CN102773100A - Ternary copper catalyst CuO-Cu2O-Cu for synthesis of dimethyldichlorosilane and its preparation method - Google Patents
Ternary copper catalyst CuO-Cu2O-Cu for synthesis of dimethyldichlorosilane and its preparation method Download PDFInfo
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Abstract
The invention relates to the field of catalysts used for synthesis of dimethyldichlorosilane, in particular to a ternary copper catalyst CuO-Cu2O-Cu for synthesis of dimethyldichlorosilane and its preparation method. The method comprises the following steps of: 1) taking copper oxide powder as a raw material, adding a reducing gas, controlling its flow to make the flow of the reducing gas introduced into per gram of CuO particles at 0.1ml/min-100ml/min, maintaining the temperature at 100DEG C-600DEG C, carrying out a reduction reaction for 0.5h-6h, thus obtaining partially reduced copper oxide; and 2) subjecting the partially reduced copper oxide obtained in step 1) to breaking and ball-milling, thus obtaining the ternary copper catalyst for synthesis of dimethyldichlorosilane. With copper oxide as the raw material, the method prepares the ternary copper catalyst CuO-Cu2O-Cu through a one-step reaction, and has the advantages of simple technological process, convenient operation, strong process controllability, and easy mass production. The prepared catalyst shows high dimethyldichlorosilane selectivity and silicon powder material conversion rate.
Description
Technical field
The present invention relates to be used for the field of the catalyst of synthesization of dimethyl dichlorosilane, particularly, the present invention relates to a kind of ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane
2The O-Cu Catalysts and its preparation method.
Background technology
1940, E.G.Rochow invented direct method synthesizing methyl-chloro-silane technology, and this technical matters is simple, yield is high, without solvent, dangerous little and be convenient to realize continuous mass production, was still industry so far and went up most economical methylchlorosilane production approach.
Copper is the classical catalyst of direct method synthesizing methyl-chloro-silane.The copper catalyst that is used for the direct method synthesizing methyl-chloro-silane uses electrolytic copper powder at first, because electrolytic copper powder is surperficial dense, specific area is little, in reaction, is difficult to form the activated centre, causes catalytic activity not high.Subsequently, the stannous chloride of high reaction activity becomes the research focus of early stage commercialization Cu-series catalyst, yet this catalyst reaction initial stage selectivity is lower, and shelf stability is not good enough, the silicon tetrachloride of by-product and trim,ethylchlorosilane separation difficulty.Since the eighties in last century, after the surface treatment of copper powder being carried out modes such as redox, the ternary copper catalyst Cu-CuO-Cu of prepared partial oxidation
2O has that catalytic activity height, selectivity are high, induction period is short and is easy to advantage such as storages, become present methylchlorosilane produce in the maximum a kind of catalyst of use.
U.S. SCM (Smith Corona Marchant) company is to ternary copper catalyst Cu-CuO-Cu
2The preparation of O is studied, and mainly adopts copper powder elder generation air oxidation, the two-step process of high-energy ball milling again.At present, main in the world organosilicon production company is like DOW CORNING, Wa Ke, Bayer etc., the catalyst that all adopts U.S. SCM Corporation to provide.
Domestic Inst. of Jilin Chemical Industry Co (CN1072870A), organosilicon research center, the Ministry of Chemical Industry Chengdu (CN1008423B) and Kunming silicon ring catalysis science and technology limited Company (CN101811057A) have also been carried out certain research to the ternary copper catalyst.At present, there are gap in the selectivity of domestic catalyst dimethyldichlorosilane and catalytic activity thereof than the catalyst of U.S. SCM Corporation, and the synthetic employed catalyst of this monomer of domestic organosilicon industry causes production cost higher mainly from external import; Because monomer dimethyldichlorosilane purposes is wide, demand is big, price is high, the small raising of copper catalyst performance all will produce huge economic benefit; Therefore, the development of the homemade copper catalyst of cheap, of fine qualities, stable performance is an organosilicon industry difficult problem anxious to be solved.
At present; What Inst. of Jilin Chemical Industry Co was studied is raw material with copper salt solution and the metal more bold and vigorous than work in copper; In the agitated reactor that has the gas bubbling 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 control of granularity and component is poor, and residual reducing agent Fe powder difficulty is removed.Organosilicon research center, the Ministry of Chemical Industry Chengdu research with copper sulphate through dehydrating prepared ternary copper catalyst Cu-CuO-Cu such as hydrogen reducing and partial oxidation
2There is the poor problem of catalyst grain size control equally in O.
Summary of the invention
The object of the present invention is to provide a kind of ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane
2O-Cu Preparation of catalysts method.
A purpose more of the present invention is to provide a kind of ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane
2The O-Cu catalyst.
According to the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane of the present invention
2O-Cu Preparation of catalysts method said method comprising the steps of:
1) with the cupric oxide powder is raw material, adds reducibility gas, control its flow; Making the reducing gas flow that is passed into every gram CuO particle is 0.1ml/min～100ml/min, and temperature is 100 ℃-600 ℃, and reduction reaction takes place; Reaction time is 0.5h～6h, obtains the cupric oxide of partial reduction;
2), obtain being used for the ternary copper catalyst of synthesization of dimethyl dichlorosilane with the broken ball milling of the cupric oxide of partial reduction in the step 1).
According to the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane of the present invention
2O-Cu Preparation of catalysts method, cupric oxide powder is the commercial oxidation copper powder in the said step 1); In addition, also comprise the cupric oxide that all kinds of mantoquita calcinings obtain, the cupric oxide that elemental copper or low price copper or its mixture oxidation form, the cupric oxide that reclaims in the waste catalyst of organic silicon monomer compound probability.
According to the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane of the present invention
2O-Cu Preparation of catalysts method, reducibility gas can be a hydrogen in the said step 1), also can be carbon monoxide, or the mixture of these two kinds of gases, or the gaseous mixture of inert gas such as carbon monoxide/hydrogen and other nitrogen, helium, argon gas.
According to the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane of the present invention
2O-Cu Preparation of catalysts method, the reactor of reduction reaction can be fixed bed, agitated bed, fluid bed, rotary kiln and rotary furnace etc. in the said step 1); Reactor is provided with heater, and its temperature is adjustable, preferred 100 ℃-600 ℃ of reduction temperature.
According to the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane of the present invention
2The particle diameter of the ternary copper catalyst that ball milling obtains O-Cu Preparation of catalysts method, said step 2) is 0.5～500 μ m.
In addition, the present invention also provides a kind of ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane
2The O-Cu catalyst, said Preparation of catalysts method may further comprise the steps:
1) with the cupric oxide powder is raw material, adds reducibility gas, control its flow; Making the reducing gas flow that is passed into every gram CuO particle is 0.1mL/min～100mL/min, and temperature is 100 ℃-600 ℃, and reduction reaction takes place; Reaction time is 0.5h～6h, obtains the cupric oxide of partial reduction;
2), obtain being used for the ternary copper catalyst of synthesization of dimethyl dichlorosilane with the broken ball milling of the cupric oxide of partial reduction in the step 1).
According to the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane of the present invention
2O-Cu Preparation of catalysts method is a raw material with the cupric oxide, and through the amount of control feeding reducibility gas, the temperature of reduction reaction, and control reaction time with its partial reduction, form and are followed successively by Cu-Cu by outer surface to inside uniformly in reactor
2The copper catalyst of the three-phase structure of O-CuO, and broken ball milling obtains containing the ternary copper catalyst of elemental copper, cuprous oxide and cupric oxide.
The preparation method of the ternary copper catalyst that the present invention proposes, in the preparation process reduction insufficient, be followed successively by Cu-Cu by outer surface to inside at each catalyst granules
2O-CuO be prone to form the copper catalyst of uniform three-phase structure, and is active high, be different from reported utilize CuO, Cu
2The ternary copper catalyst of O, three kinds of powder mixing and ball milling preparations of Cu.As required, can control different Cu-Cu through adjustment reducing gas consumption, reaction temperature, time of contact and reaction time
2The O-CuO ratio, thus prepare the ternary copper catalyst of different component content.Described catalyst is made up of the elemental copper of 1%-20% (weight), the cuprous oxide of 40%-85% (weight) and the cupric oxide of 10%-55% (weight).This catalyst shows the selectivity and the silica flour conversion of raw material of higher dimethyldichlorosilane; Its preparation technology is simple, and controllable process property is strong, is a kind of simple, cheap, eco-friendly method for preparing catalyst.
Partial reduction catalyst of the present invention as a kind of three-phase structure of homogeneous, when carrying out catalytic reaction, can contact with reactive material full and uniformly, guarantees that each catalyst granules that contacts with reactant all contains Cu, Cu
2O and CuO; With Cu, Cu
2The direct mixing and ball milling catalyst of three kinds of raw materials of O and CuO is compared, and component is more evenly distributed, and more helps Cu, Cu
2Form stronger alternate synergy between O and CuO three constituent elements.
The invention has the advantages that:
1, the present invention is raw material with the cupric oxide, and single step reaction is prepared Cu-Cu
2O-CuO ternary copper catalyst, the experimental technique route is simple, and operation is convenient, and controllable process property is strong, is easy to large-scale production;
2, the catalyst of the present invention's preparation shows the selectivity and the silica flour conversion of raw material of higher dimethyldichlorosilane.
Description of drawings
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 XRD figure of the ternary copper catalyst of embodiment 2 preparations;
Fig. 4 is the granularmetric analysis of the ternary copper catalyst of embodiment 2 preparations;
Fig. 5 is the XRD figure of the ternary copper catalyst of embodiment 3 preparations;
Fig. 6 is the granularmetric analysis of the ternary copper catalyst of embodiment 3 preparations.
The specific embodiment
Following examples further specify the present invention, but the present invention is not limited to following examples.
Get the commercial CuO powder of 10g, put into fluidized-bed reactor, feed the N of 200ml/min
2, make its fluidisation; Under 250 ℃, feed the CO gas of 7.5ml/min, reaction 120min, and broken ball milling obtains the ternary copper catalyst; The gained copper catalyst consists of after the chemical method analysis: 4%Cu, 54%Cu
2O and 42%CuO (percentage by weight, down together).
The ternary copper catalyst material of above-mentioned preparation is carried out the XRD test on the X ' Pert PRO MPD type multi-functional X-ray diffractometer that Dutch Panalytical company (PANalytical) produces.
With the ternary copper catalyst material of above-mentioned preparation in Dandong Bai Te BT-9300Z laser particle size distribution instrument carry out granularmetric analysis.
The XRD figure of the copper catalyst that Fig. 1 obtains for embodiment 1, wherein 2 θ=36.5 ° are Cu
2The characteristic peak of O is the characteristic peak of CuO by 2 θ=35.5 ° and 2 θ=38.8 a ° acromion of forming, and 2 θ=43.3 ° are the characteristic peaks of Cu, this shows that the catalyst of this method preparation is by Cu, Cu
2The ternary copper catalyst that O and CuO form.
The granularmetric analysis of the copper catalyst that Fig. 2 obtains for embodiment 1 can know that by figure this method prepares the copper catalyst particle diameter and is distributed with three peaks, and particle diameter is all less than 20 microns, and wherein most of particle diameter is the 1-2 micron.
Embodiment 2
Get the commercial CuO powder of 10g, put into agitated bed reactor, the conditioned reaction temperature is 300 ℃, feeds the H of 7.5ml/min
2, reaction 90min, and broken ball milling obtains the ternary copper catalyst; The gained copper catalyst consists of after the chemical method analysis: 3%Cu, 58%Cu
2O, 38%CuO.
The XRD figure of the copper catalyst that Fig. 3 obtains for embodiment 1, wherein 2 θ=36.4 ° are Cu
2The characteristic peak of O is the characteristic peak of CuO by 2 θ=35.5 ° and 2 θ=38.6 a ° acromion of forming, and 2 θ=43.2 ° are the characteristic peaks of Cu, this shows that the catalyst of this method preparation is by Cu, Cu
2The ternary copper catalyst that O and CuO form.
The granularmetric analysis of the copper catalyst that Fig. 4 obtains for embodiment 1 can know that by figure this method prepares the copper catalyst particle diameter basically less than 10 microns, and wherein most of particle diameter is the 1-3 micron.
Embodiment 3
Get the commercial CuO powder of 10g, put into fluidized-bed reactor, the conditioned reaction temperature is 200 ℃, feeds the N of 200ml/min
2, make its fluidisation; Regulating the CO gas flow is 6.7ml/min, and the reaction time is 180min, and broken ball milling obtains the ternary copper catalyst; The gained copper catalyst consists of after the chemical method analysis: 7%Cu, 50%Cu
2O and 43%CuO.
The XRD figure of the copper catalyst that Fig. 5 obtains for embodiment 3, wherein 2 θ=36.6 ° are Cu
2The characteristic peak of O is the characteristic peak of CuO by 2 θ=35.5 ° and 2 θ=38.8 a ° acromion of forming, and 2 θ=43.4 ° are the characteristic peaks of Cu, this shows that the catalyst of this method preparation is by Cu, Cu
2The ternary copper catalyst that O and CuO form.
The granularmetric analysis of the copper catalyst that Fig. 6 obtains for embodiment 3 can know that by figure this method prepares the copper catalyst particle diameter all less than 20 microns, and most of particle diameter is the 1-2 micron, 2.0 microns of meso-position radius.
Embodiment 4
With Cu (NO
3)
2The CuO powder 10g that calcining makes puts into fixed bed reactors, and regulating the CO flow is 10ml/min; Reaction temperature is 200 ℃; Reduction 120min, and broken ball milling obtains the ternary copper catalyst, the gained copper catalyst consists of after the chemical method analysis: 9%Cu, 80%Cu
2O and 11%CuO, its particle diameter are all less than 20 microns, and most of particle diameter is 2 microns.
Embodiment 5
With the commercial CuO powder of 20g, put into agitated bed reactor, regulating the CO flow is 2ml/min, reaction temperature is 200 ℃, reduction 360min, and broken ball milling obtains the ternary copper catalyst, the gained copper catalyst consists of after the chemical method analysis: 12%Cu, 60%Cu
2O and 28%CuO, its particle diameter are all less than 20 microns.
Embodiment 6
CuO powder 10g with simple substance Cu powder complete oxidation forms puts into fixed bed reactors, and regulating the CO flow is 10ml/min; Reaction temperature is 200 ℃; Reduction 120min, and broken ball milling obtains the ternary copper catalyst, the gained copper catalyst consists of after the chemical method analysis: 9%Cu, 68%Cu
2O and 23%CuO, its particle diameter are all less than 20 microns.
Embodiment 7
With commercial CuO powder 5g, put into fluidized-bed reactor, feed N
2Form to mix reducing gas with CO, regulating its flow is 500ml/min, and reaction temperature is 100 ℃, reduction 30min, and broken ball milling obtains the ternary copper catalyst, the gained copper catalyst consists of after the chemical method analysis: 3%Cu, 58%Cu
2O and 39%CuO, its particle diameter are all less than 20 microns, and most of particle diameter is 2 microns.
Embodiment 8
With the commercial CuO powder of 10g, put into the rotary furnace reactor, regulating the CO flow is 2ml/min, reaction temperature is 600 ℃, reduction 30min, and broken ball milling obtains the ternary copper catalyst, the gained copper catalyst consists of after the chemical method analysis: 5%Cu, 45%Cu
2O and 50%CuO, its particle diameter are all less than 20 microns.
Embodiment 9
The CuO powder that reclaims in the waste catalyst with 10g organic silicon monomer compound probability is put into fluidized-bed reactor; Feed the Ar gas of 200ml/min, make its fluidisation; Regulating the CO flow is 7.5ml/min, and reaction temperature is 200 ℃, reduction 180min, and the time of staying of material in fluid bed is 1.2s, and broken ball milling obtains the ternary copper catalyst, gained ternary copper catalyst consists of after the chemical method analysis: 13%Cu, 64%Cu
2O and 23%CuO, its particle diameter are all less than 20 microns, and most of particle diameter is the 1-2 micron, 2.2 microns of meso-position radius.
Catalytically active assessment: at diameter is in the glass fixed bed of 20mm; Adding is heated to 325 ℃ by the even contact that ternary copper catalyst 1g for preparing in silica flour 10g and the foregoing description and co-catalyst zinc powder 0.1g form, and the chloromethanes after the feeding preheating reacts; The chloromethanes flow velocity is 25mL/min; Reaction 24h obtains mix products, calculates through gas chromatographic analysis; Can obtain catalytic activity result's (seeing table 1) such as selectivity and silica flour conversion ratio of dimethyldichlorosilane, choose SCM ternary copper catalyst simultaneously and compare.
Table 1 activity rating result
(1) M
1: monomethyl trichlorosilane, M
2: dimethyldichlorosilane, M
3: tri-methyl-chlorosilane
Wherein, W is the weight of material.
Can know by table 1, through the ternary copper catalyst of method preparation of the present invention, because ternary component content is different; Catalyst activity is different; The selectivity of target product dimethyldichlorosilane is greater than 69%, the highlyest can be 86.8%, and the silicon conversion ratio is in 23%～54% scope simultaneously.
Claims (10)
1. ternary copper CuO-Cu who is used for the synthesization of dimethyl dichlorosilane
2O-Cu Preparation of catalysts method is characterized in that, said method comprising the steps of:
1) with the cupric oxide powder is raw material, adds reducibility gas, control its flow; Making the reducing gas flow that is passed into every gram CuO particle is 0.1mL/min～100mL/min, and temperature is 100 ℃～600 ℃, and reduction reaction takes place; Reaction time is 0.5h～6h, obtains the cupric oxide of partial reduction;
2), obtain being used for the ternary copper catalyst of synthesization of dimethyl dichlorosilane with the broken ball milling of the cupric oxide of partial reduction in the step 1).
2. the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane according to claim 1
2O-Cu Preparation of catalysts method; It is characterized in that cupric oxide powder is the commercial oxidation copper powder in the said step 1), the cupric oxide that the mantoquita calcining obtains; The cupric oxide that elemental copper, low price copper and composition thereof oxidation obtains, perhaps cupric oxide for reclaiming in the waste catalyst of organic silicon monomer compound probability.
3. the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane according to claim 1
2O-Cu Preparation of catalysts method is characterized in that reducibility gas comprises hydrogen and/or carbon monoxide in the said step 1).
4. the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane according to claim 3
2O-Cu Preparation of catalysts method is characterized in that reducibility gas comprises one or more in nitrogen, helium and the argon gas in the said step 1), and the reaction unit of reduction reaction is fixed bed, agitated bed, fluid bed, rotary kiln or rotary furnace.
5. the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane according to claim 1
2O-Cu Preparation of catalysts method is characterized in that, said step 2) in the particle diameter of the ternary copper catalyst that obtains of ball milling be 0.5～500 μ m.
6. ternary copper CuO-Cu who is used for the synthesization of dimethyl dichlorosilane
2The O-Cu catalyst is characterized in that, said Preparation of catalysts method may further comprise the steps:
1) with the cupric oxide powder is raw material, adds reducibility gas, control its flow; Making the reducing gas flow that is passed into every gram CuO particle is 0.1mL/min～100mL/min, and temperature is 100 ℃-600 ℃, and reduction reaction takes place; Reaction time is 0.5h～6h, obtains the cupric oxide of partial reduction;
2), obtain being used for the ternary copper catalyst of synthesization of dimethyl dichlorosilane with the broken ball milling of the cupric oxide of partial reduction in the step 1).
7. the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane according to claim 6
2The O-Cu catalyst; It is characterized in that; Cupric oxide powder is the cupric oxide that obtains of commercial oxidation copper powder or mantoquita calcining or elemental copper, the cupric oxide that obtains of copper and composition thereof oxidation, the perhaps cupric oxide for reclaiming in the waste catalyst of organic silicon monomer compound probability at a low price in the said step 1).
8. the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane according to claim 6
2The O-Cu catalyst is characterized in that, reducibility gas comprises one or more in hydrogen and the carbon monoxide in the said step 1).
9. the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane according to claim 8
2The O-Cu catalyst is characterized in that, reducibility gas comprises one or more in nitrogen, helium and the argon gas in the said step 1), and the reaction unit of reduction reaction is fixed bed, agitated bed, fluid bed, rotary kiln or rotary furnace.
10. the ternary copper CuO-Cu that is used for the synthesization of dimethyl dichlorosilane according to claim 6
2The O-Cu catalyst is characterized in that, said step 2) in the particle diameter of the ternary copper catalyst that obtains of ball milling be 0.5～500 μ m.
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| CN103127937A (en) * | 2013-02-21 | 2013-06-05 | 中国科学院过程工程研究所 | Ternary copper-based catalyst produced by using replaced copper, and production method and purpose thereof |
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| CN113976116A (en) * | 2021-10-25 | 2022-01-28 | 有研粉末新材料(合肥)有限公司 | Ternary copper Cu-Cu prepared by variable-speed ball milling2O-CuO catalyst and method therefor |
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| CN110787800B (en) * | 2019-09-10 | 2022-10-21 | 安徽德诠新材料科技有限公司 | Method for preparing superfine ternary copper catalyst at low cost |
| CN110665504A (en) * | 2019-10-22 | 2020-01-10 | 合盛硅业股份有限公司 | Preparation method of composite ternary copper powder |
| CN113019468A (en) * | 2021-03-05 | 2021-06-25 | 昆明理工大学 | Copper-based Cu-Cu2Preparation method of O-CuO ternary composite core-shell material |
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