CN102276640A - Method for converting methyl trichlorosilane to dimethyl dichlorosilane based on synthesis - Google Patents
Method for converting methyl trichlorosilane to dimethyl dichlorosilane based on synthesis Download PDFInfo
- Publication number
- CN102276640A CN102276640A CN2011101508775A CN201110150877A CN102276640A CN 102276640 A CN102276640 A CN 102276640A CN 2011101508775 A CN2011101508775 A CN 2011101508775A CN 201110150877 A CN201110150877 A CN 201110150877A CN 102276640 A CN102276640 A CN 102276640A
- Authority
- CN
- China
- Prior art keywords
- aluminium powder
- trichloro silane
- dmcs
- dimethyldichlorosilane
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a method for converting methyl trichlorosilane to dimethyl dichlorosilane based on catalysis, belonging to the field of organic catalysis. According to the invention, a reaction that methyl trichlorosilane is converted to dimethyl dichlorosilane is carried out in a gas-solid phase fixed bed reactor, an aluminite powder is used as a chlorine receiving agent and a catalyst, and activated carbon is added to be used as an absorbing agent. The method comprises the following steps: firstly, adding a mixture of aluminite powder and activated carbon in the fixed bed reactor, and introducing nitrogen so as to replace air in a device; after stopping introducing nitrogen, gasifying a reactant at the temperature of 220 DEG C, enabling the gasified reactant to flow through the fixed bed reactor, and then reacting at the temperature of 230-320 DGE C; and enabling a product to flow through an aluminium trichloride collector with the temperature of about 120 DGE C for carrying out gas-solid separation, then carrying out ice and water bath and liquid nitrogen cold trap condensation, subsequently collecting a sample for 1 hour continuously. The method provided by the invention is simple in process and is easy to carry out industrialized expanding application, the reaction is easy to control and can be continuously carried out, the conversion rate of a raw material and the yield of the product are high, and the activity of the catalyst is good.
Description
Technical field
The present invention relates to a kind of " direct method " and produce the method that by product METHYL TRICHLORO SILANE in the dimethyldichlorosilane(DMCS) process is converted into dimethyldichlorosilane(DMCS), refer in particular to: the employing methyl chloride is a methyl donor, metals such as aluminium powder, zinc powder, glass putty, magnesium powder are that chlorine receives agent and catalyzer, and add gac as sorbent material, in fixed-bed reactor, METHYL TRICHLORO SILANE is converted into the novel method of dimethyldichlorosilane(DMCS).
Background technology
Organosilicon material is that a class is a main chain with the Si-O key, on the Si atom, introduce the macromolecular compound of organic group again as half organic, half inorganic structure of side chain, therefore have the advantage of organism and inorganics concurrently, in aerospace, military technique, electric industry, weaving papermaking, building industry, chemical industry, metal and fields such as paint industry, medical medical treatment, all obtained using widely.
Methyl chlorosilane (METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane, tetramethylsilane etc.) is the important monomer during organosilicon is produced, and wherein dimethyldichlorosilane(DMCS) has the status of mainstay.Produce in the method for dimethyldichlorosilane(DMCS), the most famous is the method for the direct synthesizing methyl-chloro-silane of nineteen forty-one American Rochow invention.Through the development of over half a century, this method has become the methyl chlorosilane production method that generally adopts both at home and abroad.Use this legal system to be equipped with dimethyldichlorosilane(DMCS) in the time of (being called for short diformazan or M2), also produced a large amount of METHYL TRICHLORO SILANE (being called for short a first or M1), trimethylchlorosilane (being called for short front three or M3), dimethyl dichlorosilane (DMCS) (being called for short the hydrogeneous or MH of a first), low boiling mixture (abbreviation low-boiling-point substance) and high boiling mixture by products such as (abbreviation high boiling material).Wherein the content of METHYL TRICHLORO SILANE is up to 5～15% of crude product.Thus, the outlet of each big manufacturer a large amount of first of accumulating will become the problem that can't neglect.At home, a first is used for preparing low grade products such as silane crosslinker, methyl silicon resin and water-resisting agent more, but the market requirement is limited, and economic worth is not high, can not effectively solve a first problem of outlet.And since a first in the Si-Cl key very easily with airborne water vapour generation hydrolysis reaction, emit gases such as having corrosive hydrogenchloride, human body and surrounding buildings thing etc. is brought corrodibility, bring the pollution of potential safety hazard and environment.Therefore, pushing effect very significantly will be played to the Sustainable development of organosilicon industry in the path of an effective more economically first resource reutilization.
One first resource reutilization can also be converted into diformazan by carrying out disproportionation reaction with tetramethyl, front three, is divided into high pressure disproportionation and low pressure disproportionation.The high pressure discrimination method need react under elevated pressures, comparatively high temps, and harsh to equipment requirements, safety performance is low.Though the low pressure discrimination method does not need very high pressure, the catalyzer instability of using, the life-span is low, reacts wayward, and yield is undesirable.The organo-metallic method is shown one's talent in numerous first conversion methods, can carry out continuous reaction mainly due to this method, is easy to carry out industrial amplification production.This method is done reactant with a first and methyl chloride, adopts fixed-bed reactor, uses aluminium powder, zinc powder and glass putty etc. to receive agent and catalyzer as chlorine, adds gac or diatomite simultaneously to make sorbent material, can obtain a better first transformation efficiency and diformazan yield.But the per pass conversion that how further to improve a first is the emphasis of making great efforts at present.
Summary of the invention
For improving the each side drawback of an existing first transformation technology, it is methyl donor that the present invention adopts methyl chloride, metals such as aluminium powder, magnesium powder, zinc powder, glass putty are that chlorine receives agent and catalyzer, add gac simultaneously to make sorbent material, and METHYL TRICHLORO SILANE is converted into dimethyldichlorosilane(DMCS).
The technical solution used in the present invention is:
Using separately aluminium powder is that chlorine receives agent and catalyzer, and the interpolation gac carries out the reaction that METHYL TRICHLORO SILANE is converted into dimethyldichlorosilane(DMCS) during as sorbent material.
A kind of METHYL TRICHLORO SILANE is converted into the method for dimethyldichlorosilane(DMCS), fix in gas-solid and to carry out the reaction that METHYL TRICHLORO SILANE is converted into dimethyldichlorosilane(DMCS) in the bed bioreactor, use aluminium powder to receive agent and catalyzer as chlorine, and add gac as sorbent material, carry out according to following step: at first the mixture with aluminium powder and gac inserts in the fixed-bed reactor, opens air in the nitrogen replaceable equipment; After stopping logical nitrogen, reactant is through 220 ℃ of vaporizations, the fixed-bed reactor of flowing through, wherein activated carbon dosage is 5～20% of aluminium powder consumption in mass, wherein said METHYL TRICHLORO SILANE flow is 0.1ml/min, and the methyl chloride flow is 16ml/min, and nitrogen flow is 20ml/min; Under 230～320 ℃ temperature, react; Product carries out gas solid separation after collect 1 hour sample after ice-water bath and the liquid nitrogen cold trap condensation continuously through temperature maintenance at the aluminum chloride collector about 120 ℃.
In the technique scheme, the consumption of preferred gac is 20% of aluminium powder consumption in mass.
Also can use the arbitrary substance of aluminium powder and one of magnesium powder, zinc powder or glass putty mixed in the technique scheme, and add gac, carry out the reaction that METHYL TRICHLORO SILANE is converted into dimethyldichlorosilane(DMCS) as sorbent material as chlorine reception agent and catalyzer; Wherein activated carbon dosage is 20% of aluminium powder consumption in mass, magnesium powder, zinc powder or glass putty consumption be respectively the aluminium powder consumption in mass 3%, 3%, 0.2%.
The yield of the transformation efficiency of a first and diformazan all raises along with the rising of temperature of reaction in the aforesaid method, may cause sintering of catalyst but temperature is too high, and preferable reaction temperature is 320 ℃.
The present invention is easy through the method technology that metal catalyst is converted into dimethyldichlorosilane(DMCS) by METHYL TRICHLORO SILANE, reaction is easy to control and can carries out continuous reaction, be easy to carry out the industrialization broadened application, feed stock conversion and product yield are higher, and catalyst activity is good.
Each main ingredient composition mass content is a methyl chlorosilane 99% in the aforesaid method, methyl chloride 99%, aluminium powder 99.5% (needle-like of 0.38～0.83mm * 0.7～1.5mm), the sheet of magnesium powder 99%(30～300 μ m * 20～150 μ m * 20 μ m), zinc powder 98%(particle diameter 1～13.5 μ m's is spherical), glass putty 99%(particle diameter 3.5～50 μ m's is spherical), gac (particle of particle diameter 0.5～1.2mm), nitrogen (high purity nitrogen, 99.999%).
Description of drawings
Fig. 1: reaction process sketch of the present invention;
Fig. 2: add METHYL TRICHLORO SILANE conversion reaction result under 5 % gacs and the aluminium powder effect;
Fig. 3. add METHYL TRICHLORO SILANE conversion reaction result under 10 % gacs and the aluminium powder effect;
Fig. 4. add METHYL TRICHLORO SILANE conversion reaction result under 20 % gacs and the aluminium powder effect;
Fig. 5: add METHYL TRICHLORO SILANE conversion reaction result under 20 % gacs and aluminium powder, the effect of magnesium powder;
Fig. 6: add METHYL TRICHLORO SILANE conversion reaction result under 20 % gacs and aluminium powder, the zinc powder effect;
Fig. 7: add METHYL TRICHLORO SILANE conversion reaction result under 20 % gacs and aluminium powder, the glass putty effect;
Fig. 8: METHYL TRICHLORO SILANE conversion reaction mechanism synoptic diagram;
Annotate: in Fig. 2～7, ■ METHYL TRICHLORO SILANE transformation efficiency dimethyldichlorosilane(DMCS) yield ● trimethylchlorosilane is received zero tetramethylsilane yield.
Embodiment
Embodiment 1:
Preparation of catalysts
With the gac of table balance weighing 100g after the oven drying dehumidifying, again to the aluminium powder that wherein adds the certain mass ratio, stirring is dispersed in the gac aluminium powder, and joining diameter is that 16 mm length are in the fixed-bed reactor of 510 mm.If no special instructions, said amount ratio is mass ratio in the following method.
The reaction of methyl aluminum chloride method METHYL TRICHLORO SILANE gas-solid inversion of phases
To join in the fixed-bed reactor with the metal catalyst aluminium powder that gac mixes, install reaction unit (as Fig. 1), feed the air of nitrogen replaceable equipment inside, stop logical nitrogen after 10 minutes.Steam after 220 ℃ of vaporizations feeds fixed-bed reactor with a first and methyl chloride, and the controlling reactor temperature is respectively 230 ℃, 260 ℃, 290 ℃, 320 ℃ and carries out the reaction of METHYL TRICHLORO SILANE gas-solid inversion of phases.Reaction is carried out continuously, and product carries out that gas-solid is separated after after collecting 1 hour continuously after ice bath and the liquid nitrogen cold trap condensation, sample thief is used its composition of gas chromatographic analysis immediately through aluminum chloride collector (about 120 ℃ of temperature maintenance).After finishing, experiment stops a logical first and methyl chloride, nitrogen protection cooling down.
The condition of gas-chromatography is:
Test column: OV-1701 capillary column; Sampler temperature: 180 ℃; Detector temperature: 180 ℃; Detector type: FID; H
2Pressure: 0.1 MPa; Carrier gas: high purity nitrogen; Press before the post: 0.25 MPa; Temperature Cheng Sheng: 36 ℃ of initial temperatures, begin after 11 minutes to heat up, 30 ℃/min is warming up to 180 ℃, keeps 2 min; Sample size: 1 μ L; Toluene is internal standard substance; The transformation efficiency of a first in the assay products, the yield of diformazan, front three, tetramethyl.
The transformation efficiency of one first, the calculation formula of the yield of diformazan, front three, tetramethyl is as follows:
X
M1?=?[M1
in-M1
out]/[M1
in]
Y
Mi?=?[Mi
out]/[M1
in]
Wherein, M1 represents a first, and Mi represents diformazan, front three, tetramethyl (i=2,3,4).
Repeat above-mentioned experimental procedure, but the ratio of change gac is 5%, 10%, 20%, experimental result is respectively as Fig. 2, Fig. 3, shown in Figure 4.
Experimental result shows, obviously do not increase when the METHYL TRICHLORO SILANE transformation efficiency adds the gac reaction behind the adding gac, and the increase with the gac additional proportion increases: the transformation efficiency of METHYL TRICHLORO SILANE is up to 20% when adding the gac of 5 % ratios, the yield of dimethyldichlorosilane(DMCS), trimethylchlorosilane reaches 15 % respectively, 3.5%, the tetramethylsilane trace; Increase the gac ratio by 10% o'clock, the transformation efficiency of METHYL TRICHLORO SILANE is up to 35 %, and the yield of dimethyldichlorosilane(DMCS), trimethylchlorosilane, tetramethylsilane reaches 33 % respectively, 6 %, 0.6 %; When continuing to increase the gac ratio to 20 %, the transformation efficiency of METHYL TRICHLORO SILANE is up to 44 %, and the yield of dimethyldichlorosilane(DMCS), trimethylchlorosilane reaches 41%, 4 % respectively.This is because gac has adsorption, increased raw material especially reaction intermediate methyl aluminum chloride in the residence time of reaction bed, thereby improved the transformation efficiency of METHYL TRICHLORO SILANE.In addition, rising along with temperature of reaction, the transformation efficiency of METHYL TRICHLORO SILANE and the yield of dimethyldichlorosilane(DMCS) also increase, when temperature of reaction surpasses more than 290 ℃, the content of dimethyldichlorosilane(DMCS) obviously raises in the product, this is because elevated temperature has increased the energy of reaction system, thereby improves speed of response.
Embodiment 2
Preparation of catalysts
Add with embodiment 1 but therein and account for aluminium powder consumption 3% magnesium powder in mass, stir it is uniformly dispersed.
The reaction of methyl aluminum chloride method METHYL TRICHLORO SILANE gas-solid inversion of phases
Keeping the adding proportion of gac is 20%, uses aluminium powder and magnesium powder to do chlorine and receives agent and catalyzer, and the result of conversion reaction respectively as shown in Figure 5.
As shown in Figure 5, added the magnesium powder and make catalyzer in aluminium powder, activity increases again: the transformation efficiency of METHYL TRICHLORO SILANE can reach 50%, and the yield of dimethyldichlorosilane(DMCS) reaches 41%.
Embodiment 3
Preparation of catalysts
Add with embodiment 1 but therein and account for aluminium powder consumption 3% zinc powder in mass, stir it is uniformly dispersed.
The reaction of methyl aluminum chloride method METHYL TRICHLORO SILANE gas-solid inversion of phases
Keeping the adding proportion of gac is 20%, uses aluminium powder and zinc powder to do chlorine and receives agent and catalyzer, and the result of conversion reaction respectively as shown in Figure 6.
As shown in Figure 6, added zinc powder and make catalyzer in aluminium powder, activity increases again: the transformation efficiency of METHYL TRICHLORO SILANE can reach 54%, and the yield of dimethyldichlorosilane(DMCS) reaches 47%.
Embodiment 4
Preparation of catalysts
Add with embodiment 1 but therein and account for aluminium powder consumption 0.2% glass putty in mass, stir it is uniformly dispersed.
The reaction of methyl aluminum chloride method METHYL TRICHLORO SILANE gas-solid inversion of phases
Keeping the adding proportion of gac is 20%, uses aluminium powder and zinc powder to do chlorine and receives agent and catalyzer, and the result of conversion reaction respectively as shown in Figure 7.
As shown in Figure 7, added glass putty and make catalyzer in aluminium powder, activity increases again: the transformation efficiency of METHYL TRICHLORO SILANE can reach 59%, and the yield of dimethyldichlorosilane(DMCS) reaches 57%.
Claims (3)
1. a METHYL TRICHLORO SILANE is converted into the method for dimethyldichlorosilane(DMCS), it is characterized in that fixing and carry out the reaction that METHYL TRICHLORO SILANE is converted into dimethyldichlorosilane(DMCS) in the bed bioreactor in gas-solid, use aluminium powder to receive agent and catalyzer as chlorine, and add gac as sorbent material, carry out according to following step: at first the mixture with aluminium powder and gac inserts in the fixed-bed reactor, opens air in the nitrogen replaceable equipment; After stopping logical nitrogen, reactant is through 220 ℃ of vaporizations, the fixed-bed reactor of flowing through, wherein activated carbon dosage is 5～20% of aluminium powder consumption in mass, wherein said METHYL TRICHLORO SILANE flow is 0.1ml/min, and the methyl chloride flow is 16ml/min, and nitrogen flow is 20ml/min; Under 230～320 ℃ temperature, react; Product carries out gas solid separation after collect 1 hour sample after ice-water bath and the liquid nitrogen cold trap condensation continuously through temperature maintenance at the aluminum chloride collector about 120 ℃.
2. a kind of METHYL TRICHLORO SILANE according to claim 1 is converted into the method for dimethyldichlorosilane(DMCS), it is characterized in that the consumption of gac is 20% of aluminium powder consumption in mass.
3. a kind of METHYL TRICHLORO SILANE according to claim 1 is converted into the method for dimethyldichlorosilane(DMCS), its feature is mixed as chlorine reception agent and catalyzer at the arbitrary substance of last use aluminium powder and one of magnesium powder, zinc powder or glass putty, and add gac as sorbent material, carry out the reaction that METHYL TRICHLORO SILANE is converted into dimethyldichlorosilane(DMCS); Wherein activated carbon dosage is 20% of aluminium powder consumption in mass, magnesium powder, zinc powder or glass putty consumption be respectively the aluminium powder consumption in mass 3%, 3%, 0.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101508775A CN102276640A (en) | 2011-06-07 | 2011-06-07 | Method for converting methyl trichlorosilane to dimethyl dichlorosilane based on synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101508775A CN102276640A (en) | 2011-06-07 | 2011-06-07 | Method for converting methyl trichlorosilane to dimethyl dichlorosilane based on synthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102276640A true CN102276640A (en) | 2011-12-14 |
Family
ID=45102423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101508775A Pending CN102276640A (en) | 2011-06-07 | 2011-06-07 | Method for converting methyl trichlorosilane to dimethyl dichlorosilane based on synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102276640A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465579A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Process for synthesizing (CH3)2 SiCl2 by utilizing CH3 SiCl2 |
| US20050113592A1 (en) * | 2003-08-05 | 2005-05-26 | Ge Bayer Silicones Gmbh & Co. | Method for preparing chlorosilane |
-
2011
- 2011-06-07 CN CN2011101508775A patent/CN102276640A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465579A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Process for synthesizing (CH3)2 SiCl2 by utilizing CH3 SiCl2 |
| US20050113592A1 (en) * | 2003-08-05 | 2005-05-26 | Ge Bayer Silicones Gmbh & Co. | Method for preparing chlorosilane |
Non-Patent Citations (1)
| Title |
|---|
| 王雪飞: "甲基三氯硅烷转化反应及组合工艺研究", 《浙江大学硕士学位论文》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103007995B (en) | A kind of composite catalyst preparing trichlorosilane for catalytic hydrogenation of silicon tetrachloride | |
| CN103212386B (en) | High purity full porous silica gel-bonded chromatography immobile phase preparation method | |
| CN101824046B (en) | Method for generating dimethyldichlorosilance by utilizing disproportionation reaction | |
| CN105968366B (en) | A kind of liquid borosilicate resin and its preparation method and application | |
| RU2010142993A (en) | METHOD AND SYSTEM FOR PRODUCING PURE SILICON | |
| CN103664440B (en) | Methanol conversion produces the method for aromatic hydrocarbons | |
| CN105854934A (en) | Preparation and application of green environment-friendly immobilized platinum catalyst | |
| CN102250133B (en) | Method for preparing dimethyl dichlorosilane by using disproportionation method | |
| CN103709187A (en) | New technology of synthesizing dimethyldichlorosilance | |
| CN103846101B (en) | A kind of C-SiC catalyst and Synthesis and applications thereof | |
| CN101531674A (en) | Preparation method of methyl chlorosilane | |
| CN104945428A (en) | Method for preparing dimethyl dichlorosilane | |
| CN103087320A (en) | Preparation method of hydroxyl-terminated polymethylphenyl silicone oil | |
| CN102875585B (en) | A kind of method preparing tetramethyl divinyl disiloxane | |
| CN102140107A (en) | Method for disproportionating methyl chlorosilane | |
| CN104387413A (en) | Production method for preparing trialkoxysilane by adopting direct method | |
| CN107537576B (en) | Immobilized catalyst of silane coupling molecular sieve and double-salt ionic liquid | |
| CN102276640A (en) | Method for converting methyl trichlorosilane to dimethyl dichlorosilane based on synthesis | |
| CN105753895B (en) | A kind of preparation method of dimethyldichlorosilane | |
| CN106243145B (en) | A kind of method of fixed bed reaction synthesizing trimethoxy silane | |
| CN102381944B (en) | Method for synthesizing C-13 and C-14 labelled bisphenol A and C-13 and C-14 labelled tetrabromobisphenol A | |
| CN100999530A (en) | Process of preparing dimethyl dichloro silicane by organosilicon high and low boiling matter | |
| CN102659829A (en) | Recycling method of by-products in direct method production of methyl chlorosilane | |
| Zhang et al. | Synthesis of propylene glycol methyl ether over amine modified porous silica by ultrasonic technique | |
| CN205709892U (en) | A kind of Disilicoethane process units |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111214 |