high, and because what adopt is complex catalyst system, has certain interaction and optimum synergistic effect between each component; When the alienation of some component or the activity decline of poisoning and just can cause whole system, catalyst is prone to inactivation.
The present invention plan siliceous waste catalyst after the simple physical chemical treatment as the catalyst in the synthesising gas systeming carbinol technology.
Summary of the invention
The object of the present invention is to provide a kind of catalyst of low-temp synthesis of methanol.
A purpose more of the present invention has been to provide a kind of Preparation of catalysts method of low-temp synthesis of methanol.
According to the Preparation of catalysts method of low-temp synthesis of methanol of the present invention, said method comprises produces broken, the screening of waste catalyst that methylchlorosilane produces, the step of cleaning with organic solvent then with direct method.
Preparation of catalysts method according to low-temp synthesis of methanol of the present invention; Wherein, Said waste catalyst prepares the waste catalyst that produces in the organic silicon monomer methylchlorosilane process for " direct method " fluidized-bed process; Mainly contain silicon, one or more in copper and the/carbon etc., and in the components such as zinc, iron, aluminium and tin of trace one or more.The waste catalyst granular size is 0.5 micron～100 microns; Its pore structure size is in 2 nanometers～10 micron; Wherein silicone content is 10～95wt%, and copper content is at 2～50wt%, carbon content 5～20wt%; Waste catalyst in this scope all is suitable for the present invention, and has good effect during as the catalyst for methanol of synthesis gas low temperature system.
Preparation of catalysts method according to low-temp synthesis of methanol of the present invention; In said step 1); The solid residue waste catalyst that produces in the organosilicon compound probability is cleaned one time or multipass with organic solvent, filter back drying in drying box, obtain silicon/carbon/copper porous complex; It can be used as silicon/carbon/copper porous complex catalyst of using in the synthesising gas systeming carbinol, and said organic solvent can be: one or more in ethanol, benzene, toluene, chloroform, acetone, oxolane, the ether.
Preparation of catalysts method according to low-temp synthesis of methanol of the present invention; In said step 2) in; Can carry out modifying and decorating to the waste catalyst in the step 1) through straightforward procedures such as oxidation, reduction, pyrolysis; Obtain containing one or more silica-based composite porous in the elements such as copper, carbon, zinc, iron, aluminium and tin, these method of modifying can change the pore structure, component, content of regulation and control complex etc., and the catalytic performance of the silica-based porous complex after the modification has in various degree and improves.
Preparation of catalysts method according to low-temp synthesis of methanol of the present invention; Said step 2) the oxidation processes concrete operations in are: place high temperature furnace to calcine at air organosilicon compound probability solid residue waste catalyst; Calcining heat is at 100～900 ℃, and calcination time is 0.5～10h, naturally cools to room temperature after the calcining; Obtain silicon/cupric oxide porous complex, it can be used as the catalyst in the synthesising gas systeming carbinol.
Preparation of catalysts method according to low-temp synthesis of methanol of the present invention; Wherein, said step 2) reduction in is handled and can be handled waste catalyst separately, also can combine oxidation processes to carry out the modifying and decorating of waste catalyst; Concrete is that the above-mentioned silicon/cupric oxide porous complex that obtains is reduced down in 300～900 ℃ in hydrogeneous high purity inert gas; Recovery time is 2～10h, and under this atmosphere, is cooled to room temperature, or uses reducing agent at liquid-phase reduction; Obtain silicon/copper porous complex at last, it can be used as the catalyst in the synthesising gas systeming carbinol.Said high purity inert gas comprises nitrogen, helium, argon gas etc., and described reducing agent is one or more in the solution reduction agent such as formaldehyde, glucose, boric acid hydrogen sodium.
Preparation of catalysts method according to low-temp synthesis of methanol of the present invention; Wherein, Said step 2) the heat treatment concrete operations in are: with organosilicon compound probability solid residue waste catalyst in high purity inert gas in 800～2500 ℃ of following heat treatments, the processing time is 0.5～10h, and under this atmosphere, is cooled to room temperature; Obtain and can make catalyst as the silicon/graphitized carbon/copper porous complex of synthesising gas systeming carbinol, said high purity inert gas comprises nitrogen, helium, argon gas etc.
Above-mentioned cleaning, oxidation, reduction and heat treated purpose are in order to remove the organic silicon monomer on waste catalyst surface, to help improving the quantity in activated centre, the content of each active component of the step of going forward side by side joint, thereby the activity of such catalysts that raising is made by waste catalyst.
In sum; Organosilicon is synthetic to be two fields that research direction is different with synthesising gas systeming carbinol; At present; Research about the catalyst of synthesising gas systeming carbinol all is confined to utilize methods such as infusion process, the precipitation method, flame combustion process, mechanical milling method, skeleton synthetic method, and this specific catalyst prepares the process cost height, produced simultaneously discarded object can cause problems such as environmental pollution.Inventor of the present invention breaks through the limitation of existing research thinking; Consider the state of development and the demand of two research fields macroscopically; In conjunction with the characteristic of organosilicon synthesis of solid residue and the performance requirement of the catalyst in the synthesising gas systeming carbinol; At first find and through experimental verification the waste catalyst that produces in the preparation organic silicon monomer methylchlorosilane process can be used as the catalyst in the synthesising gas systeming carbinol technology, use the solid residue that technical scheme of the present invention has been utilized the organosilicon compound probability, greatly reduced cost; The twice laid of organosilicon compound probability and the high-performance and low-cost requirement of synthesising gas systeming carbinol have been solved when producing economic benefit again; 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 catalyst as synthesising gas systeming carbinol of the present invention's preparation, cost of material is cheap, and method of operating is simple, is easy to large-scale production;
3, the catalyst of the present invention's preparation shows higher methyl alcohol synthesizing activity and heat endurance;
4, the catalyst favorable reproducibility of the present invention's preparation helps controlling product quality.
Description of drawings
Fig. 1 prepares the XRD figure of catalyst for embodiment 1 among the present invention;
Fig. 2 prepares the XRD figure of catalyst for embodiment 2 among the present invention;
Fig. 3 prepares the SEM figure of catalyst for embodiment 1 among the present invention;
Fig. 4 obtains SEM figure for the catalyst of 2 preparations of embodiment among the present invention;
Fig. 5 obtains TG figure for the catalyst of 1 preparation of embodiment among the present invention;
Fig. 6 obtains TG figure for the catalyst of 2 preparations of embodiment among the present invention.
The specific embodiment
Following examples further specify method of the present invention, but the present invention is not limited to following examples.
Waste catalyst that following examples are used as the effect of co-catalyst under is produced in chlorosilane monomer process unreacted completely silicon and copper beaded catalyst powder at copper as major catalyst and zinc as elemental silicon and chloromethanes, and the porous complex formed of the carbon distribution that produces owing to the carbonaceous organic material pyrolysis in the process.Embodiment 1-5 is for adopting the catalyst of the synthetic waste catalyst of organic silicon monomer through the synthesising gas systeming carbinol of modification Processing of Preparation, and comparative example 1 is for adopting the commercial catalysts of synthesising gas systeming carbinol.Comparative example 2 is the catalyst according to the synthesising gas systeming carbinol of patent CN101327431 preparation.
Embodiment 1
" direct method " fluidized-bed process that the organosilicon industry is generally adopted prepares the waste catalyst 5g that produces in the organic silicon monomer methylchlorosilane process; The waste catalyst granular size is 0.5 micron～100 microns, and its pore structure size is in 2 nanometers～10 micron, and wherein silicone content is 84wt%; Copper content is at 6wt%; Carbon content 10wt%, respectively wash twice with ether, the ethanol of 100mL after, filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours.
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 observed surface topography at the JSM6700 model field emission scanning electron microscope that company of NEC produces.
The TG/DTA6300 model that the catalyst material of above-mentioned preparation is produced at Japanese SEICO is made earnest efforts carrying out on the analyzer TG test.
The catalyst material of above-mentioned preparation is carried out the ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, the result sees table 1.
The XRD figure of the catalyst that Fig. 1 obtains for embodiment 1; Wherein 2 θ=28.6 ° are the characteristic peak of Si, are the characteristic peaks of Cu by a ° peak of forming, 2 θ=43.3, and 2 θ=26.6 ° are the characteristic peaks of C; This shows, use the synthetic catalyst of the method to be silicon/carbon/copper catalyst.
The SEM figure of the catalyst that Fig. 3 obtains for embodiment 1 can be known that by figure this synthetic catalyst is a loose structure.
The TG figure of the catalyst that Fig. 5 obtains for embodiment 1 can be known that by figure this synthetic catalyst carbon containing is about 8%.
Embodiment 2
" direct method " fluidized-bed process that the organosilicon industry is generally adopted prepares the waste catalyst 5g that produces in the organic silicon monomer methylchlorosilane process, and the waste catalyst granular size is 0.5 micron～100 microns, and its pore structure size is in 2 nanometers～10 micron; Wherein silicone content is 84wt%; Copper content is at 6wt%, carbon content 10wt%, respectively wash twice with benzene, the chloroform of 100mL after; Filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours; Put into Muffle furnace,, be cooled to room temperature in 100 ℃ of heating 10h.The catalyst material of above-mentioned preparation is carried out the ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, the result sees table 1.
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=26.6 ° are the characteristic peaks of C, this shows, use the synthetic catalyst of the method to be silicon/carbon/copper oxide catalyst.
The SEM figure of the copper catalyst that Fig. 4 obtains for embodiment 2 can be known that by figure this synthetic catalyst is a loose structure.
The TG figure of the catalyst that Fig. 6 obtains for embodiment 2 can be known that by figure this synthetic catalyst carbon containing is about 5%.
Embodiment 3
" direct method " fluidized-bed process that the organosilicon industry is generally adopted prepares the waste catalyst 5g that produces in the organic silicon monomer methylchlorosilane process, and the waste catalyst granular size is 0.5 micron～100 microns, and its pore structure size is in 2 nanometers～10 micron; Wherein silicone content is 84wt%, and copper content is at 6wt%, carbon content 10wt%; After 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 900 ℃ of heating 0.5h, feed inert gas afterwards, in 800 ℃ of heating 10h; Be cooled to room temperature, obtain silicon/cupric oxide porous complex catalyst as synthesising gas systeming carbinol.The catalyst material of above-mentioned preparation is carried out the ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, the result sees table 1.
Embodiment 4
" direct method " fluidized-bed process that the organosilicon industry is generally adopted prepares the waste catalyst 5g that produces in the organic silicon monomer methylchlorosilane process, and the waste catalyst granular size is 0.5 micron～100 microns, and its pore structure size is in 2 nanometers～10 micron; Wherein silicone content is 84wt%; Copper content is at 6wt%, carbon content 10wt%, respectively wash twice with acetone, the oxolane of 100mL after; The filtration back in 100 ℃ of vacuum drying 2 hours, feeds N simultaneously in vacuum drying chamber
2And H
2Reduce, 900 ℃ of reduction temperatures, recovery time 2h, gas flow is respectively 50SCCM, obtains the silicon/carbon/copper porous complex catalyst as synthesising gas systeming carbinol.The catalyst material of above-mentioned preparation is carried out the ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, the result sees table 1.
Embodiment 5
" direct method " fluidized-bed process that the organosilicon industry is generally adopted prepares the waste catalyst 5g that produces in the organic silicon monomer methylchlorosilane process, and the waste catalyst granular size is 0.5 micron～100 microns, and its pore structure size is in 2 nanometers～10 micron; Wherein silicone content is 84wt%, and copper content is at 6wt%, carbon content 10wt%; After respectively washing twice with toluene, the oxolane of 100mL, filter the back in vacuum drying chamber in 100 ℃ of vacuum drying 2 hours, put into Muffle furnace; In 600 ℃ of heating 2h, feed inert gas afterwards, in 2500 ℃ of heating 0.5h; Be cooled to room temperature, feed N simultaneously
2And H
2Reduce, 300 ℃ of reduction temperatures, recovery time 10h, gas flow is respectively 50SCCM, obtains the silicon/copper porous complex catalyst as synthesising gas systeming carbinol.The catalyst material of above-mentioned preparation is carried out the ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, the result sees table 1.
The comparative example 1
The C306 type catalyst that takes by weighing the industrialized synthesising gas systeming carbinol of 0.15g carries out catalytic evaluation.Above-mentioned catalyst material is carried out the ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, the result sees table 1.
The comparative example 2
Prepare the catalyst of synthesising gas systeming carbinol according to patent CN101327431, take by weighing 0.15g and carry out catalytic evaluation.The catalyst material of above-mentioned preparation is carried out the ICP test on U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer, the result sees table 1.
Evaluating catalyst
Take by weighing this catalyst of 0.15g, place the high pressure heating kettle, add 40ml 2-butanols, use unstripped gas V as solvent
(CO): V
(CO2): V
(H2): V
(Ar)Air is 3 times in=33: 5.27: balance: the 3.02 displacement stills, the blowing pressure 1.0MPa.After air is got rid of in the still, be inflated to 3.0MPa in the room temperature downhill reaction still, begin afterwards to stir; Stir speed (S.S.) 2000rpm, and temperature risen to 170 ℃, after 6h is carried out in reaction; Stop to stir; Cooling is collected airbag with the gas in the agitated reactor and is detected, and catalyst for methanol active testing result sees table 2.
Metallic element is formed the ICP test result in table 1, each embodiment catalyst
| Numbering | Embodiment | Cu(％) | Zn(％) | Fe(％) | Al(％) |
| 1 | Embodiment 1 | 2.97 | 0.144 | 0.23 | 0.15 |
| 2 | Embodiment 2 | 3.29 | 0.43 | 0.6 | 0.45 |
| 3 | Embodiment 3 | 2.27 | 0.39 | 0.43 | 0.39 |
| 4 | Embodiment 4 | 3.5 | 0.27 | 0.35 | 0.29 |
| 5 | Embodiment 5 | 3.6 | 0.33 | 0.41 | 0.35 |
| 6 | The comparative example 1 | 39 | 22 | 0.5 | 10 |
| 7 | The comparative example 2 | 32 | 23 | - | 13 |
Table 2, catalyst activity result
Can be known by table 1, be the catalyst of feedstock production with the waste catalyst, and its copper content is lower, and below 5%, and copper content is higher relatively in the commercial catalysts, generally more than 30%.Can know that by table 2 though be that the catalyst activity constituent content of feedstock production is low with the waste catalyst, show than the better methanol activity of commercial catalysts, selectivity and yield are all than higher.Therefore be raw material with the waste catalyst, after simple physics or chemical treatment, can obtain the catalyst of the synthesising gas systeming carbinol of better performances.
Claims (10)
1. the Preparation of catalysts method of a low-temp synthesis of methanol is characterized in that, said method comprises produces broken, the screening of waste catalyst that methylchlorosilane produces, the step of cleaning with organic solvent then with direct method.
2. according to the Preparation of catalysts method of the said low-temp synthesis of methanol of claim 1, it is characterized in that said waste catalyst prepares through the direct method fluidized-bed process that methylchlorosilane produces, the particle diameter after its fragmentation, the screening is 0.5～100 micron.
3. according to the Preparation of catalysts method of the said low-temp synthesis of methanol of claim 1, it is characterized in that said organic solvent is one or more in ethanol, benzene, toluene, chloroform, acetone, oxolane and the ether.
4. according to the Preparation of catalysts method of the said low-temp synthesis of methanol of claim 1, it is characterized in that, said method comprising the steps of:
To clean the waste catalyst that obtains with organic solvent and carry out one or more processing in oxidation processes, reduction processing and the heat treatment, obtain the catalyst of low-temp synthesis of methanol.
5. according to the Preparation of catalysts method of the said low-temp synthesis of methanol of claim 4, it is characterized in that,
Said oxidation processes is calcined 0.5～10h for the waste catalyst that cleaning is obtained down at 100～900 ℃;
Said reduction is treated to waste catalyst that cleaning is obtained in the high purity inert gas of hydrogen, and 300～900 ℃ of reduction down, the recovery time is 2～10h, and under this atmosphere, is cooled to room temperature, and said high purity inert gas is nitrogen, helium or argon gas; Perhaps, use reducing agent that the waste catalyst that cleaning obtains is reduced in liquid phase, described reducing agent is one or more in formaldehyde, glucose and the boric acid hydrogen sodium;
Said heat treatment is down heated 0.5～10h at 800～2500 ℃ for the waste catalyst that cleaning is obtained in inert gas, and under this atmosphere, is cooled to room temperature, and said high purity inert gas is nitrogen, helium or argon gas.
6. the catalyst of a low-temp synthesis of methanol is characterized in that, said Preparation of catalysts method comprises produces broken, the screening of waste catalyst that methylchlorosilane produces, the step of cleaning with organic solvent then with direct method.
7. according to the catalyst of the said low-temp synthesis of methanol of claim 6, it is characterized in that said waste catalyst prepares the waste catalyst that methylchlorosilane produces for the direct method fluidized-bed process, the particle diameter after its fragmentation, the screening is 0.5～100 micron.
8. be the synthesis gas low temperature system catalyst for methanol of raw material according to the said waste catalyst that produces with direct method production methylchlorosilane of claim 6; It is characterized in that said organic solvent is one or more in ethanol, benzene, toluene, chloroform, acetone, oxolane and the ether.
9. according to the catalyst of the said low-temp synthesis of methanol of claim 6, it is characterized in that said Preparation of catalysts method may further comprise the steps:
To clean the waste catalyst that obtains with organic solvent and carry out one or more processing in oxidation processes, reduction processing and the heat treatment, obtain the catalyst of low-temp synthesis of methanol.
10. according to the catalyst of the said low-temp synthesis of methanol of claim 9, it is characterized in that,
Said oxidation processes is calcined 0.5～10h for the waste catalyst that cleaning is obtained down at 100～900 ℃;
Said reduction is treated to waste catalyst that cleaning is obtained in the high purity inert gas of hydrogen, and 300～900 ℃ of reduction down, the recovery time is 2～10h, and under this atmosphere, is cooled to room temperature, and said high purity inert gas is nitrogen, helium or argon gas; Perhaps, use reducing agent that the waste catalyst that cleaning obtains is reduced in liquid phase, described reducing agent is one or more in formaldehyde, glucose and the boric acid hydrogen sodium;
Said heat treatment is down heated 0.5～10h at 800～2500 ℃ for the waste catalyst that cleaning is obtained in inert gas, and under this atmosphere, is cooled to room temperature, and said high purity inert gas is nitrogen, helium or argon gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841448A (en) * | 2015-04-02 | 2015-08-19 | 中国科学院过程工程研究所 | Organic silicon waste contact body borne nickel-based methanation catalyst and preparation method therefor |
| CN107473935A (en) * | 2017-08-08 | 2017-12-15 | 中国科学院成都有机化学有限公司 | A kind of method of low temperature liquid phase synthesis gas ethanol |
| CN110813291A (en) * | 2019-10-11 | 2020-02-21 | 中国科学院过程工程研究所 | Method for preparing copper-based composite catalyst by using waste contact in production of organosilicon monomer trimethoxy silane and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841448A (en) * | 2015-04-02 | 2015-08-19 | 中国科学院过程工程研究所 | Organic silicon waste contact body borne nickel-based methanation catalyst and preparation method therefor |
| CN107473935A (en) * | 2017-08-08 | 2017-12-15 | 中国科学院成都有机化学有限公司 | A kind of method of low temperature liquid phase synthesis gas ethanol |
| CN107473935B (en) * | 2017-08-08 | 2021-01-08 | 中国科学院成都有机化学有限公司 | Method for preparing ethanol from low-temperature liquid-phase synthesis gas |
| CN110813291A (en) * | 2019-10-11 | 2020-02-21 | 中国科学院过程工程研究所 | Method for preparing copper-based composite catalyst by using waste contact in production of organosilicon monomer trimethoxy silane and application |
| CN110813291B (en) * | 2019-10-11 | 2021-04-13 | 中国科学院过程工程研究所 | Method for preparing copper-based composite catalyst by using waste contact in production of organosilicon monomer trimethoxy silane and application |
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|---|---|
| CN102773102B (en) | 2014-11-05 |
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