CN102649061B - Ternary copper catalyst used in synthesis of dimethyl dichlorosilane and preparation method of ternary copper catalyst - Google Patents
Ternary copper catalyst used in synthesis of dimethyl dichlorosilane and preparation method of ternary copper catalyst Download PDFInfo
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Abstract
The invention relates to the field of a catalyst used in synthesis of dimethyl dichlorosilane, in particular to a ternary copper catalyst used in synthesis of the dimethyl dichlorosilane and a preparation method of the ternary copper catalyst. The preparation method according to the invention comprises the following steps of: (1) dissolving a copper salt into a mixed solvent of polybasic alcohol and water to obtain solution with copper ion concentration of 0.0025-0.25 g/mL; and (2) dropwise adding pH regulator aqueous solution into the solution obtained by the step (1) under a stirring condition, transferring the solution into a reaction kettle after the pH value of the solution is 6-13, reacting at 100-250 DEG C for 2-30 hours to obtain brown precipitate, and washing and drying the precipitate to obtain the ternary copper catalyst. The ternary copper catalyst prepared by the invention has the advantages of simple experimental process route, convenience in operation, entire process performed in the reaction kettle, no need of any complex experimental equipment, high reaction speed, easiness for large-scale production and capability of showing higher selectivity for the dimethyl dichlorosilane and higher conversion rate for a silicon powder raw material.
Description
Technical field
The present invention relates to the field for the synthesis of the catalyst of dimethyldichlorosilane, particularly, relate to a kind of ternary copper catalyst for the synthesis of dimethyldichlorosilane and preparation method thereof.
Background technology
Organosilicon material has the dual property of inorganic material and organic material simultaneously, and high-low temperature resistant, electric insulation, the excellent specific property such as weather-proof, corrosion-resistant, nonpoisonous and tasteless, be widely used in the fields such as electronics, automobile, oil, chemical industry, building, Aero-Space.Methylchlorosilane be prepare organosilicon material most important, be also the organic silicon monomer of consumption maximum, be basis and the pillar of whole organosilicon industry.E.G.Rochow is in the direct synthesis methylchlorosilane technology of invention in 1940, because technique is simple, yield is high, without solvent, dangerous little and be convenient to realize continuous mass production, is still so far the unique method of industrial production methylchlorosilane.The method is under copper catalyst effect, by silica flour and chloromethanes reaction, to be generated the series monomers of methylchlorosilane.
This course of reaction is complicated, accessory substance is more, its selective and yield is also one of major criterion of weighing " direct method " production technology level, and one of the important channel of improving the selective and yield of dimethyldichlorosilane is exactly to improve copper catalyst selectively and the conversion ratio of silicon raw material.
Copper is the classical catalyst of direct synthesis methylchlorosilane.The activity of copper catalyst not only with its chemical composition, particle diameter distributes, surface state and preparation method are relevant, but also jointly to form the method for contact relevant with silica flour and co-catalyst.Copper catalyst is used electrolytic copper powder at first, and because the surface of electrolytic copper powder is dense, specific area is little, is difficult to form activated centre in reaction, causes catalytic activity not high.Business-like Cu-series catalyst is copper powder or the stannous chloride of partial oxidation at present.Stannous chloride is because self stability is bad, deposit process perishable, make to react repeated variation, in addition form in contact process and produce silicon tetrachloride with silica flour, the latter's boiling point and trim,ethylchlorosilane are very approaching, and form azeotropic mixture, make the refining more difficult of methylchlorosilane, so cuprous chloride catalyst is eliminated gradually.The cuprous chloride catalyst using is in the past compared, ternary copper catalyst CuO-Cu
2o-Cu has strong, the selective height of catalytic activity, induction period is short and be easy to the advantages such as storage, is to use maximum a kind of catalyst during current methylchlorosilane is produced.
The method of synthesis of ternary copper catalyst is mainly copper powder to be carried out to the modes such as redox to process at present.The CN85103904 of U.S. SCM Corporation is studied the preparation of ternary copper catalyst, mainly adopts the first air oxidation of copper powder, then the two-step process of high-energy ball milling.Inst. of Jilin Chemical Industry Co CN1072870A has studied that to take copper salt solution and the metal more bold and vigorous than work in copper be raw material, in the reactor with gas sparging device, adopt precipitate reduction-suspension oxidation one-step method directly to make the ternary copper catalyst that is rich in cuprous oxide, cupric oxide, copper.The Ministry of Chemical Industry Chengdu organosilicon research center CN1008423B has studied with copper sulphate through dehydrating, and the techniques such as hydrogen reducing and partial oxidation are prepared ternary copper catalyst CuO-Cu
2o-Cu.Kunming silicon ring catalysis science and technology limited Company CN101811057A takes the method for copper powder, cuprous oxide, cupric oxide the ball milling of metering and prepares ternary copper catalyst.Adopt said method Kaolinite Preparation of Catalyst, preparation condition and catalytic component content are difficult to control, and technique more complicated, need to be used more special device and equipment, the unstable properties of catalyst.Solvent-thermal method Kaolinite Preparation of Catalyst, its process route is succinct, and reaction fast, is a kind of method of efficient quick, cheap, eco-friendly Kaolinite Preparation of Catalyst.
At present, cupric oxide (CuO), cuprous oxide (Cu
2o) and the solvent process for thermosynthesizing of elemental copper (Cu) in succession reported.The distinguishing feature of comparing solvent thermal reaction with other syntheti c routes is reaction condition as mild as a dove, can stablize metastable phase, prepares novel substance, develop new syntheti c route etc.CN101318688A has reported a kind of solvent process for thermosynthesizing of preparing cupric oxide that reacts by presoma, with CuCl
2solution is initial reactant, adds ammoniacal liquor and is adjusted to pH=10-14, uses ethanol to make solvent, at high temperature [Cu (NH
3)
4]
2+with excess of ammonia water generation hydro-thermal reaction, obtain alkali formula Cu
2(OH)
3cl presoma, then, 300-500 ℃ of annealing 2 hours, forms cupric oxide.CN101805010A has reported a kind of solvent process for thermosynthesizing of cuprous oxide, it is dissolved in the water a certain amount of soluble metal mantoquita and polyvinylpyrrolidone to form the solution of clarification, then add a certain amount of reducing agent, obtain yellow-orange suspension and be cuprous oxide material.The people such as Teo (J.J.Teo, Y.Chang, H.C.Zeng.Langmuir, 2006,22,7369-7377) take DMF as solvent, Cu (NO
3)
2wei Tong source, utilizes solvent-thermal method to synthesize Cu at 150-200 ℃
2o nano material, and on this basis again by adding ethanol to carry out mixed solvent thermal response, by Cu
2o further reduction has obtained Cu nano material.The present invention intends preparing CuO-Cu with solvent-thermal method
2o-Cu ternary copper catalyst.Yet prepare CuO-Cu with solvent-thermal method
2o-Cu have not been reported, and carries out the research invention of this respect, has great importance.
Summary of the invention
The present inventor proposes and has completed the present invention in order to address the above problem.In the reaction of silica flour and chloromethanes, generate in the reaction of methylchlorosilane series monomers, this catalyst generates dimethyldichlorosilane to reaction and has higher selectively, and silica flour conversion ratio is higher simultaneously.
The object of this invention is to provide the preparation method for the synthesis of the ternary copper catalyst of dimethyldichlorosilane.
A further object of the present invention is to provide the ternary copper catalyst for the synthesis of dimethyldichlorosilane of preparing by said method.
Preparation method according to the ternary copper catalyst for the synthesis of dimethyldichlorosilane of the present invention, comprises the following steps:
1) mantoquita is dissolved in the mixed solvent of polyalcohol and water, obtains the solution that copper ion concentration is 0.0025g/mL-0.25g/mL;
2) under stirring condition, to above-mentioned steps 1) dropwise add pH adjusting agent in the solution that obtains, the pH value for the treatment of solution is 6-13, solution is transferred in reactor, in 100 ℃-250 ℃ reaction 2-30h, obtain brown precipitation, after washing of precipitate is dry, can obtain ternary copper catalyst.
The preparation method of the ternary copper catalyst that the present invention proposes, is to take mantoquita as raw material, and the mixed solvent and the pH value conditioning agent that add polyalcohol and water to form, after reaction kettle for reaction certain hour, are dried and can make after filtration.In solvent thermal reaction, one or more presomas are dissolved in nonaqueous solvents, under liquid phase or super critical condition, are dispersed in reactant in liquid phase and are uniformly dispersed and more active at atomic scale, easily impel reaction to carry out.This process is relatively simple and be easy to control, and in enclosed system, can effectively prevent volatilization and the presoma of preparation to air-sensitive of noxious material.In addition, phase composition, pattern and the particle size of product are easy to control.
The ternary copper catalyst that uses this law to make is comprised of copper, cuprous oxide and cupric oxide.As required, can control different CuO-Cu by changing the conditions such as solvent ratios, reaction temperature, reaction time, pH value
2o-Cu ratio, thus make three component copper catalysts of required constituent content.Described catalyst is comprised of the cupric oxide of the elemental copper of 1-60% (weight), the cuprous oxide of 20-70% (weight) and 5-60% (weight).Whole technical process is carried out in reactor, preferred liner polytetrafluoroethylene (PTFE) or enamel reaction still, and process route is succinct, and reaction fast, is a kind of efficient quick, cheap, the eco-friendly method of preparing ternary copper catalyst.
The method according to this invention, described mantoquita is that in one or more mixtures in copper nitrate, copper sulphate, copper chloride, Schweinfurt green, solution, copper ion concentration is 0.0025g/mL-0.25g/mL.
The method according to this invention, the preferred ethylene glycol of described polyalcohol, propane diols, butanediol or glycerine, its ratio shared in mixed solvent is 10-75% (volume ratio).
The method according to this invention, described pH value conditioning agent is selected from alkali or the ammoniacal liquor of the metallic element of the first main group and the second main group, and pH value scope is 6-13, and the concentration of the aqueous solution of described pH adjusting agent is 1-5M.Described reaction temperature is 100-250 ℃.The described reaction time is 2h-30h.
According to the ternary copper catalyst for the synthesis of dimethyldichlorosilane of the present invention, it is prepared by the method comprising the following steps:
1) mantoquita is dissolved in the mixed solvent of polyalcohol and water, obtains the solution that copper ion concentration is 0.0025g/mL-0.25g/mL;
2) under stirring condition, to above-mentioned steps 1) dropwise add pH adjusting agent in the solution that obtains, the pH value for the treatment of solution is 6-13, solution is transferred in reactor, in 100 ℃-250 ℃ reaction 2-30h, obtain brown precipitation, after washing of precipitate is dry, can obtain ternary copper catalyst.
The concrete preparation method that the copper sulphate of take is according to an embodiment of the invention example is as follows:
(1) obtain solution A first: a certain amount of copper sulphate is dissolved in the mixed solvent of 40mL ethylene glycol and water, dissolves under 300-500 rev/min of rotating speed stirs, obtain the solution that copper ion concentration is 0.0025g/mL-0.25g/mL.
(2) ammonia spirit of secure ph conditioning agent solution B: 1-5M.
(3) after A solution dissolves completely, under 300-600 rev/min of rotating speed magnetic agitation, dropwise add B solution, treat that the pH value of solution, to 6-13, is transferred to solution in polytetrafluoroethylene (PTFE) reactor, in 100 ℃-250 ℃ reaction 2-30h, obtain brown precipitation.
(4) after washing of precipitate is dried, at 60-100 ℃ of vacuum drying 6h, can obtain ternary copper catalyst.
The invention has the advantages that:
1, the present invention prepares CuO-Cu first with solvent-thermal method
2o-Cu ternary copper catalyst, experimental technique route is simple, and operation is convenient, and whole technical process is carried out in reactor, and without any complex experiment equipment, reaction fast, is easy to large-scale production;
2, the catalyst that prepared by the present invention shows the conversion ratio of the selective and silica flour raw material of higher dimethyldichlorosilane.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the ternary copper catalyst of embodiment 1 preparation.
Fig. 2 is the granularmetric analysis of the ternary copper catalyst of embodiment 1 preparation.
Fig. 3 is the SEM figure of the ternary copper catalyst of embodiment 1 preparation, and multiplication factor is respectively 1000 times, 10000 times.
Fig. 4 is the TEM figure of the ternary copper catalyst of embodiment 1 preparation, and multiplication factor is 5000 times.
Fig. 5 is the XRD figure of the ternary copper catalyst of embodiment 2 preparations.
Fig. 6 is the granularmetric analysis of the ternary copper catalyst of embodiment 2 preparations.
Fig. 7 is the XRD figure of the ternary copper catalyst of embodiment 3 preparations.
Fig. 8 is the granularmetric analysis of the ternary copper catalyst of embodiment 3 preparations.
The specific embodiment
Following examples further illustrate the present invention, but the present invention is not limited to following examples.
Take 0.5g Cu (CH
3cOO)
2be dissolved in the glycerin solution of 40mL 15% (volume ratio), the sodium hydroxide solution that adds the 1M configuring, regulate pH value to 6, be positioned over 120 ℃ of reaction 15h of inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 28%Cu (percentage by weight, lower same), 49%Cu
2o and 23%CuO.
On the X ' PertPRO MPD type Multi-functional X ray diffractometer that the ternary copper catalyst material of above-mentioned preparation is produced in Dutch Panalytical company (PANalytical), carry out XRD test.
The ternary copper catalyst material of above-mentioned preparation is carried out to granularmetric analysis at Dandong Bai Te BT-9300Z laser fineness gage.
The JSM6700 model field emission scanning electron microscope observation surface topography that the ternary copper catalyst material of above-mentioned preparation is produced in company of NEC.
The JEM-2100 lanthanum hexaboride transmission electron microscopy observation particle information that the ternary copper catalyst material of above-mentioned preparation is produced in company of NEC.
Fig. 1 is the XRD figure of the copper catalyst that obtains of embodiment 1, and wherein 2 θ=36.4 ° are Cu
2the characteristic peak of O, the acromion being comprised of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, 2 θ=43.3 ° are the characteristic peaks of Cu, as can be seen here, with the synthetic catalyst of the method, are by CuO, Cu
2the ternary copper catalyst that O and Cu form.
Fig. 2 is the granularmetric analysis of the copper catalyst that obtains of embodiment 1, and as seen from the figure, the particle diameter of this synthetic copper catalyst is all less than 20 microns, and wherein most of particle diameter is 2 microns.
Fig. 3 is the SEM figure of the copper catalyst that obtains of embodiment 1, and as seen from the figure, the particle of this synthetic copper catalyst is amorphous, and major part is less than 10 microns, and part coalesces together disorderly.
Fig. 4 is the TEM figure of the copper catalyst that obtains of embodiment 1, an optional particle, and as seen from the figure, the particle of this synthetic copper catalyst is solid.
Take 1g Cu (NO
3)
2be dissolved in the glycerin solution of 40mL 40% (volume ratio), the sodium hydroxide solution that adds the 3M configuring, regulate pH value to 9, be positioned over 180 ℃ of reaction 24h of inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 11%Cu, 68%Cu
2o and 21%CuO.
Fig. 5 is the XRD figure of the copper catalyst that obtains of embodiment 2, and wherein 2 θ=36.4 ° are Cu
2the characteristic peak of O, the acromion being comprised of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, 2 θ=43.3 ° are the characteristic peaks of Cu, as can be seen here, with the synthetic catalyst of the method, are by CuO, Cu
2the ternary copper catalyst that O and Cu form.
Fig. 6 is the granularmetric analysis of the copper catalyst that obtains of embodiment 2, and as seen from the figure, the particle diameter of this synthetic copper catalyst is all less than 20 microns, and wherein most of particle diameter is 2 microns.
Take 2g CuSO
4be dissolved in the butanediol aqueous solution of 75% (volume ratio) of 40mL, the sodium hydroxide solution that adds the 5M configuring, regulate pH value to 13, be positioned over 250 ℃ of reaction 30h of inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 43%Cu, 44%Cu
2o and 13%CuO.Fig. 5 is the XRD figure of product, and Fig. 6 is granularmetric analysis.
Fig. 7 is the XRD figure of the copper catalyst that obtains of embodiment 3, and wherein 2 θ=36.4 ° are Cu
2the characteristic peak of O, the acromion being comprised of 2 θ=35.5 ° and 2 θ=38.7 ° is the characteristic peak of CuO, 2 θ=43.3 ° are the characteristic peaks of Cu, as can be seen here, with the synthetic catalyst of the method, are by CuO, Cu
2the ternary copper catalyst that O and Cu form.
Fig. 8 is the granularmetric analysis of the copper catalyst that obtains of embodiment 3, and as seen from the figure, the particle diameter of this synthetic copper catalyst is all less than 40 microns, and wherein most of particle diameter is 20 microns.
Take 5g Cu (CH
3cOO)
2be dissolved in the aqueous solution of propylene glycol of 40mL 60% (volume ratio), the ammonia spirit that adds the 1M configuring, regulate pH value to 7, be positioned over 150 ℃ of reaction 2h of inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 10%Cu, 52%Cu
2o and 38%CuO.The particle diameter of this ternary copper catalyst is all less than 20 microns.
Take 8g CuCl
2be dissolved in the glycol water of 40mL 30% (volume ratio), the aqua calcis that adds the 2M configuring, regulate pH value to 10, be positioned over 200 ℃ of reaction 10h of inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 22%Cu, 63%Cu
2o and 15%CuO.The particle diameter of this ternary copper catalyst is all less than 20 microns.
Take 0.5g CuCl
2and 0.5g CuSO
4be dissolved in the glycerin solution of 40mL 20% (volume ratio), the potassium hydroxide solution that adds the 2M configuring, regulate pH value to 8, be positioned over 100 ℃ of reaction 6h of inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 5%Cu, 50%Cu
2o and 45%CuO.The particle diameter of this ternary copper catalyst is all less than 20 microns.
Embodiment 7
Take 3g CuSO
4be dissolved in the aqueous solution of propylene glycol of 40mL 50% (volume ratio), the aqua calcis that adds the 5M configuring, regulate pH value to 11, be positioned over 220 ℃ of reaction 20h of liner enamel reaction still, after reaction finishes, product filtered, water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 60%Cu, 23%Cu
2o and 17%CuO.The particle diameter of this ternary copper catalyst is all less than 20 microns.
Embodiment 8
Take 5g Cu (NO
3)
2and 5g CuSO
4be dissolved in the butanediol aqueous solution of 65% (volume ratio) of 40mL, the potassium hydroxide solution that adds the 1M configuring, regulate pH value to 6, be positioned over 200 ℃ of reaction 12h of liner enamel reaction still, after reaction finishes, product filtered, water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 30%Cu, 54%Cu
2o and 16%CuO.The particle diameter of this synthetic copper catalyst is all less than 40 microns.
Embodiment 9
Take 0.5g Cu (NO
3)
2, be dissolved in 10% the glycol water of 40mL, add the sodium hydroxide solution of the 2M configuring, regulate pH value to 8, be positioned over 100 ℃ of reaction 12h of liner enamel reaction still, after reaction finishes, product is filtered, and water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying chamber.Gained copper catalyst is composed as follows after chemical method is analyzed: 25%Cu, 60%Cu
2o and 15%CuO.The particle diameter of this synthetic copper catalyst is all less than 40 microns.
Catalytically active assessment: in the glass fixed bed that is 15mm at diameter, add by silica flour 10g, the homogeneous mixture that the ternary copper catalyst 1g preparing in zinc powder 0.1g and above-described embodiment forms, be heated to 325 ℃, the chloromethanes passing into after preheating reacts, and chloromethanes speed is 25mL/min, reaction 24h, obtain mix products, through gas chromatographic analysis, calculate, can obtain the catalytic activity results (in Table 1) such as selective and silica flour conversion ratio of dimethyldichlorosilane.
As shown in Table 1, the ternary copper catalyst of preparing by method of the present invention is selectively greater than 58% to dimethyldichlorosilane, the highlyest can be 83.3%, and silicon conversion is in 23%～40% scope simultaneously.
Table 1 activity rating result
Note: (1) M
1: Trichloromethyl silane, M
2: dimethyldichlorosilane, M
3: tri-methyl-chlorosilane
(2)
Wherein, the weight that W is material.
Claims (10)
1. for the synthesis of a preparation method for the ternary copper catalyst of dimethyldichlorosilane, it is characterized in that, said method comprising the steps of:
1) mantoquita is dissolved in the mixed solvent of polyalcohol and water, obtains the solution that copper ion concentration is 0.0025g/mL-0.25g/mL;
2) with pH adjusting agent regulating step 1) the pH value of the solution that obtains is 6-13, and solution is transferred in reactor, in 100 ℃-250 ℃ reaction 2-30h, obtains brown precipitation, after washing of precipitate is dry, can obtain ternary copper catalyst.
2. preparation method according to claim 1, is characterized in that, described polyalcohol is ethylene glycol, propane diols, butanediol or glycerine, and its volume ratio shared in mixed solvent is 10-75%.
3. preparation method according to claim 1, is characterized in that, described mantoquita is one or more in copper nitrate, copper sulphate, copper chloride, Schweinfurt green.
4. preparation method according to claim 1, is characterized in that, described pH value conditioning agent is selected from alkali or the ammoniacal liquor of the metallic element of the first main group or the second main group, and the concentration of the aqueous solution of described pH adjusting agent is 1-5M.
5. preparation method according to claim 1, is characterized in that, described reactor is inner liner polytetrafluoroethylene or enamel reaction still.
6. for the synthesis of a ternary copper catalyst for dimethyldichlorosilane, it is characterized in that, described catalyst is prepared by the method comprising the following steps:
1) mantoquita is dissolved in the mixed solvent of polyalcohol and water, obtains the solution that copper ion concentration is 0.0025g/mL-0.25g/mL;
2) under stirring condition, in the solution obtaining to above-mentioned step 1), dropwise add the pH value conditioning agent aqueous solution, the pH value for the treatment of solution is 6-13, solution is transferred in reactor, in 100 ℃-250 ℃ reaction 2-30h, obtain brown precipitation, after washing of precipitate is dry, can obtain ternary copper catalyst.
7. catalyst according to claim 6, is characterized in that, described polyalcohol is ethylene glycol, propane diols, butanediol or glycerine, and its volume ratio shared in mixed solvent is 10-75%.
8. catalyst according to claim 6, is characterized in that, described mantoquita is one or more in copper nitrate, copper sulphate, copper chloride, Schweinfurt green.
9. catalyst according to claim 6, is characterized in that, described pH value conditioning agent is selected from alkali or the ammoniacal liquor of the metallic element of the first main group or the second main group, and the concentration of the aqueous solution of described pH adjusting agent is 1-5M.
10. catalyst according to claim 6, is characterized in that, described reactor is inner liner polytetrafluoroethylene or enamel reaction still.
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| CN103127936B (en) * | 2013-02-04 | 2015-11-18 | 中国科学院过程工程研究所 | A kind of method of liquid phase ball milling partial reduction method Kaolinite Preparation of Catalyst and Ternary copper catalyst |
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| 邹家禹.用于甲基氯烷合成的铜催化剂的制备及评价.《有机硅材料及应用》.1996,(第4期),1-5. |
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