JPH0480740B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a catalyst composition for producing organohalogensilane by reacting powdered silicon metal and an organohalogen compound. In particular, the present invention provides a method for reacting powdered silicon metal with an organohalide, preferably an alkyl halide such as methyl chloride, in the presence of a copper catalyst composition and such catalyst containing critical amounts of tin, aluminum, iron and zinc. The present invention relates to a method for producing organohalogensilanes, preferably methylchlorosilanes.

Prior Art Prior to the present invention, it was known that alkylhalosilanes could be prepared by directly reacting an organic chloride with elemental silicon in the presence of a copper catalyst, as described, for example, in Rochow, U.S. Pat. No. 2,380,995. It is well known as described in . In fact, this reaction
in a stirred bed reactor of the type described in U.S. Pat. No. 2,449,821 to Sellers et al., in a fluidized bed reactor of the type described in U.S. Pat. No. 2,389,931 to Reed et al., or in a rotary kiln. Usually done. Generally, this reaction is carried out by passing the organic halide in vapor form over the surface of powdered silicon metal and maintaining the reaction mixture at an elevated temperature. Typically, elemental silicon is mixed with finely divided copper powder, as described in the Rochow patent. Here, copper acts as a catalyst for the reaction between organic halide and silicon.

In the production of organohalosilanes by the direct method proposed by Rochow, two main reaction products are obtained: organotrihalosilane T and diorganodihalosilane D. It is preferable to generate as much diorganodihalosilane as possible. The diorganodihalosilanes can be further reacted to produce polydiorganosiloxane polymers useful in making room temperature vulcanizable and thermosetting rubber compositions. However, the reaction of organic halides with elemental silicon using Rochow's direct method has the disadvantage of producing an excess of organotrihalosilane and an insufficient amount of diorganohalosilane. Furthermore, other by-products,
For example, polysilane residues and hydrogen-containing monomeric silanes are also produced. Therefore, there has been a continuing need for catalysts and methods that maximize the production of diorganodihalosilanes and minimize the production of organotrihalosilanes and other by-products in Rochow's direct reaction. .

Rochow et al. teach in US Pat. No. 2,383,818 that the use of copper oxide rather than elemental copper can increase the reactivity of the reaction mixture and give higher yields of diorganodihalosilanes. However, it should be noted that by substituting a copper oxide catalyst for a copper catalyst, the ratio of organotrihalosilane to diorganodihalosilane is not necessarily reduced.

Gilliam, US Pat. No. 2,464,033, states that the yield of diorganodihalosilanes can be further improved when zinc is used in combination with a copper catalyst. Although such zinc promoters provide only a small increase in reaction rate, they improve the selectivity of the reaction and can therefore significantly increase the yield of diorganodihalosilanes.

US Pat. No. 3,069,452 to Rossmy discloses a new type of copper catalyst that improves the yield of diorganodihalosilanes in direct processes. Generally, Rossmy's catalyst is a brittle, easily grindable silicone compound with a silicon content that can vary from 1 to 50% by weight.
It is a copper alloy. The efficiency of this catalyst is improved by using promoters such as aluminum or zinc.

Petrov et al. “Synthesis of Organosilicon Monomers”
Monomers)”, C.N. Turton and T.
CNTurton and TITurton, Consultants
Copper was found to be the best catalyst, but the direct method also applied silver, aluminum, zinc, nickel, cobalt to silicon or silicon-copper mixtures (1964)). reported that addition of other metals that are more electropositive than iron and silicon also promotes this effect. However, according to Petrov et al., these elements are generally of no value on their own and merely improve the properties of the silicon-copper mixture to some extent. Petrov et al. also show that trace amounts of metals have a significant effect on the activity of contact mixtures, e.g. trace amounts of metals such as lead, tin and bismuth can be present even in very small amounts, e.g. 0.01-0.005%. , teaches significantly reducing the activity of silicon-copper alloys.

Bazant is a “Direct Synthesis of Organohalogen Silanes”.
organohalogensilanes)”institute
Institute of Chemical Process Fundamentals, Ciekoslovak Academy of Sciences, Plug, Ciekoslovakia.
of Chemical Process Fundamentals,
Czechoslovak Academy of Sciences, Prague;
Czechoslovakia (1965)) confirmed that elemental copper acts as a catalyst in the direct method in the same sense as in other catalytic reactions.
Furthermore, Bazant states that the form in which copper is introduced into the contact mass does not have any significant effect, and that the formulation into the contact mass recommended as an accelerator does not affect the intended method. If so, they are said to reduce the conversion to dimethyldichlorosilane. A very effective ingredient is aluminum, the inclusion of small amounts (up to 1%) increases the overall reaction rate.

Bazant further reports that the inclusion of small amounts of impurities incorporated into the silicon lattice appears to have a decisive influence on the activity of the contact aggregates.

Eaborn and Bott
“Synthesis and Reactions of Silicon-Carbon Bonds”
Bond) summarizes the prior art and points out the contradictory results of a number of researchers. It has been reported that most of the improved techniques involved changes in the catalyst. or involve the use of metals other than copper not as catalysts at all; changes in the manufacturing method of contact aggregates or the amount of trace impurities in the copper or silicon (which are often not measured or stated). Variations in can also have a significant effect on the reaction rate and selectivity of the reaction.
Bott concludes that results are often difficult to reproduce, even when done by the same researcher. Another difficulty recognized was that the effectiveness of promoters varied significantly depending on the method of preparation of the contact mass and the type of impurities present. Furthermore, copper-silicon alloy and copper-
Silicon mixtures often have different effects.

U.S. Pat. No. 4,218,387 to Maas et al. is a typical example supporting the conclusion of Eaborn and Bott that changes in catalyst preparation have a significant effect on reactivity and selectivity. Maas et al. found that increased catalytic reactivity was obtained when the oxidation of elemental copper to cuprous oxide was carried out using a lower partial pressure of oxygen compared to the oxygen partial pressure of air. .

Radosavlyevich et al.
“Influence of Some Admixtures on the activity of catalyst assemblies for the direct synthesis of methylchlorosilanes”
Activity of Cantact Masses for Direct
Synthesis of Methylchlorosilanes”, Institute of Inorganic Chemistry, Belgrade, Yugoslavia.
of Inorganic Chemistry, Belgrade;
Yugoslavia (1965)), the addition of a small amount of silver to the contact mass obtained by reacting powdered silicon and methyl chloride in the presence of cuprous chloride increases the yield of methylchlorosilanes. It was found that tin and calcium chloride increased the production rate of methylchlorosilanes, whereas tin and calcium chloride decreased the production rate of methylchlorosilanes.

R.Voorhoeve is
“Organohalosilanes-Precursors to silicones
Silicones)”, Elsevier Publishing Company, Amsterdam, Netherlands (Elsevier
Publishing Company, Amsterdam;
(Netherlands) pointed out that experimental results using direct methods rarely agree with each other and reproducibility is extremely poor. Voorhoeve notes that the cause of the failure remains a mystery, but it is probably related to one of the biggest problems with direct synthesis: the effects of impurities. Although there have been a number of related studies, they have been almost entirely confined to silicon and copper, which exist in imprecisely defined states. Voorhoeve notes that one finding in his research is that the presence of iron in silicon-copper contact mixtures, even when present in fairly high amounts (up to 5%), has a slight effect on the reaction with methyl chloride. states that it appears to be only.
Voorhoeve also reports that the effectiveness of tin is uncertain. Although tin was reported to be ineffective, subsequent studies showed the presence of antimony in the alloy used, so the results were inconclusive. Voorhoeve further acknowledges that iron often has only a small, imperceptible, deleterious effect on selectivity.

We have determined that such unpredictable results are due to impurities contained in the precipitated natural copper commonly used in direct processes (i.e., copper derived from leachate recovery processes), and we It is intended to provide a synthetic copper catalyst composition that avoids the disadvantages of. First, it was determined that the copper used should be copper, such as in the electrolyte, to minimize the possibility of impurities that would adversely affect the reaction between the organohalide and elemental silicon. Impurities are then added in various combinations to determine the optimal matrix to give maximum reactivity and selectivity.
Selectivity is the ratio of organotrihalosilanes to diorganodihalosilanes (T/D) and maximizes the yield of diorganodihalosilanes while minimizing other by-products, i.e. It should be noted that the lower the ratio, the higher the selectivity of the process. The reactivity or inherent reaction rate, as indicated by the rate constant, is also defined as the number of grams of silane formed per number of grams of silicon metal introduced into the reaction mixture per hour. For a more detailed explanation of the selectivity T/D and Kp values mentioned above, see Ward et al., US Patent Application SN 518,236, filed July 28, 1983.

In addition to providing a catalyst composition with suitable reactivity and selectivity, the present invention is intended to minimize the high boiling residue content of the organohalosilane crude product stream. Residue is defined as the product in the methylchlorosilane crude product with an atmospheric pressure boiling point above 70°C. The residue consists of materials such as disilanes, disiloxanes, disylmethylenes and other higher boiling components such as trisilanes and trisiloxanes. The amount of residue remaining in prior art processes was typically about 10% by weight. Minimizing the amount of residue not only increases the yield of monomeric product in the direct process, but also reduces the need for a subsequent step to produce additional amounts of organohalosilane from the disilane. .

In a similar attempt to circumvent the drawbacks of prior art catalysts and organohalosilanes production processes made from copper ore leaches, Ward et al.
A contact assembly comprising a silicon, copper catalyst and a mixture of tin and zinc promoters gives a Kp value about twice that given by a system containing a tin promoter or a system containing a zinc promoter;
It has also been recognized that it simultaneously provides improved selectivity over contact assemblies containing zinc or tin promoters.
Additionally, the residue content of the crude product ranges from about 10% by weight to 1% by weight.
It decreased to a low level of ~2% by weight.

SUMMARY OF THE INVENTION One object of the present invention is to provide a copper catalyst from electrolytic grade copper useful as a catalyst for the reaction of elemental silicon and organohalogen compounds.

It is another object of the present invention to contain critical amounts of certain components or impurities to provide suitable reaction rates and suitable selectivities while minimizing residues resulting from the reaction of elemental silicon with organohalogen compounds. To provide a copper catalyst containing.

Yet another object of the present invention is to provide a method for producing organohalosilanes, such as organochlorosilane, from elemental silicon and organohalogen compounds, such as methyl chloride.

In accordance with the above objects and other objects which will become apparent from the detailed description of the invention set forth below, the invention consists essentially of: (a) a mixture of Cu°, Cu ₂ O and CuO; (b) about 200 to about 5000 ppm tin to copper; and (c) about 50 to about 5000 ppm aluminum to copper.

The present invention further provides that an organohalogen compound, such as methyl chloride, and powdered silicon metal are combined in a reactor with the following components consisting essentially of: (a) a mixture of Cu°, Cu ₂ O and CuO; (b) copper. (c) about 50 to about 5000 ppm aluminum relative to copper; and (c) about 50 to about 5000 ppm aluminum relative to copper. It provides:

In addition to tin and aluminum promoters, the copper catalyst of the present invention may contain iron and zinc, but the catalyst must be substantially free of lead, which acts as a catalyst poison.

It is particularly preferred to carry out the process of the invention in a fluidized bed reactor in a continuous manner by elutriating the catalyst-containing silicon-containing material from the reactor and recycling it. This method helps maximize yield based on silicon material feed.

An inert gas such as methyl chloride or argon or mixtures thereof can be used to fluidize the bed of silicon particles with or without catalyst material in the reactor. The silicon present in the fluidized bed is 700
It can have a particle size of less than a micron and has an average particle size of greater than 20 microns and less than 300 microns. Preferably, the average diameter of the silicon particles is in the range of 100-150 microns.

DETAILED DISCLOSURE OF THE INVENTION According to one form of the invention, the following components consist essentially of: (a) a mixture of Cu°, Cu ₂ O and CuO; about
5000 ppm of tin or tin-containing compounds; and (c) approximately 50 ppm, calculated as aluminum relative to copper.
A copper catalyst composition is provided comprising: ~5000 ppm of aluminum or an aluminum-containing compound.

Such copper catalyst compositions may further contain up to about 7500 ppm iron or iron-containing compounds, calculated as iron to copper, and about 0.01 to 0.5 parts zinc per part copper. It is important that the catalyst composition of the present invention is substantially free of lead, which acts as a catalyst poison. Substantially free of lead means containing as little lead as possible, and not exceeding 2000 ppm based on copper.

According to another aspect of the invention, an organohalogen compound, preferably an alkyl halide, most preferably methyl chloride, and powdered elemental silicon metal are combined in a reactor in the presence of an effective amount of a copper catalyst composition as described above. A method for producing organohalosilanes, particularly methylchlorosilanes, is provided, comprising reacting:

Copper is in the form of free or elemental copper, a mixture of cuprous oxide and cupric oxide and about
Constituting 0.1 to about 10% by weight. More preferably,
Such copper mixture comprises about 0.5% to about 5.0% by weight of the contact mass. Typically, elemental copper comprises from about 5 to about 20% by weight of the copper mixture, cuprous oxide comprises from about 25 to about 60% by weight of the copper mixture, and cupric oxide comprises from about 25 to about 60% by weight of the copper mixture. Comprising about 25 to about 50% by weight. More preferably, elemental copper ranges from about 14 to about 18% by weight, cuprous oxide ranges from about 39 to about 50% by weight, and cupric oxide ranges from about 35 to about 43% by weight. range.

Ideally, the mixture of elemental copper, cuprous oxide and cupric oxide is used to minimize any impurities that may be present that could adversely affect reactivity or selectivity in the catalytic reaction step. Manufactured from electrolytic grade copper scrap. Briefly, in the case of recovery methods, such partially oxidized copper is produced by passing a solution of copper compounds over scrap iron to precipitate metallic copper in the form of a fine precipitate. can do. This precipitate is then treated by thermometallurgical methods to cause oxidation of the copper.

Other methods for making the copper mixtures of the present invention are well known to those skilled in the art and are described in, for example, Maas et al., US Pat. No. 4,218,387.

One preferred example of partially oxidized copper that can be used as a source of copper in the production of the catalyst of the present invention is generally characterized by the following composition.

Component weight% Cu゜ 7-10% Cu ₂ O 50-52% CuO 37-40% Sn 200ppm relative to copper Al 20ppm relative to copper Fe 400ppm relative to copper Pb 20ppm relative to copper Insoluble components Approximately 0.05% The amount of tin present in the catalyst of the present invention can range from about 200 to about 5000 ppm relative to copper.

Tin is preferably added as elemental tin of at least 99% purity, e.g. as -325 mesh tin metal fine powder, but may also be added as tin halides, tin oxides, alkylated tin, such as tetramethyltin and alkyltin halides. It can also be added in the form of

Other suitable tin sources can be determined without undue experimentation. Tin metal or tin-containing compounds are approximately 300~ calculated as tin to copper.
It is also preferred that it be present in a range of about 1800 ppm.

The aluminum or aluminum-containing compound is present in an amount ranging from about 50 to about 5000 ppm, calculated as aluminum. Aluminum is preferably added as elemental aluminum or aluminum oxide (Al ₂ O ₃ ), although other suitable aluminum compounds may be used to determine their suitability without undue experimentation. According to a more preferred embodiment, the aluminum or aluminum-containing compound has an aluminum content of from about 100 to
It is added in an amount in the range of about 2000 ppm.

Iron or iron-containing compounds may optionally be added in amounts ranging from trace amounts up to 7500 ppm relative to copper.

Additionally, zinc or zinc-containing compounds may also be incorporated into the catalyst of the present invention in accordance with the teachings of Ward et al., US Patent Application No. 518,236, cited above.

In carrying out the process of the invention, the catalyst of the invention contains 0.5 to 10% by weight of copper to silicon, 200 to 5000 ppm tin to copper, 50 to 5000 ppm tin to copper.
from 0.01 per part of iron and copper from trace amounts up to 7500 ppm for aluminum and optionally copper
The catalyst is introduced into the reaction mixture at a rate sufficient to maintain the catalyst in the reactor with an average composition of 0.5 parts of zinc.

The silicon used in the process of the invention is usually obtained with a silicon purity of at least 98% by weight, which then has a particle size of less than 700 microns and an average particle size of less than 700 microns.
Grinded into silicon fine particles that are 20 microns to 300 microns. Preferably, the average particle size of the silicon particles is in the range of 100 to 150 microns. The ground silicon particles are then fed into a suitable reactor as required. Although fluidized bed reactors are preferred, the process of the invention may also be carried out in other types of reactors such as fixed bed and stirred bed types. It is preferred to use a fluidized bed reactor since it provides optimum selectivity and maximum yields of chlorosilanes, especially diorganodichlorosilanes. The process of the invention can be carried out at temperatures in the range 250-350<0>C, more preferably in the range 260-330<0>C. The reaction can occur under continuous conditions or as a batch reaction. If desired,
A contact mass of powdered silicon and copper-tin-aluminum catalyst can be formed prior to contact with methyl chloride to promote the formation of methylchlorosilanes.

When the process of the present invention is carried out using a fluidized bed reactor, the conversion of methyl chloride to methylchlorosilane is increased by using a higher pressure.
It is advantageous to carry out the reaction under a pressure of 10 atmospheres.

Methyl chloride gas can be passed continuously to the reactor to fluidize the reaction mixture and gaseous methylchlorosilanes and unreacted methyl chloride can be continuously removed from the reactor.
The gaseous crude product mixture and entrained reactant fines are removed from the fluidized bed reactor and passed through one or more cyclones where larger particulate matter is separated from the product gas stream. These catalytically active particles can be returned to the reactor and utilized for further reactions, thereby maximizing the yield of dimethyldichlorosilane from silicon.
The smaller particles are removed with the product stream and the product stream is then purified and condensed.

The purified methyl chloride is heated and recycled to the fluidized bed reactor to form additional amounts of methylchlorosilanes. The crude methylchlorosilane stream is passed to a distillation column to distill off the various chlorosilane fractions formed in the reaction in essentially pure form. Dimethyldichlorosilane and other chlorosilanes thus produced need to be distilled and purified so that they can be utilized in the production of silicone materials such as room temperature vulcanizable compositions and thermosetting silicone rubbers. . The details of how to prepare organochlorosilanes from elemental silicon and silicone compositions from such organochlorosilanes are well known to those skilled in the art.

EXAMPLES Examples of the present invention are shown below in order to enable those skilled in the art to better understand the specific implementation of the present invention, but these are merely for illustrative purposes and are not intended to limit the present invention in any way. In the examples, all parts are by weight unless otherwise indicated.

Example 1 50 parts of chemical grade silicon powder with a BET specific surface area of 0.5 m ² /g and nominal composition of the following: component weight ppm aluminum 2800 calcium 500 iron 5000 titanium 400 (the balance being mainly silicon); The following composition: Component weight % Cu ₂ O 40.6 CuO 41.4 Free Cu 14.5 Fe 0.69 Pb 0.11 Sn 0.42 Al 0.24 Si 0.95 (approximately 1% by weight means a median particle size value of approximately 5 microns and a BET ratio of approximately 3 m ² /g) A mechanical mixture of 2.9 parts of copper oxide material based on the precipitate and 0.25 parts of fine zinc powder was formed with a surface area of 0.25 parts of fine zinc powder; The reactor was charged to a 1 inch internal diameter stainless steel stirred bed reactor controlled at 0.degree. C. to provide a total throughput of 0.25 mole/hour of an equimolar mixture of methyl chloride and dimethyldichlorosilane vapors through the reactor. supplied at such a rate. After 1 hour, the feed was switched to a feed of methyl chloride gas alone, which was fed at a molar feed rate comparable to the feed rate of the binary feed used for activation of the contact mass. Generation of methylchlorosilane was immediately observed, and a maximum Kp of about 45 g/Hr.gSi was measured. The composition of the product was monitored by gas chromatography and at a silicon utilization of 43% (based on the silicon charge of the first batch) the following composition was obtained:

Component weight % (CH ₃ ) ₂ SiCl ₂ , D 77.68 CH ₃ SiCl ₃ , T 7.94 (CH ₃ ) ₃ SiCl, M 3.08 CH ₃ SiHCl ₂ , MH 0.21 (CH ₃ ) ₂ SiHCl, M ₂ H 0.08 Residue 10.66 Crude T/D 0.102 Example 2 50 parts of the same powdered silicon metal as in Example 1 and the following composition: Ingredient weight % Cu ₂ O 56.7 CuO 34.9 Free Cu 7.3 Fe 0.024 Pb 0.027 Sn 0.140 Al 0.0125 Si Trace (Only trace amounts of material are believed to be acid-insoluble in this free-flowing powder with a median particle size value of about 4 microns and a BET specific surface area of about 2 m ² /g)
A second mechanical mixture was prepared using 2.9 parts of a mixed copper oxide catalyst based on electrolytic copper with 0.25 parts of the same zinc as in Example 1.

The tin and aluminum described above were intentionally added to the relatively pure copper approximately midway through the mixed copper oxide manufacturing process, but prior to the oxidative firing step.

The direct reaction for producing methylchlorosilanes was carried out in the same manner as in Example 1. Approximately 38g/
The maximum Kp of hr.gSi was measured. The product composition obtained for a silicon utilization of approximately 45% (based on the initial silicon batch charge) was as follows.

Component weight % (CH ₃ ) ₂ SiCl ₂ , D 78.80 CH ₃ SiCl ₃ , T 7.20 (CH ₃ ) ₃ SiCl, M 2.96 CH ₃ SiHCl ₂ , MH 0.37 (CH ₃ ) ₂ SiHCl, M ₂ H 0.07 Residue 10.04 Crude T/D 0.091 The results of the above examples demonstrate that a synthetic catalyst system has been provided that exhibits performance comparable to or superior to natural precipitate-based copper oxide based catalysts.

Example 3 Based on electrolytic copper with 50 parts of the same powdered silicon metal as in Examples 1 and 2 and trace amounts of the following metals: component weight % Fe 0.66 Sn 0.10 Al 0.21 in the initial copper melt. A third mechanical mixture was prepared using 2.9 parts of mixed copper oxide catalyst.

The distribution and physical properties (eg, BET specific surface area and median particle size values) of Cu ₂ O, CuO, and free Cu were approximately the same as the catalysts of Examples 1 and 2. Example 1
As in and 2, an additional 0.25 part of zinc powder was incorporated into the mechanical mixture of the contact mass.

A direct method reaction was carried out in the same manner as in Examples 1 and 2 for the production of methylchlorosilanes. about
A maximum Kp value of 23 g/hr.gSi was measured. Approximately 28%
The following product composition was obtained for a silicon utilization (based on the silicon charge of the first batch):

Component weight % (CH ₃ ) ₂ SiCl ₂ , D 80.97 CH ₃ SiCl ₃ , T 8.22 (CH ₃ ) ₃ SiCl, M 2.19 CH ₃ SiHCl ₂ , MH 1.26 (CH ₃ ) ₂ SiHCl, M ₂ H 0.25 Residue 6.9 Crude T/D 0.102 Thus, synthetic compositions incorporating Sn, Al and Fe in a contact mass with Zn such that the ratio of Cu/Zn and other trace metals is kept within a specified range. A net increase in the desired components was obtained.

Claims (1)

[Claims] 1. The reaction of an organohalogen compound with powdered silicon consists essentially of the following components: (a) a mixture of Cu°, Cu ₂ O and CuO, (b) calculated as tin relative to copper. 200~5000ppm
of tin or tin-containing compounds; and (c) from 50 to 50, calculated as aluminum to copper.
A process for producing organohalosilanes consisting of methylchlorosilanes, characterized in that the process is carried out in the presence of an effective amount of a catalyst consisting of 5000 ppm of aluminum or an aluminum-containing compound. 2 If the catalyst is further calculated as iron versus copper,
A process according to claim 1, which essentially contains up to 7500 ppm of iron or iron-containing compounds. 3 The catalyst is further calculated as zinc per part of copper.
A process according to claim 1, which essentially contains 0.01 to 0.5 parts of zinc or zinc-containing compounds. 4 The catalyst is further calculated as zinc per part of copper.
A process according to claim 2, which essentially contains 0.01 to 0.5 parts of zinc or zinc-containing compounds. 5. The manufacturing method according to claim 1, wherein the catalyst does not substantially contain lead. 6. The method of claim 1, wherein the powdered silicon and the catalyst form a contact mass, and the catalyst constitutes 0.1 to 10% by weight of the contact mass. 7. The method of claim 1, wherein the catalyst constitutes 0.5-5.0% by weight of the contact mass. 8 Elemental copper constitutes 5-20% by weight of the catalyst, cuprous oxide constitutes 25-60% by weight of the catalyst, and cupric oxide constitutes 25-50% by weight of the catalyst. The manufacturing method described in Scope 1. 9 Elemental copper constitutes 14-18% by weight of the catalyst, cuprous oxide constitutes 39-50% by weight of the catalyst, and cupric oxide constitutes 35-43% by weight of the catalyst. The manufacturing method described in Scope 1. 10. The method of claim 1, wherein the partially oxidized copper of the catalyst is produced from essentially high purity electrolytic grade scrap. 11 Partially oxidized copper is produced by passing a solution of a copper compound over scrap iron to form a fine precipitate and partially oxidizing the copper in the precipitate by thermometallurgical methods. A manufacturing method according to claim 10. 12. The production method according to claim 1, wherein the organohalogen compound is methyl chloride. 13. The process according to claim 1, which is carried out under continuous conditions in a fluidized bed reactor. 14. The process according to claim 1, which is carried out in a stirred bed reactor. 15. The production method according to claim 1, which is carried out in a fixed bed reactor. 16. The manufacturing method according to claim 1, which is operated in 16 batches. 17. The process according to claim 1, which is carried out at a temperature in the range of 250° to 350°C. 18. The manufacturing method according to claim 1, wherein tin metal fine powder is used as a source of tin for the catalyst. 19. The production method according to claim 1, wherein aluminum metal fine powder or aluminum oxide powder is used as a source of aluminum for the catalyst. 20 Methyl chloride and powdered silicon are mixed in a reactor with essentially the following components: (a) 5 to 20% by weight of the catalyst, elemental copper, 25 to 20% by weight of the catalyst;
60% by weight cuprous oxide and 25-50% by weight of catalyst
(b) 200 to 5000 ppm calculated as tin to copper;
tin or tin-containing compounds; (c) 50 to 50, calculated as aluminum to copper;
5000 ppm of aluminum or aluminum-containing compounds; (d) up to 7500 ppm of iron or iron-containing compounds, calculated as iron to copper; and (e) 0.01 to 0.5 part of zinc or zinc, calculated as zinc per part of copper. The catalyst is reacted in the presence of an effective amount of a catalyst comprising: a compound containing the catalyst;
A sufficient proportion is introduced to maintain a catalyst content of 0.1 to 10% by weight of the silicon contact mass and the reaction is
The production rate of dimethyldichlorosilane is increased, while the weight ratio of methyltrichlorosilane to dimethyldichlorosilane is reduced and the methylchlorosilane in the resulting methylchlorosilane crude product is A process for producing methylchlorosilanes that retains or reduces the weight percent of the product with an atmospheric boiling point above 70°C. 21 Based on the silicon-copper catalyst contact assembly
A mixture of 0.1 to 10% by weight of elemental copper, cuprous oxide and cupric oxide, calculated as tin per part of copper.
200 to 5000 ppm of tin or tin-containing compounds, and 50 to 5000 ppm calculated as aluminum per part of copper
Powdered silicon-copper catalyst contact assembly for producing organohalosilanes consisting of methylchlorosilanes consisting essentially of 5000 ppm aluminum or aluminum-containing compounds. 22 Furthermore, calculate it as iron per part of copper.
22. A contact mass according to claim 21, essentially comprising up to 7500 ppm of iron or iron-containing compounds. 23 Furthermore, calculated as zinc per part of copper, it is 0.01
22. A contact mass according to claim 21, essentially containing ~0.5 part of zinc or a zinc-containing compound. 24. The contact assembly of claim 21, wherein the copper consists essentially of 5-20% by weight elemental copper, 25-60% by weight cuprous oxide and 25-50% by weight cupric oxide. thing.