CN85106520A

CN85106520A - Catalyst composition and using method

Info

Publication number: CN85106520A
Application number: CN 85106520
Authority: CN
Inventors: 阿兰·里特泽; 雷·沃尔顿·谢德; 道格拉斯·约翰·鲍登; 乔治·弗里德; 里克·施明克; 维恩·利梅·巴克斯
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 1984-02-13
Filing date: 1985-08-29
Publication date: 1987-03-11

Abstract

Proposed a kind of method for preparing organo-halogen-silane, this method is included under the significant quantity catalyzer existence condition, makes halogenated organic compound and Powdered pasc reaction, and said catalyzer is made up of following ingredients basically: (a) Cu ⁰, Cu ⁺And Cu ⁺⁺Mixture, (b) about 200 to 5000ppm tin or sn-containing compounds, (is the tin content of base in copper), and (c) about 50 to 5000ppm aluminium or aluminum contained compound (is the aluminium content of base in copper).

Description

Catalyst composition and using method

The invention relates to the catalyst composition that catalytic powder powder Pure Silicon Metal and organic fontanel are used for silane for the organic fontanel of prepared in reaction between the compound.More particularly, the invention relates to the tin, aluminium, iron and the plumbous copper catalyst composition that contain key content, and in the presence of this catalyzer the organic fontanelle compound of catalysis, alkyl compound fontanelle such as methyl chloride preferably, and the reaction between the powdery metal silicon, to produce organic fontanel for silane, the method for methylchlorosilanes particularly.

People know before the present invention, and for example Rochow is at United States Patent (USP) the 2nd, 380, point out in 995: in the presence of copper catalyst, utilize the method for direct reaction between organic chloride and the elemental silicon, can prepare the alkyl fontanel for silane.In fact, in the sort of stirred bed reactor that this reaction is normally put down in writing on No. the 2nd, 449,821, people's such as Sellers United States Patent (USP), at people's such as Reed United States Patent (USP) the 2nd, in the fluidized-bed reactor of being put down in writing on 389, No. 931 or in rotary kiln, carry out.This reaction is to pass to organic fontanelle compound steam at the powdery metal silicon face generally speaking, this reaction mixture is remained on to carry out under the temperature of raising simultaneously.Put down in writing in the Rochow patent of mentioning as mentioned like that, typical method is, elemental silicon is mixed with the copper powder of fully pulverizing, usefulness copper is as catalyst for reaction between organic fontanelle compound of catalysis and the silicon.

When preparing organic fontanel for silane with the Rochow direct method, two kinds of principal reaction products are organic three fontanels for silane (T) and two organic two fontanels for silane (D).Wish that two organic two fontanels that generate are big as far as possible for the silane amount,, generate preparation room temperature vulcanizate compositions and the useful polydiorganosiloxane polymkeric substance of hot sulfurization rubber combination because this material can further react.Regrettably, utilize the Rochow direct method carry out organic fontanel for silane and two organic two fontanels in shortage for silane, in addition, also generate other by product, for example polysilane resistates and contain the hydrogen of silane monomer.Therefore, people continue to seek make two organic two fontanels for silane output maximum, make organic three fontanels some Catalyst And Methods for silane and other by product minimum that in the reaction of Rochow direct method, generates.

People such as Rochow are at United States Patent (USP) the 2nd, 383, disclose in No. 818, do not use elemental copper, and use the oxide compound of copper can increase the reactivity of material, so that two organic two fontanels are increased for the productive rate of silane.But should be noted that the oxide catalyst Alloy instead of Copper catalyzer that uses copper, organic three fontanels are reduced for the ratio between the silane for silane and two organic two fontanels.

In No. the 2nd, 464,033, the United States Patent (USP) of Gilliam, show, when using copper catalyst, use zinc simultaneously, make two organic two fontanels be able to further raising for the production rate of silane.Though this zinc promotor only makes speed of response that a small amount of increase is arranged,, thereby two organic two fontanels are significantly increased for silane quantity because the selectivity of this reaction improves.

Rossmy is at United States Patent (USP) the 3rd, 069, disclosed a kind of new copper catalyzer of two organic two fontanels of direct method for the silane productive rate that be used to improve in No. 452.In general, the catalyzer of Rossmy is a kind of brittle, easy ground silicon-copper alloy, and silicone content wherein can change in the 1-50% scope by weight.The efficient of this catalyzer improves such as promotor such as aluminium or zinc because of using.

People such as Petrov at " organosilane monomer synthetic " [through the English version of original author's approval, be translated from Russian, translator: C.N.Turton and T.I.Turton, consulting office (1964)] report in the book and say, though it is found that copper is best catalyzer, but in silicon or in silicon-copper mixture, add silver, aluminium, zinc, nickel, cobalt, iron and other than the bigger metal of the positive polarity of silicon after, this direct method also is accelerated.But according to people's such as Petrov viewpoint, these elements do not have independent value generally speaking, and they can only improve the character of silicon-copper mixture to a certain extent.People such as Petrov point out that also trace-metal has very big influence for the activity of contact mixture, and these metalloids such as the lead of trace, tin and bismuth for example are even content minimum (0.01 to 0.005%) also can obviously reduce the activity of silicon-copper alloy.

Bazant is in " organic fontanel is directly synthetic for silane " (Czechoslovakia, Prague, Ceskoslovenska Akademie Ved, chemical process principle institute, 1965) determine in the book, in direct method, elemental copper and the same catalyzer that plays a part in other catalyzed reaction.Bazant also discloses, this form that copper imports in the contact substance is not significant, if suggestion can influence this method as the filler that joins in the contact substance of promotor, these fillers can reduce the transformation efficiency of dimethyl dichloro-silane so.The most effective material that mixes is an aluminium, and small amount of aluminum (being up to 1%) increases overall reaction rate.As if Bazant also points out, adds the small amount of impurities filler in the silicon crystal lattice, have decisive influence for the activity of this contact substance.

Eaborn and Bott are entitled as at one piece in " silicon-carbon bond synthetic with reaction " and have summed up the argument in the prior art, point out a lot of researchists' the mutual contradiction of conclusion.These two authors also declare, it is to change catalyzer that the reaction conditions of original direct method is proposed to improve maximum aspects.These improvement comprise and change method prepare silicon-copper contact substance, add metal outside promotor, the use copper as catalyzer or do not use catalyzer in catalyzer.Change the method for preparing contact substance, perhaps change trace impurity content in copper or the silicon (often not having to determine or do not mention) for this point, also can this speed of reaction of remarkably influenced and selectivity.Based on this, Eaborn and Bott conclude that identical even staff also often is difficult to reappear these results.Another difficulty of noticing is that the effect of promotor is because of the preparation method of contact substance and the contaminant characteristics considerable change of existence.And copper-silicon alloy usually is subjected to different influences with copper-silicon mixture.

No. the 4th, 218,387, people's such as Maas United States Patent (USP) is to confirm that Eaborn and Bott conclusion change the good illustration that the method that prepare catalyzer has remarkable influence to reactivity and selectivity one by one.People such as Maas find, in less than air under the condition of oxygen partial pressure, are after the Red copper oxide with the dioxygen oxidation elemental copper, make the catalytic activity raising of catalyzer.

People such as Radosavlyevich find, in the presence of cuprous chloride, after in the contact substance that generates by Powdered silicon and methyl chloride reaction, adding trace silver, reduced the productive rate of methylchlorosilanes, and tin and calcium chloride have increased the speed that generates methylchlorosilanes, this situation and " some filler verify direct synthesizing methyl chloro silane with the active influence of contact substance " literary composition (Yugoslavia, Belgrade, inorganic chemistry research institute, 1965) middle report identical.

R.Voorhoeve points out that in " organic fontanel is for the precursor of silane-polysiloxane " (Holland, Amsterdam, Elsevier publishing company) book the experimental result that obtains with direct method is seldom consistent, and reproducibility is poor.Voorhoeve says, the reason of failure still is a mystery, but one of several greatest problem that this may existence when directly synthetic are relevant, promptly relevant with the influence of impurity.Though relevant research is not rare, these researchs almost all are confined to not the accurately silicon and the copper of finite-state.As if one of discovery of Voorheve is the iron that exists in silicon-copper contact substance, even its amount quite big (up to 5%) only has very little influence for the reaction with methyl chloride.Voorhoeve also discusses, and the influence of tin is indefinite; Though once reported its not influence, and studies have shown that afterwards in the used alloy to have antimony, so these results be not conclusive.Voorhoeve notices that further iron has injurious effects to selectivity, although this influence is usually very little, usually is difficult to perceive.

The applicant thinks, the result that this class can not be foretold is owing to some contained impurity in the normally used sedimentary tough-pitch copper catalyzer (i.e. the copper that obtains from the leach liquor removal process) in this direct method cause, so set about preparing synthetic copper catalyst composition, with the shortcoming of avoiding existing in the prior art.At first definite, the copper of use should be electrolysis level copper, so that the foreign matter content that makes to organic fontanelle compound and elemental silicon reaction may have harmful effect is reduced to minimum.Add impurity according to various combinations then, can provide highest response and optionally best matrix so that determine.It should be noted that, selectivity is meant organic three fontanel silane and the ratio (T/D) of organic two fontanels for silane, and the minimizing of other by product, so that make two organic two fontanels reach maximum for the productive rate of silane, the result is that this ratio is more little, and the selectivity of this method is strong more.In addition, the reactive or intrinsic speed of reaction that is shown by rate constant is defined as: by the gram number of per hour introducing the several silane that produce of Pure Silicon Metal gram in the reaction mixture.About above-mentioned T/D than and the going through of Kp value, can submission on July 28 nineteen eighty-three, application number is 518,236 the patent application of awaiting the reply jointly (applicant: find Ward etc.).

Except that proposing to have appropriate reaction and optionally the catalyst composition, the applicant sets about making organic fontanel to reduce to minimum for the high boiling residue content in the thick product flow of silane.Resistates can be defined as: the boiling point under the normal atmosphere that exists in thick methylchlorosilanes is higher than 70 ℃ product.Resistates by disilane class, sily oxide class, disilmethylene alkanes and such as three silicane and trisiloxanes class other more high boiling material like this some materials form.The typical content of the resistates that keeps in the processing method in prior art is approximately 10%(weight).Make resistates be reduced to minimum, can not only improve the monomer productive rate of direct method, but also reduce subsequently the processing requirements when disilane produces extra organic fontanel for silane.

In the prior art from the catalyzer of copper mine leach liquor preparation and produce organic fontanel for the shortcoming the silane method, people such as Ward have done similar test, find, contain silicon, copper catalyst, the contact substance that also contains tin and zinc promotor simultaneously, the Kp value is reached be approximately tin or zinc to help the twice of catalyst system, also improved selectivity simultaneously, make its selectivity surpass zinc or tin helps the catalytic Contact material.And the resistates of thick product is from about 10%(weight) be reduced to 1～2%(weight), see the patent application of awaiting the reply jointly that submit to July 28 nineteen eighty-three, applicant Ward etc., application number is 518,236.

The object of the invention is to provide a kind of copper catalyst with the electrolysis copper production that is used for reacting between catalytic elements silicon and the organic fontanel compound.

Another object of the present invention provides a kind of appointment composition of critical quantity or copper catalyst of impurity of containing, so that produce suitable speed of reaction and suitable selectivity, make simultaneously by elemental silicon and organic fontanel and be reduced to minimum for the resistates amount that reaction generated between the compound.

A further object of the present invention provide a kind of by organic fontanels such as elemental silicon and for example methyl chlorides for compound, prepare the method for organic chlorosilane.

According to foregoing invention purpose and other purpose of reflecting when of the present invention by following detailed description, by the invention provides a kind of copper catalyst composition of forming by following material substantially:

(a) Cu ⁰, Cu ⁺And Cu ⁺⁺Mixture,

(b) about 200 to about 5000ppm tin or sn-containing compound, and (is the tin content of base in copper), and

(c) about 50 to about 5000ppm aluminium or aluminum contained compound (is the aluminium content of base in copper).

The Cu that is provided ⁺And Cu ⁺⁺, preferentially select monovalence copper and cupric oxide compound, fontanelle compound, carbonate or carboxylate salt or its mixture for use.The fontanelle compound example that is suitable for has fluorochemical, muriate, bromide and iodide.The concrete carboxylate salt that is suitable for comprises formate, acetate and oxalate.Generally speaking, these carboxylate radicals should be vaporized under the service temperature of reactive material, and this service temperature will more discuss fully below.Usually, should not use the copper compound of sulfur-bearing hydrochlorate, sulphite, nitrate, nitrite, phosphoric acid salt or phosphite to prepare catalyzer of the present invention.But, under the condition that needn't do too much test, just can determine easily whether certain particular compound can be used among the catalyzer of the present invention by those skilled in the art.The catalyst composition of the present invention that override is selected for use, form by following material basically:

(a) Cu ⁰, Cu ₂The mixture of O and CuO,

(b) about 200 to about 5000ppm tin, (is base in copper) and

(c) about 50 to about 5000ppm aluminium (is base in copper).

On the other hand, the invention provides a kind of method for preparing organic fontanel for silane, this method is included in the significant quantity catalyst composition of being made up of following material basically and exists down, makes the organic fontanel of methyl chloride and so on for reacting between compound and the powdery metal silicon in reactor:

(a) Cu ⁰, Cu ⁺And Cu ⁺⁺Mixture,

(b) about 200 to about 5000ppm tin, (is base in copper) and

(c) about 50 to about 5000ppm aluminium (is base in copper).

In the copper catalyst of the present invention, except that containing tin and aluminum cocatalyst, iron and zinc can also be contained, but the lead of poisonous substance effect must be substantially devoid of.

Especially preferentially select for use and implement the inventive method in a continuous manner in fluidized-bed reactor, what have catalyzer in this fluidized-bed reactor contains silicon materials from wherein being eluriated out, and can make it to circulate again.Calculate according to the silicon materials feed rate, this method makes productive rate increase to maximum.

Can use methyl chloride or argon gas and so on rare gas element or its mixture contains or do not contain silicon particle layer fluidization in this reactor of catalyzer.Be present in the silicon particle size in this fluidized-bed, can be less than 700 microns, its particle size average greater than 20 microns, less than 300 microns.The mean diameter of this silicon particle preferably is between 100 to 150 microns.

One aspect of the present invention provides a kind of catalyst composition of being made up of following composition basically:

(a) Cu ⁰, Cu ⁺And Cu ⁺⁺Mixture,

(c) about 50 to about 5000ppm aluminium or aluminum contained compound (is the aluminium content of base in copper)

The cuprous ion source is an example with following compound: cuprous fluoride, cuprous chloride, cuprous bromide, Red copper oxide, cuprous carbonate, cuprous acetate and oxalic acid are cuprous.The example in cupric ion source has cupric chloride, cupric fluoride, cupric bromide, cupric oxide, copper carbonate, Tubercuprose, venus crystals and cupric oxalate.The source that other of cupric ion and cuprous ion is suitable for can be found by those skilled in the art under the condition of not doing too much test.What override was selected for use is to provide Cu with the Red copper oxide form ⁺, provide Cu with the cupric oxide form ⁺⁺Certainly, any mixture of above-claimed cpd can use and without prejudice to literal of the present invention and spirit.Be clear that from above-mentioned explanation the catalyst composition of the present invention that override is selected for use is made up of following composition basically:

(a) Cu ⁰, Cu ₂The mixture of O and CuO,

This copper catalyst composition can also comprise up to approximately 7500ppm iron or iron containing compounds (is the iron level of base in copper) and with respect to every part of copper amount from about 0.01 to 0.5 part of zinc.The important point is, this catalyst composition should not comprise the lead of poisonous substance effect substantially.What is called is not leaded substantially to be meant that lead content is as far as possible little, and is no more than 2000ppm lead (is base in copper).Be to be understood that unless otherwise indicated, all umber all is meant parts by weight.Therefore, for example (is base in copper) 1000ppm metal or contain certain metallic compound is meant to contain 1000 parts of these metals of weight in per 1,000,000 parts of weight copper.

Another aspect of the present invention provides a kind of method for preparing organic fontanel for silane, the above-mentioned copper catalyst composition that this method is included in significant quantity exists down, in reactor, make organic fontanel for reacting between compound (preferentially select for use fontanel for alkane, override is selected methyl chloride for use) and the Powdered elemental silicon.

Copper exists with the form of mixtures of free or elemental copper, monovalence copper compound and cupric compound, and the content in contact substance is about 0.1% to about 10%(weight).The further preferred content of this copper mixture is about 0.5% to about 5.0%(weight in the contact substance).In typical case, elemental copper account for this copper mixture weight about 5% to about 20%, the monovalence copper compound account for this copper mixture weight about 25% to about 60%, cupric compound accounts for about 25% to about 50% of this mixture weight.Under further preferred condition, elemental copper content is about 14% to about 18%(weight), the monovalence copper compound is about 39% to about 50%(weight), cupric compound is about 35% to about 43(weight) %.

In the concrete catalyzer that override of the present invention is selected for use, the mixture of elemental copper, Red copper oxide and cupric oxide is with the preparation of electrolysis level copper scale, so that the possibility that the impurity of reactive and selectivity variation will be existed is reduced to minimum.In preparation process, can be simply with making copper compound solution prepare the oxidized copper of this part by the method for iron filings, this method causes metallic copper to deposit out with the sedimentary form of particulate.Then, this precipitation is carried out pyrometallurgical smelting, make the copper oxidation.Other method for preparing copper compound of the present invention, be that those of skill in the art are known in the art, people's such as s United States Patent (USP) the 4th, 218 for example, those methods of being introduced in 387 mention that sincerely this patent No. is to be incorporated in its content in the present patent application.

In the copper source that can use when making catalyzer of the present invention, the example of the copper of a preferred partial oxidation can roughly be expressed as follows:

Composition weight %

Cu ⁰7-10%

Cu ₂O 50-52%

CuO 37-40%

Sn 200ppm(is base in copper)

Al 20ppm(is base in copper)

Fe 400ppm(is base in copper)

Pb 20ppm(is base in copper)

Insolubles about 0.05%

If do not prepare to use the copper of partial oxidation, before disposing, need only make monovalence copper compound and cupric compound thorough mixing so.The preparation of other monovalence copper compound of this class and cupric compound need not to discuss, because these materials can have been bought on market, perhaps is easy to be prepared by those of ordinary skill in this technical field.

The tin amount that exists in catalyzer of the present invention can be base in copper about 200 to about 5000ppm(by weight) in the scope.Though preferably should add tin with purity 99% the element tin form of being at least, for example add metallic tin powder by 325 orders (ASTM), also can be with fontanel tin, stannic oxide, tin tetramethide and so on alkylation tin and tin alkyl fontanelle compound form adding tin.Under the condition of not doing too much test, can determine other tin that is suitable for source.The most preferred scope that exists of metallic tin or sn-containing compound is for about 300 to about 1800ppm(being the tin content of base in copper).

Press the aluminium weight content and calculate, the scope that exists of aluminium or aluminum contained compound is about 50 to about 5000ppm.Preferentially select for use with element aluminum or with aluminum oxide (Al ₂O ₃) form adding aluminium, just can determine the aluminum compound that other is suitable for but need not too much test.In a preferred specific embodiments, it is the aluminium content of base in copper that aluminium or aluminum contained compound add-on are in from about 100 to about 2000ppm() within the scope.

Can choose the quantity that adds iron or iron containing compounds wantonly, calculate, be in from trace to about 7500ppm scope according to weight with respect to copper.

In addition, according to of the record of July 28 nineteen eighty-three, in catalyzer of the present invention, can also contain zinc or zinc compound by (its application number is 518,236) in the application of awaiting the reply jointly of people such as Ward proposition.Mention that sincerely this application number is also to merge to its content among the application.

When implementing the inventive method, under given pace, catalyzer of the present invention to be introduced in the reaction mixture, this speed is enough to keep catalyst reactor and has following average composition:

0.5-10%(weight) copper (Cu ⁰, Cu ⁺And Cu ⁺⁺) (is base in silicon),

200-5000ppm tin (is base in copper)

50-5000ppm aluminium (is base in copper), and optional composition trace is to 7500ppm iron (is the tin content of base in copper) and 0.01-0.5 part zinc/1 part of copper.

The silicon of Shi Yonging is that purity is at least 98%(weight usually in the methods of the invention) silicon, it is crushed to granularity less than 700 microns, mean particle size greater than 20 microns, less than 300 microns.The mean diameter of this silicon grain is preferentially selected for use and is in 100 to 150 micrometer ranges.Then when needed, will send in the appropriate reaction device through this particulate Si of pulverizing.Though the inventive method is preferentially selected fluidized-bed reactor for use, also can use other type of reactor, for example fixed-bed reactor and stirred bed reactor.Because when using fluidized-bed reactor, chlorosilane, particularly selectivity the best of two organic dichloro-silane, the output maximum is so preferentially select it for use.Can in 250-350 ℃ of scope, implement method of the present invention, but preferred temperature range is 260-330 ℃.Reaction can be carried out or periodical operation continuously.In case of necessity, can be with before methyl chloride contact, the contact substance that preparation is made up of Powdered silicon and copper-Xi-Al catalysts is beneficial to produce methylchlorosilanes.

When using fluidized-bed reactor, be preferably under the 1-10 atmospheric pressure and implement the inventive method, because under elevated pressures, the conversion rate that methyl chloride is converted into methylchlorosilanes increases.

Can make methyl chloride gas by reactor continuously,, and gaseous state methylchlorosilanes and unreacted methyl chloride are flowed out so that make the reactive material fluidization.This gasiform crude reaction product mixture and the reaction particles of being taken out of flow out from fluidized reactor, by one or more cyclonic separator, the larger particles material are separated from the product air-flow then.These particles with katalysis can be sent into this reactor again, in this process, further utilize in addition, so that make the productive rate of producing dimethyl dichloro-silane by silicon reach maximum.Less particle is purified and condensation this gaseous substance then along with product flow flows out.

The methyl chloride of heating through purifying, and the process fluidized-bed reactor circulates further production methylchlorosilanes.This thick methylchlorosilanes air-flow is fed in the Distallation systm, so that distill out the substantially pure fraction of the various chlorosilanes of being made by present method.Must distill and purify the dimethyl dichloro-silane that makes like this and other chlorosilane, can room temperature-vulcanized composition and the polysiloxane such as silicon rubber of baking so that for example can be used to produce.Those of skill in the art are familiar with being produced by elemental silicon the method for organic chlorosilane in this technical field, also understand the method for preparing silicon composition with this organic chlorosilane.

In order to make this technical field those of skill in the art can implement the present invention better, proposed the following example with illustrational mode, but be not limited to these.Unless otherwise indicated, all umber is all calculated by weight.

Embodiment 1

Prepare a kind of mechanical mixture, wherein contain 50 parts of chemical pure silica flours, 2.9 parts of sedimentable matter and 0.25 part of thin zinc powders that the oxide compound with copper is a major ingredient.The BET(cloth Shandong Nao E-Ai Meite-Taylor of silica flour) the specific surface area value is 0.5m ²/ g, its standard is composed as follows:

Composition ppm(by weight)

Aluminium 2800

Calcium 500

Iron 5000

Titanium 400

(all the other are the silicon that accounts for major ingredient).Sedimentable matter composed as follows:

Composition weight %

Cu ₂O 40.6

CuO 41.4

Free copper 14.5

Fe 0.69

Pb 0.11

Sn 0.42

Al 0.24

Si 0.95

(acid non-soluble substance that approximately contains 1% weight in this free-pouring powder, the mean particle size of this free flowing powder are approximately 5 microns, and its BET specific surface value is approximately 3m ²/ g).This mixture is added in the stainless steel stirred bed reactor of 1 inch of internal diameter, this temperature of reactor is controlled under 300 ℃, and make equimolar methyl chloride and dimethyl dichloro-silane vapour mixture stream by this reactor, make total through-put reach per hour 0.25 mole.After 1 hour, opening for feed is transferred on the methyl chloride gas source specially, it is suitable with the binary gas charging of using as the activation contact substance to make it mol ratio.Observed the methylchlorosilanes generation immediately, the Kp maximum value that records is approximately 45 Grams Per Hours gram silicon.Form with vapor-phase chromatography monitoring product, calculate according to the silicon material of initial adding, it is composed as follows that consumption silicon amount reaches the product that recorded at 43% o'clock:

Composition weight %

（CH ₃） ₂Si Cl ₂，D 77.68

CH ₃Si Cl ₃，T 7.94

（CH ₃） ₃Si Cl，M 3.08

CH ₃Si HCl ₂，MH 0.21

（CH ₃） ₂Si HCl，M ₂H 0.08

Resistates 10.66

Crude product T/D 0.102

Embodiment 2

Use 50 parts as the powdery metal silicon that uses among the embodiment 1, blended copper oxide catalyst and 0.25 part of zinc of 2.9 parts of copper, prepared second kind of mechanical mixture as using among the embodiment 1.This blended copper oxide catalyst is equipped with the electrolysis copper, and it is composed as follows:

Composition weight %

Cu ₂O 56.7

CuO 34.9

Free Cu 7.3

Fe 0.024

Pb 0.027

Sn 0.140

Al 0.0125

The Si trace

(it is believed that in this free-pouring powder having only trace substance is acid non-soluble substance, the mean particle size of this free flowing powder is approximately 4 microns, and its BET specific surface area is approximately 2m ²/ g).

Before oxidizing roasting, be bordering on preparation process mid-term, in purified relatively copper, on purpose add tin and aluminium.

This direct method generates the reaction of methylchlorosilanes, is to carry out according to the mode identical with embodiment 1.Record maximum Kp value and be approximately 38 Grams Per Hours gram silicon.The product that is equivalent to about 45% consumption silicon amount (calculating according to the silicon that begins to add) is composed as follows:

Composition weight %

（CH ₃） ₂Si Cl ₂，D 78.80

CH ₃Si Cl ₃，T 7.20

（CH ₃） ₃Si Cl，M 2.96

CH ₃Si HCl ₂，MH 0.37

（CH ₃） ₂Si HCl，M ₂H 0.07

Resistates 10.04

Crude product T/D 0.091

Thereby being designed to a kind of synthetic catalyst system, verified its performance is to natural, similar or better based on the copper oxide system of throw out.

Embodiment 3

Use as 50 parts of powdery metal silicon and 2.9 parts of blended copper oxide catalysts in embodiment 1 and 2, prepared the third mechanical mixture.This blended copper oxide is equipped with the electrolysis copper, and adds following trace-metal in initial copper melts:

Composition weight %

Fe 0.66

Sn 0.10

Al 0.21

Cu ₂The distribution situation of O, CuO and free copper and physicals (for example BET specific surface area and average granularity) are close with catalyzer in embodiment 1 and 2.As in embodiment 1 and 2, also adding in this contact substance mechanical mixture has 0.25 part of zinc powder.

This direct method generates the reaction of methylchlorosilanes, according to embodiment 1 and 2 in identical mode carry out.After measured, according to the silicon material calculating of initial adding, the following products that consumption silicon amount is equivalent to about 28% is formed, and its maximum Kp value is approximately 23 Grams Per Hours gram silicon:

Composition weight %

（CH ₃） ₂Si Cl ₂，D 80.97

CH ₃Si Cl ₃，T 8.22

（CH ₃） ₃Si Cl，M 2.19

CH ₃Si HCl ₂，MH 1.26

（CH ₃） ₂Si HCl，M ₂H 0.25

Resistates 6.9

Crude product T/D 0.102

Therefore, add Sn, Al and Fe in utilizing the contact substance of zinc, make the ratio of Cu/Zn and other trace-metal remain in the stated limit, this synthesizing formula causes required clean product composition to be increased.

Claims

1, a kind of method for preparing organic fontanel for silane is characterized in that, in the presence of the significant quantity catalyzer of being made up of following composition, makes organic fontanel for compound and Powdered pasc reaction, and said catalyzer is made up of following composition basically:

(a) Cu ⁰, Cu ⁺And Cu ⁺⁺Mixture,

(b) about 200 to about 5000ppm tin or aluminum contained compound (is the tin content of base with copper),

(c) about 50 to about 5000ppm aluminium or aluminum contained compound (is the aluminium content of base with copper)

2, in accordance with the method for claim 1, wherein said catalyzer is made up of following composition basically:

(a) Cu ^o, Cu ₂The mixture of O and CuO,

(b) about 200 to about 5000ppm tin or sn-containing compound (is the tin content of base with copper), and

3, in accordance with the method for claim 1, Cu wherein ⁺And Cu ⁺⁺Use with compound form, said compound is selected for use in one group of material that fontanelle compound, carbonate and carboxylate salt and composition thereof are formed by monovalence copper and cupric oxide compound.

4, in accordance with the method for claim 1, wherein elemental copper accounts for about 5% to about 20% of this catalyst weight, the monovalence copper compound account for this catalyst weight about 25% to about 60%, cupric compound accounts for about 25% to about 50% of this catalyst weight.

5, according to claim 1 or 2 described methods, wherein said catalyzer also contains basically and is up to about 7500ppm iron or iron containing compounds (is the iron level of base with copper)

6, according to claim 1 or 2 described methods, wherein said catalyzer calculates according to the zinc in every part of copper, also contains about 0.01 basically to about 0.5 part of zinc or zinc compound.

7, in accordance with the method for claim 5, wherein said catalyzer calculates according to the zinc in every part of copper and also contains about 0.01 basically to about 0.5 part of zinc or zinc compound.

8, according to claim 1 or 2 described methods, wherein said catalyzer is substantially free of lead.

9, according to claim 1 or 2 described methods, the content of wherein said catalyzer in contact substance is about 0.1% to about 10%(weight).

10, according to claim 1 or 2 described methods, the content of wherein said catalyzer in contact substance is about 0.5 to about 5.0%(weight).

11, in accordance with the method for claim 2, wherein said elemental copper account for this catalyst weight about 5% to about 20%, Red copper oxide account for this catalyst weight about 25% to about 60%, cupric oxide accounts for about 25% to about 50% of this catalyst weight.

12, in accordance with the method for claim 2, wherein said elemental copper account for this catalyst weight about 14% to about 18%, Red copper oxide account for this catalyst weight about 39% to about 50%, cupric oxide accounts for about 35% to about 43% of this catalyst weight.

13, in accordance with the method for claim 2, wherein the copper of the partial oxidation in the catalyzer with highly purified electrolysis level copper scale preparation basically.

14, in accordance with the method for claim 13, wherein the copper of partial oxidation is to use the compound solution with copper to pass through on iron filings, forming fine precipitation, and with the pyrometallurgical method partial oxidation should precipitation in the method preparation of copper.

15, according to claim 1 or 2 described methods, wherein said organic fontanel is a methyl chloride for compound.

16, according to claim 1 or 2 described methods, the operate continuously in fluidized-bed reactor of this method is implemented.

17, according to claim 1 or 2 described methods, this method is implemented in stirred bed reactor.

18, according to claim 1 or 2 described methods, this method is implemented in fixed-bed reactor.

19, according to claim 1 or 2 described methods, this method is operated with intermittent mode.

20, according to claim 1 or 2 described methods, this method is to implement under certain temperature in 250～350 ℃ of temperature ranges.

21, according to claim 1 or 2 described methods, wherein use the source of metallic tin powder as tin in the catalyzer.

22, according to claim 1 or 2 described methods, wherein use metallic aluminium powder or aluminum oxide powder source as aluminium in the catalyzer.

23, a kind of method for preparing methylchlorosilanes, it is characterized in that, this method can improve the formation speed of dimethyl dichloro-silane, reduce the weight ratio between methyl three chloro silane and the dimethyl dichloro-silane simultaneously, keep or reduce in the thick product of methylchlorosilanes that generates the weight percentage that under barometric point boiling point is higher than 70 ℃ product, this method comprises:

In the presence of the significant quantity catalyzer of forming by following composition basically, in reactor, make methyl chloride and Powdered pasc reaction:

(a) by about 5% to about 20%(weight) element copper catalyst, about 25% is to about 60%(weight) cuprous oxide catalysis agent and about 25% is to about 50%(weight) mixture formed of copper oxide catalyst,

(b) about 200 to about 5000ppm tin or sn-containing compound (is the tin content of base in copper), and

(c) about 50 to about 5000ppm aluminium or aluminum contained compound (is the aluminium content of base in copper),

(d) be up to about 7500ppm iron or iron containing compounds (is the iron level of base in copper), and

(e) calculate according to every part of contained zinc of copper, 0.01 to 0.5 part of zinc or the wherein said catalyzer of zinc compound, be in that to be enough to keep catalyst reactor content be about 0.1 to about 10%(weight) catalyzer one this speed of silicon contact substance under, be admitted to Powdered silicon, wherein said reaction is to carry out under certain temperature in 250～350 ℃ of scopes.

24, a kind of Powdered silicon-copper catalyst contact substance is characterized in that, this contact substance is mainly by 0.1～10%(weight) copper catalyst form, said copper catalyst mainly is made up of following composition:

(a) Cu ⁰, Cu ⁺And Cu ⁺⁺Mixture,

(b) about 200 to about 5000ppm tin or sn-containing compound (is the tin content of base in copper),

25, according to the described contact substance of claim 24, wherein said Cu ⁺And Cu ⁺⁺Use with compound form, said compound is selected for use in one group of material that fontanelle compound, carbonate and carboxylate salt and composition thereof are formed from by monovalence copper and cupric oxide compound.

26, according to the described contact substance of claim 24, wherein elemental copper accounts for about 5% to about 20% of its catalyst weight, the monovalence copper compound account for its catalyst weight about 25% to about 60%, cupric compound accounts for about 25% to about 50% of its catalyst weight.

27,, wherein also contain basically and be up to 7500ppm iron or iron containing compounds (is the iron level of base in copper) according to the described contact substance of claim 24.

28,, wherein also contain about 0.1 basically to about 0.5 part of zinc or zinc compound (calculating) by the zinc in every part of copper according to the described contact substance of claim 24.

29, according to the described contact substance of claim 24, wherein said copper basically by from about 5% to about 20%(weight) elemental copper, from about 25% to about 60%(weight) Red copper oxide from about 25% to about 50%(weight) cupric oxide forms.

30, a kind of catalyst composition is characterized in that, this catalyst composition is made up of following composition basically:

(a) Cu ⁰, Cu ⁺And Cu ⁺⁺Mixture,

31, according to the described composition of claim 30, this catalyst composition is made up of following composition basically:

(a) Cu ⁰, Cu ₂The mixture of O and CuO,

(b) about 200 to about 5000ppm tin (is base in copper), and

(c) about 50 to about 5000ppm aluminium (is base in copper).

32, according to the described composition of claim 30, wherein Cu ⁺And Cu ⁺⁺Use with compound form, said compound is selected for use in one group of material that fontanelle compound, carbonate and carboxylate salt and composition thereof are formed from by monovalence copper and cupric oxide compound.

33, according to the described composition of claim 30, wherein elemental copper accounts for about 5% to about 20% of said composition weight, the monovalence copper compound account for said composition weight about 25% to about 60%, cupric compound accounts for about 25% to about 50% of said composition weight.

34,, wherein also contain basically and be up to 7500ppm iron or iron containing compounds (is the iron level of base in copper) according to claim 30 or 31 described compositions.

35,, wherein also contain about 0.01 basically to about 0.5 part of zinc or zinc compound (calculating) by the zinc in every part of copper according to claim 30 or 31 described compositions.

36,, wherein also contain basically from about 0.01 to about 0.5 part of zinc or zinc compound (calculating) by the zinc every part of copper according to the described composition of claim 34.

37, according to the described composition of claim 31, wherein elemental copper account for said composition weight about 5% to about 20%, Red copper oxide account for said composition weight about 25% to about 60%, cupric oxide accounts for about 25% to about 50% of said composition weight.

38, according to the described composition of claim 31, wherein elemental copper account for said composition weight about 14% to about 18%, Red copper oxide account for said composition weight about 39% to about 50%, cupric oxide accounts for about 35% to about 43% of said composition weight.