CN1174988C - Technique of combination processing organic phosphorus and organosilicon monomer - Google Patents
Technique of combination processing organic phosphorus and organosilicon monomer Download PDFInfo
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- CN1174988C CN1174988C CNB021252815A CN02125281A CN1174988C CN 1174988 C CN1174988 C CN 1174988C CN B021252815 A CNB021252815 A CN B021252815A CN 02125281 A CN02125281 A CN 02125281A CN 1174988 C CN1174988 C CN 1174988C
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Abstract
Chloralkane generated in the production process of an organic compound containing phosphoryl or thionophosphoryl is recovered and purified, and the chloralkane is used for synthesizing organic group chlorosilane; in order to eliminate the influence of impurities of water, alcohol, etc. in the recovered chloralkane, 0.1 to 10 wt% of Zn element is introduced into catalysts for synthesizing the organic group chlorosilane; hydrochloric acid generated in the process of organic group polysiloxane or organic group silanol prepared from the organic group chlorosilane is recovered, and the hydrochloric acid is used for producing an organic compound containing phosphorus. Cl element formed in the two products is cyclically used, which can reduce environmental pollution and can respectively reduce production costs.
Description
Technical field
The present invention relates to the production technology of organophosphorus and organosilicon product coproduction, more this production technology of particular words is one of main raw material by producing as organosilane monomer behind the chloroparaffin by-product reclaiming clean that produces in will organophosphorus producing, and the production technique of one of the raw material produced as organophosphorus of the hydrogenchloride that produces during organosilane monomer produced.
Background technology
Silicoorganic compound are meant that containing the Si-C key, containing an organic radical at least is the compound that directly links to each other with Siliciumatom, by its organosilicon material that makes, excellent performance, be widely used in every field such as space flight, aviation, boats and ships, automobile, electronic apparatus, industry light industry textile industry, petrochemical complex, building materials, energy development, daily health care, development rapidly; And organosilane monomer is the basis of organosilicon industry, comprises methyl chlorosilane, ethyl chloride silane, phenyl chlorosilane and vinyl chlorosilane etc., and with the consumption maximum of methyl chlorosilane, consumption accounts for more than 90% (weight) of sum.
The synthetic main employing direct method production of methyl chlorosilane at present, promptly under heating condition, and under copper catalyst (also claiming the Si-Cu contact) effect, in fluidized-bed, carry out gas-solid phase reaction generation methyl chlorosilane monomer by methyl chloride and silica flour, through hydrolysis or alcoholysis post polymerization methyl polysiloxane (being called for short DMC) circlewise, it is to contain three ring (D to methyl chlorosilane again
3), Fourth Ring (D
4), five rings (D
5) mixture, generally use its principal monomer raw material as the synthesizing organo-silicon material; Also there is the synthesis material of part organosilicon material to be linear polymer (methyl silanol) without Cheng Huan.Chlorine is a kind of very important resource in organosilicon industry, but the overwhelming majority is not chloride in the organosilicon finished product, and the chlorine element only plays the intermediate axle beam effect in the organosilane monomer building-up process.Therefore the chlorine element being circulated to be utilized effectively in the organosilane monomer production process is the common requirement of environment and economic benefit, external major company such as Dow Corning, Wacker, GE pays much attention to the recycle research of chlorine element, the utilization ratio of chlorine element surpasses 80%, and the existing chlorine element circulation approach that generally adopts is shown in (Fig. 1).
Organophosphorus is meant the organic compound that contains phosphoric, refers in particular in the present invention to contain array structure down
(wherein R is a S[sulphur] or O[oxygen], R
1, R
2, R
3Be H or C independently of one another
1-C
6Alkyl such as methyl, ethyl, vinyl, propyl group and phenyl etc.) compound, produce and application process in alkoxyl group hydrolysis generation chloroparaffin often, P-C key or P-O key also may break to form chloroparaffin, its generative process is as follows:
Chloroparaffin is one of main by product of this type of reaction, and in actual applications, methyl chloride accounts for significant proportion.Therefore the chlorine element also is a kind of valuable source that needs recycle in organophosphorus industry.
Term " organophosphorus " used among the present invention is meant alkyl phosphite, for example two or more mixture of phosphorous acid mono alkyl ester, trimethyl phosphite or its; Glyphosate; And phosphate pesticide, for example Trichlorphon, SD-1750, Kitazine, omethoate etc.
Term " organosilane monomer " used among the present invention is meant, can use general formula R
nSiH
mX
4-n(R is methyl, ethyl, vinyl, phenyl, propyl group etc. in expression; X is halogen such as F, Cl, Br, I; N is the integer of 1-3, the integer of m=0-2) compound, be called alkyl halogen silanes, be preferably methyl chlorosilane; By alkyl polysiloxane or the alkylsilanol that alkyl halogen silanes makes, be preferably DMC or methyl silanol or its mixture.
The objective of the invention is to realize the chlorine element recycle between organophosphorus and the organosilane monomer, thereby make the chlorine element obtain wider low-costly effectively utilize.The material that contains said structure in the organophosphorus is a lot, for the ease of specifying, the present invention is technical scheme that example illustrate chlorine element recycle with dimethylphosphite with the glyphosate that is raw material with it, chemical classes technical professional is easy to the present invention is done some improvement, and these improvement also should be included within the present invention.
Dimethylphosphite is a kind of important chemical material and intermediate, is widely used, and domestic dimethylphosphite overall throughput has reached 100,000 tons.Dimethylphosphite is a raw material production with methyl alcohol and phosphorus trichloride, and byproduct chloromethane and hydrochloric acid.Methyl chloride has to stimulate and anesthetic action, the major injury central nervous system organs such as human liver, kidney of unifying.Pesticide producing producer methyl chloride recovery technologies such as dimethylphosphite of China and Trichlorphon fall behind, and the methyl chloride foreign matter content of recovery is low, can not be used for organic synthesis, can only be as solvent or cooling agent, some producer does not reclaim, and directly enters atmosphere, causes severe contamination.
Glyphosate is all commercial a kind of efficient, the low toxicity of (MONSANTO) company 1974, a steriland herbicide that Environmental compatibility is good of U.S. Meng Shan, because developing rapidly of resistance glyphosate genetically modified crops, further promoted the quick growth of glyphosate, at present it is consumption maximum, fastest-rising agricultural chemicals in the world, calendar year 2001 sales volume be about 3,000,000,000 dollars.
Glyphosate production technology has two, the one, be IDA (iminodiethanoic acid) method of representative with U.S. Monsanto Company, be main raw material promptly with diethanolamine, phosphorus trichloride, formaldehyde etc., the 2nd, the alkyl phosphite method is a main raw material with dimethylphosphite or trimethyl phosphite, Padil, Paraformaldehyde 96, hydrochloric acid promptly.China thanomin industry starting evening, development cause domestic diethanolamine price higher slowly, and U.S. Monsanto Company applied for the patent (application number 00118844) of IDA method being subjected to the restriction of this factor in China, and China generally adopts the alkyl phosphite method.This technology is very fast in my development, and throughput has reached 70,000 tons/year at present.
The contriver is a tame comprehensive chemical industry Listed Company, and glyphosate throughput has reached more than 20,000 tons/year, the production technology level advanced person.Developed the recovery technology of methyl chloride.And applied for national inventing patent (ZL99119970.7).
Summary of the invention
The present invention is according to the characteristics of organophosphorus and organosilicon production, and the organophosphorus and the organosilane monomer joint process based on the recycle of chlorine element of exploitation have improved raw material availability, and its working cycle is as (Fig. 2) with (Fig. 3).
The characteristics of this technology are in a creative way dimethylphosphite and glyphosate production and organosilane monomer production the recycling of compound (methyl chloride, hydrochloric acid) by chloride element to be combined; reduced three waste discharge on the one hand; protected ecotope, all right on the other hand first mate's degree reduces the production cost of dimethylphosphite, glyphosate and organosilane monomer multiple product.Chlorine element of the present invention recycle is compared with the chlorine element circulation during the organosilane monomer that generally adopts is synthetic, and its difference is: 1. the chlorine element in organophosphorus and two industries of organosilicon is carried out recycle; 2. reduce the supporting quantity of organosilane monomer synthetic methyl chloride significantly, make social resources obtain more reasonably using.
Below the explanation methyl chloride utilizes technology between glyphosate, dimethylphosphite, the production of methyl chlorosilane monomer.
The production process of alkyl phosphite method glyphosate is: add Paraformaldehyde 96 in containing the methanol solution of triethylamine, be heated to 40-50 ℃ of dissolving, add glycine then, at room temperature the dissolving back adds dimethylphosphite or trimethyl phosphite, 60-70 ℃ of following condensation, form intermediate:
This intermediate in the presence of hydrochloric acid, the reaction that under 50-120 ℃, is hydrolyzed, equation is:
From reaction process, contain CH in the tail gas of generation
3Cl, CH
2(OCH
3)
2, CH
3OH, H
2Components such as O, HCl, air, its weight (%) consists of:
| Methyl chloride | Air | Methyl alcohol | Methylal | Water | Hydrogenchloride | Other |
| 20-80 | 8-20 | 2-15 | 4-20 | 2-10 | 1-5 | 1-5 |
Patent of invention ZL99119970.7 discloses the recovery method of glyphosate byproduct chloromethane, adopts this technology or behind its similar technology reclaiming clean, still contains impurity such as micro-methylal, water, methyl alcohol in the methyl chloride, and its weight ratio is:
| Methyl chloride % | Methylal ppm | Water ppm | Methyl alcohol ppm | Dme | Residue ppm | HCLppm |
| 90-99.99 | ≤100 | ≤80 | ≤100 | ≤100 | ≤50 | ≤50 |
And synthesizing methyl-chloro-silane requires very harsh to methyl chloride, content is greater than more than 99.95%, and the control to trace impurities such as methyl alcohol, water, monochloroethane is very high, the influence in methyl chlorosilane is synthetic of these impurity and methylal is very big: in a single day the moisture of trace enter system in the methyl chloride, even hydrolysis and polymerization generation superpolymer such as the product dimethyldichlorosilane(DMCS) in the system, cover catalyst surface, make catalyst deactivation.Dme is the by product that is obtained by methanol dehydration in the sepn process, its boiling point (24 ℃) and methyl chloride are very near (very difficulty eliminates), can participate in the reaction high refuse of generation in the reaction system or be thermally cracked to charcoal and carbide when it enters, catalyst surface is poisoned, methyl alcohol also has same influence, impurity hydrochloric acid will promote the generation of impurity such as trichlorosilane, monomethyl chlorosilane, and will be unfavorable to the selectivity that improves dimethyldichlorosilane(DMCS) simultaneously.During the sulfuric acid dehydration, methyl chloride may be carried sulfur oxide and acid mist secretly, to reacting unfavorable.Synthetic (carrying out in the fluidized-bed) temperature of methyl chlorosilane is more than 280 ℃, and at the inner hot spot that easily produces of Si-Cu contact, methylal at high temperature easily decomposes charing, and deposition is at catalyst surface, and reactive behavior and selectivity can reduce rapidly, cause parking.Because bringing into of many impurity causes catalyst deactivation, selectivity, transformation efficiency and the yield that reacts all caused negative impact.
The Cu that adopts United States Patent (USP) (US4450882, US4503165) and morning twilight chemical research institute invention disclosed patent (application number 87104211) to make, CuO, Cu
2O three component catalysts choose, and the life-span is long, but if with reclaiming methyl chloride as the raw material synthesizing methyl-chloro-silane, catalyst life sharply descends, and economy is very poor.
Because necessary improvement original methyl chlorosilane production technique, particularly catalyst system, the present invention reaches to reduce temperature of reaction and reduce the formation of reacting hot spot by the improvement to catalyst system and makes the recovery methyl chloride be applicable to methyl chlorosilane production.The technical scheme of concrete catalyst treatment is: with the Cu-series catalyst of commercially available (morning twilight chemical research institute is on sale) is the ZnCL of 0.05-10% in mass concentration
2Soak down at 10-40 ℃ in the solution, soak time is 5-120 minute, treats to soak into fully after-filtration, 100-200 ℃ of oven dry down, needs nitrogen protection in oven dry and the process of cooling.Employing comes synthesizing methyl-chloro-silane through the catalyzer and the recovery methyl chloride of this art breading, and every technico-economical comparison all meets or exceeds the level of synthetic methyl chloride.
Because dimethylphosphite is synthetic in anhydrous system, impurity contained in its tail gas is than the easier processing of glyphosate tail gas, and methyl chloride recovery technology is similar in technology that is adopted and the glyphosate.The impurity that mainly contains in the methyl chloride that reclaims is compound such as the trimethyl phosphite that contains phosphoric, also contain a spot of phosphoric in the Pure Silicon Metal, therefore synthetic without any disadvantageous effect to methyl chlorosilane of the trace amounts of phosphorus element in the methyl chloride, moisture then can be controlled within the standard range.Therefore this methyl chloride can adapt to above-mentioned catalyst system.
Illustrate that with hydrogenchloride or hydrochloric acid the chlorine element utilizes technology between glyphosate, dimethylphosphite, the production of methyl chlorosilane monomer again.
Need the concentrated hydrochloric acid (weight concentration is more than 20%) of a large amount of (2.5-4.5 ton/ton) in the alkyl phosphite technology glyphosate production, and produce a large amount of hydrochloric acid (weight content is 20-36.5%) in organosilane monomer and the dimethylphosphite production.Therefore impurities is mainly phosphorous acid, methyl alcohol and methyl chloride in the dimethylphosphite by-product hydrochloric acid, and described impurity all is included in the glyphosate synthetic system, and can be directly used in glyphosate synthetic for described hydrochloric acid.The hydrochloric acid that reclaims from the organosilane monomer hydrolytic process then owing to contain organic radical silanol and organopolysiloxane, can influence the quality of the former powder of the finished product glyphosate, therefore must handle this hydrochloric acid.Organic radical silanol and the organopolysiloxane solubleness in dilute hydrochloric acid is very little, in dilute hydrochloric acid, form more stable system after the emulsification, its content folding silicon meter can reach 5%, by adding effectively breakdown of emulsion of electrolytical method, make organism and water layering, thereby make organic radical silanol and organopolysiloxane return hydrolyzing process easily.Used ionogen is oxygen-free acid or oxygen acid root salt, can be Na as positively charged ion
+, Mg
2+, Ca
2+, K
+Deng, negatively charged ion is F
-, Cl
-, SO
4 2-, NO
3 -, CO
3 2-, OH
-Deng, add-on is 0.05～1% of a dilute hydrochloric acid total amount.Handle by this method, dissolved machine base silanol and organopolysiloxane are reduced in the 1000ppm.
Methyl chloride synthesis procedure during methyl chlorosilane is produced, after the water that generates and reactant hydrogenchloride and methyl alcohol generate the dilute hydrochloric acid that contains methyl alcohol and methyl chloride separate, because content low (below 25%) is worth low, normally carry out biochemical treatment after the neutralization, back up to standard discharging.The present invention proposes a kind of application method of this abraum salt acid,, can replace water to carry out the absorption of the hydrogenchloride in the dimethylphosphite production with it because of the hydrochloric acid of wherein contained impurity composition and dimethylphosphite recovery is close.But the mass transfer force of dilute hydrochloric acid absorbing hydrogen chloride is big not as water, in order to reduce this influence, can adopt freeze cycle to absorb, absorption liquid is cooled to (30～40 ℃) below the gas phase temperature, behind multistage absorption, concentration can increase to more than 30%, can be used for glyphosate production.
Chlorine element recycle between dimethylphosphite of the present invention, glyphosate, the methyl chlorosilane monomer three has not only solved the problem of environmental pollution that the said products is produced, and makes the chlorine resource obtain comprehensive utilization, can reduce production costs significantly.It is other Chemicals of raw material and the coproduction of organosilane monomer that this technology can also be generalized to the phosphoric acid ester.The adjustment that this technology is done also belongs to content of the present invention with combination.
Embodiment
Embodiment: be preheated to 200-280 ℃ after the methyl chloride vaporization with metering, enter fluidized-bed reactor, again silica flour and catalyzer are brought into by the methyl chloride air-flow, after reaction starts, control top layer temperature is 280-350 ℃, product separates through cyclonic separator from reactor head, the solid phase Returning reactor, and gas phase enters its composition of dust post analysis that washing tower removes deentrainment.
Embodiment 1: methyl chloride derives from alkyl phosphite method glyphosate production, and content is 99.95%, and the methylal weight content is 30ppm, and the monomer synthetic catalyst is commercially available, and through above-mentioned processing, wherein the zinc weight content is 0.75%.
Embodiment 2: methyl chloride derives from alkyl phosphite method glyphosate production, and content is 98.7%, and the methylal weight content is 100ppm, and the monomer synthetic catalyst is commercially available, and through above-mentioned processing, wherein the zinc weight content is 0.95%.
Embodiment 3: methyl chloride derives from alkyl phosphite method glyphosate production, and content is 99.5%, and it is 60ppm that methylal must be measured content, and the monomer synthetic catalyst is commercially available, and through above-mentioned processing, wherein the zinc weight content is 0.3%.
Embodiment 4: methyl chloride derives from alkyl phosphite method glyphosate production, and content is 91.0 ± 1.0%, and the monomer synthetic catalyst is commercially available, unprocessed.
Embodiment 5: methyl chloride derives from alkyl phosphite method glyphosate production, and content is 99.95%, and the monomer synthetic catalyst is commercially available, unprocessed.
Embodiment 6: methyl chloride derives from dimethylphosphite production, and content 〉=99.95%, monomer synthetic catalyst are commercially available, unprocessed.
Embodiment 7: methyl chloride derives from Trichlorphon production, and content 〉=98.5%, monomer synthetic catalyst are commercially available, and through above-mentioned processing, wherein the zinc weight content is 0.4%.
Embodiment 8: methyl chloride derives from omethoate production, and content 〉=98.5%, monomer synthetic catalyst are commercially available, and through above-mentioned processing, wherein the zinc weight content is 0.4%.
Embodiment 9: methyl chloride derives from SD-1750 production, and content 〉=98.5%, monomer synthetic catalyst are commercially available, and through above-mentioned processing, wherein the zinc weight content is 0.4%.
Embodiment 10: methyl chloride derives from Kitazine production, and content 〉=98.5%, monomer synthetic catalyst are commercially available, and through above-mentioned processing, wherein the zinc weight content is 0.4%.
Embodiment 11 (Comparative Examples): it is synthetic that methyl chloride derives from methyl alcohol hydrochlorinate method, and content 〉=98.5%, monomer synthetic catalyst are commercially available, unprocessed.
The experimental result tabulation
| Lot number | Working time (hr) | Washing property of contact (g/kg.hr) | Dimethyldichlorosilane(DMCS) selectivity (%) | Silica flour unit consumption (t/t) | Methyl chloride unit consumption (t/t) |
| 1 | 299 | 148.2 | 83.5 | 0.240 | 0.857 |
| 2 | 143 | 124.0 | 80.1 | 0.270 | 0.936 |
| 3 | 201 | 140.7 | 82.5 | 0.250 | 0.875 |
| 4 | 82 | 92.2 | 73.0 | 0.320 | 1.102 |
| 5 | 152 | 125.1 | 82.0 | 0.250 | 0.891 |
| 6 | 240 | 140.3 | 83.2 | 0.241 | 0.859 |
| 7 | 224 | 135.2 | 82.1 | 0.249 | 0.885 |
| 8 | 220 | 135.0 | 82.2 | 0.248 | 0.885 |
| 9 | 222 | 135.0 | 82.1 | 0.248 | 0.884 |
| 10 | 220 | 135.0 | 82.0 | 0.249 | 0.885 |
| 11 | 242 | 140.1 | 82.1 | 0.251 | 0.876 |
Claims (27)
1, a kind of organophosphorus production and to adopt halohydrocarbon, silica flour be joint process between the organosilane monomer of raw material is produced is characterized in that: realize the coproduction of organophosphorus and organosilane monomer by the recycle of chlorine element.
2, according to the production technique of claim 1, the feature of described recycle is:
1. the compound with the chloride element that produces in the organophosphorus production process reclaims or reclaims and purifies;
2. the compound of the chloride element that will reclaim is used for the synthetic of organosilane monomer;
3. the compound of the chloride element in the organosilane monomer production is applied to the production of organophosphorus.
3, according to the production technique of claim 1 or 2, the structural formula of described organophosphorus is
Or
Wherein R is S or O, R
1, R
2, R
3Be H or C independently of one another
1-C
6Alkyl.
4, according to the production technique of claim 1 or 2, the compound of described chloride element is one or more the mixture in methyl chloride, hydrochloric acid, the hydrogenchloride.
5, according to the production technique of claim 1 or 2, described organosilane monomer is alkyl chlorosilane and poly-alkylsiloxane and alkylsilanol.
6, according to the production technique of claim 1 or 2, described organosilane monomer is methyl chlorosilane or methyl polysiloxane or methyl silanol.
7, according to the production technique of claim 1 or 2, described organophosphorus is phosphorous acid mono-methyl, dimethylphosphite, trimethyl phosphite or is the mixture that contains one or more compounds in these three kinds of compounds.
8, according to the production technique of claim 1 or 2, described organophosphorus is one or more the combination in dimethylphosphite, glyphosate, the phosphate pesticide.
9, production technique according to Claim 8, described phosphate pesticide are Trichlorphon, SD-1750, Kitazine, omethoate.
10, according to the production technique of claim 2, being characterized as of described coproduction technology: behind the byproduct chloromethane reclaiming clean that produces in the dimethylphosphite production process, it is monomeric synthetic to be used for methyl chlorosilane.
11, according to the production technique of claim 2, being characterized as of described coproduction technology: will be that it was monomeric synthetic to be used for methyl chlorosilane after byproduct chloromethane that the glyphosate production process of raw material produces reclaimed with dimethylphosphite or trimethyl phosphite.
12, according to the production technique of claim 2, being characterized as of described coproduction technology: will be that it was monomeric synthetic to be used for methyl chlorosilane after byproduct chloromethane that the production process of Trichlorphon, SD-1750, Kitazine, the omethoate of main raw material produces reclaimed with dimethylphosphite or trimethyl phosphite.
13, according to the production technique of claim 2, being characterized as of described coproduction technology: the dilute hydrochloric acid that produces in the methyl chloride synthesis procedure in the methyl chlorosilane monomer production process is reclaimed, through dimethylphosphite hydrochloric acid recovery process its concentration is raise, can be used for glyphosate production.
14, according to the production technique of claim 2, being characterized as of described coproduction technology: behind the hydrochloric acid or hydrogenchloride reclaiming clean that produce in the methyl chlorosilane monomer hydrolytic process, be used for glyphosate production.
15, according to the production technique of claim 14, being characterized as of the hydrochloric acid that produces in the described hydrolytic process:
1. contain in feature impurity methyl silanol, the methyl polysiloxane one or more; 2. the weight content of impurity is counted 0.1ppm to 2% with silicon; 3. wherein the weight content of hydrogenchloride is 15-36.5%.
16, according to the production technique of claim 10, being characterized as of the methyl chloride of recovery: contain phosphoric in the 1. contained impurity, feature impurity is trimethyl phosphite; 2. the weight content of phosphoric is 0.1-10000ppm; 3. the weight content of methyl chloride is 20-99.99%.
17, according to the production technique of claim 10, being characterized as of the methyl chloride of recovery: 1. its weight content is 99.00-99.99%; 2. the weight content of trimethyl phosphite is 1-100ppm.
18, according to the production technique of claim 11, being characterized as of the methyl chloride of recovery: 1. contain feature impurity methylal; 2. the weight content of methylal is 0.1-10000ppm; 3. the weight content of methyl chloride is 20-99.99%.
19, according to the production technique of claim 11, being characterized as of the methyl chloride of recovery: 1. its weight content is 99.00-99.99%; 2. the weight content of methylal is 1-100ppm.
20, according to the production technique of claim 12, being characterized as of the methyl chloride of recovery: the weight content of methyl chloride is 20-99.99%.
21, according to the production technique of claim 12, wherein the weight content of the methyl chloride of Hui Shouing is 99.00-99.99%.
22, according to the production technique of claim 13, being characterized as of wherein said dimethylphosphite hydrochloric acid recovery process: contain feature component methyl alcohol in the 1. described dilute hydrochloric acid, the weight content of methyl alcohol is 10ppm-2%, and the weight content of hydrogenchloride is 1-25%; 2. replace water to carry out the absorption that dimethylphosphite is produced tail gas with dilute hydrochloric acid replacement or part; 3. adopt freezing or cooling and absorbing technology, absorption temperature is-30-50 ℃.
23, according to the production technique of claim 22, the weight content of hydrogenchloride is 12-23% in the wherein said dilute hydrochloric acid.
24,, be used for being characterized as of hydrochloric acid of glyphosate after the described recovery according to the production technique of claim 15:
1. the weight content of impurity is counted 0.1ppm-1000ppm with silicon; 2. the weight content of hydrogenchloride is 20-36.5%.
25, according to any one production technique of claim 10-12, wherein the methyl chloride that reclaims is used for being characterized as of methyl chlorosilane monomer synthetic catalyzer: wherein contain the compound of zinc powder or zinc, in zinc, its weight content is 0.1-10%.
26, according to the production technique of claim 25, described zn cpds is the divalent salts of zinc.
27, according to the production technique of claim 25, being characterized as of described catalyzer: wherein containing weight content is zinc chloride or the zinc carbonate of 0.5-0.8% (in zinc).
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