CN106243145A - A kind of method of fixed bed reaction synthesizing trimethoxy silane - Google Patents

A kind of method of fixed bed reaction synthesizing trimethoxy silane Download PDF

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Publication number
CN106243145A
CN106243145A CN201610626664.8A CN201610626664A CN106243145A CN 106243145 A CN106243145 A CN 106243145A CN 201610626664 A CN201610626664 A CN 201610626664A CN 106243145 A CN106243145 A CN 106243145A
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silica flour
fixed bed
catalyst
reaction
trimethoxy silane
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CN201610626664.8A
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CN106243145B (en
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卢志鹏
殷恒波
薛武平
王爱丽
胡靖�
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CHANGSHU 3F ZHENFU NEW MATERIALS Co.,Ltd.
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Jiangsu University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Abstract

The present invention relates to trimethoxy silane synthesis technical field, a kind of method refering in particular to fixed bed reaction synthesizing trimethoxy silane.By silica flour and methanol under Cu-series catalyst effect direct reaction and obtain, it is characterized in that: silicon power raw material and catalyst are carried out pretreatment, microwave treatment is carried out after the silica flour by Cu-lyt., eliminating surface silica dioxide and copper oxide mixed grinding, screening, by silica flour catalyst mixture tabletting after process, sieve, obtain silica flour catalyst mixture；Silica flour catalyst mixture is placed in fixed bed reactors and carries out gas phase catalytic reaction with methanol.The fixed bed reactors production capacity that the marked feature of the present invention is used is big, easy and simple to handle.In course of reaction, catalyst has good catalysis activity and stability.

Description

A kind of method of fixed bed reaction synthesizing trimethoxy silane
Technical field
The present invention relates to trimethoxy silane synthesis technical field, refer in particular to a kind of fixed bed reaction synthesizing trimethoxy silane Method, belong to chemistry organic catalysis field.
Background technology
Trimethoxy silane (being called for short TMS) is the important source material producing silane coupler etc., prepares organosilicon material One of base stock.It had both contained hydrolyzable siloxane bond, had again active si-h bond, can carry out a series of instead Should, as combined polymerization, copolycondensation, disproportionation etc. are reacted, prepare the downstream product of a series of high added values.These products are widely used in The initiation material of coupling agent processed, textile fabric surface treatment agent, insulation agent etc..
The most industrially, trimethoxy silane is to be reacted by trichlorosilane and methanol and obtained, this complex process, yield Low, course of reaction produces with substantial amounts of HCl, etching apparatus, pollute environment, relatively costly, and also product separating-purifying is relatively Difficulty.Research find trimethoxy silane can by silica flour and methanol under copper catalyst effect direct reaction and obtain, react Formula is:
Si+CH3OH→HSi(OCH3)3+H2
The advantage of this reaction maximum is that molecule utilization rate is high, process route environmental protection.Existing research is essentially all employing Liquid phase reactor and intermittent reaction device, the shortcoming of intermittent reaction device is that production capacity is weak, is not suitable for continuously, and intermittent reaction Middle reactant liquor is long with catalyst contact time, causes target product selectivity to decline.Therefore research and development are applied to this reaction Successive reaction be significant.
Catalyst occupies the status of particular importance, classical copper System Catalyst in Direct Synthesis of Trialkoxysilane It is most effective most common catalyst in current all proof catalyst, in Cu-series catalyst, the catalysis activity of CuCl The highest.Currently, when selecting catalyst system and catalyzing, two trend are had to merit attention: one is to use promoter, and two is to add activity Agent.Promoter shows 3 aspects to the effect of catalyst: (1) reduces reaction activity, accelerates induction and response speed, Thus improve reaction spatiotemporal efficiency；(2) improve reaction selectivity, reduce side reaction and produce, obtain more purpose product；(3) For currently used more CuCl, contribute to reducing its chlorinty.Additionally, due to the silicon dioxide on silicon power raw material surface Layer can hinder reaction to carry out, and the cuprous chloride catalyst of silicon power raw material and use exists the problem of loose contact admittedly, therefore Silicon power raw material and catalyst are carried out pretreatment, it is possible to reduce the pot-life of reaction, increase reactivity.
Summary of the invention
A kind of method that it is an object of the invention to provide fixed bed reaction synthesizing trimethoxy silane, the method is with silica flour Being raw material with methanol, use Cu-series catalyst, the method is applicable to atmospheric fixed bed reactor.
A kind of method of fixed bed reaction synthesizing trimethoxy silane, by silica flour and methanol under Cu-series catalyst effect straight Connect reaction and obtain, it is characterised in that: silicon power raw material and catalyst are carried out pretreatment, by Cu-lyt., eliminates surface two Microwave treatment is carried out, by silica flour-catalyst mixture pressure after process after the silica flour of silicon oxide and copper oxide mixed grinding, screening Sheet, sieve, obtain silica flour-catalyst mixture；Silica flour-catalyst mixture is placed in fixed bed reactors and carries out with methanol Gas phase catalytic reaction.
The present invention use polishing and microwave pretreatment to prepare silica flour-catalyst mixture, silica flour-catalyst mixture In containing silica flour, copper oxide, Cu-lyt., copper oxide and Cu-lyt. are respectively 1-3% and 1-with the quality of silica flour than scope 5%, preparation process is as follows:
(1) first silica flour Fluohydric acid. is carried out pretreatment, remove the silicon dioxide of silicon powder surface: take a certain amount of silica flour As in plastic beaker, add the Fluohydric acid. stirring with silica flour same volume and react 5 minutes, then reactant is first used deionization Water is again by washing with alcohol, and the silica flour after washing is placed in 60 DEG C of vacuum drying ovens and is dried 12h and prepares stand-by silica flour.
(2) weigh the silica flour of certain mass, copper oxide, Cu-lyt. are placed in mortar grinding, sieve with the sieve of 180 mesh Point, the silica flour-catalyst mixture sieved is moved in microwave oven, microwave treatment 5min, by pretreated silica flour-catalyst Mixture, in 12MPa tabletting, crosses 40-60 sieve, prepares standby silica flour-catalyst mixture.
(3) by methanol, after overflash, (gasification temperature 200 DEG C) entrance is mounted with silica flour-catalyst described in step (2) Carrying out gas phase catalytic reaction in the fixed bed reactors (long 20cm, internal diameter 0.5cm) of mixture, wherein loaded catalyst is 2g, sample introduction flow velocity 4-8mL/h, carrier gas N2Flow velocity is 20ml/min, and reaction is carried out at ambient pressure, reaction temperature 220-260 DEG C, Continuous sampling l h at given temperature, ice-water bath condensation is collected product gas chromatogram and is analyzed.
The fixed bed reactors production capacity that the marked feature of the present invention is used is big, easy and simple to handle.In course of reaction Catalyst has good catalysis activity and stability.Such as, the catalyst of the present invention, reaction temperature 240 DEG C reaction bar are used Under part, the conversion per pass of methanol can reach 73%, and the selection performance of trimethoxy silane reaches 85%.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention will be further described
Embodiment 1
(1) first silica flour Fluohydric acid. is carried out pretreatment, remove the silicon dioxide of silicon powder surface.Take the silica flour of 10g extremely In plastic beaker, add the Fluohydric acid. stirring reaction 5min with silica flour same volume, then reactant is first used deionized water Again by washing with alcohol, the silica flour after washing is placed in 60 DEG C of vacuum drying ovens and is dried 12h and prepares stand-by silica flour.
(2) weigh 5g silica flour, 0.15g Cu-lyt., 0.05g copper oxide are placed in mortar grinding, sieve with the sieve of 180 mesh Point, the silica flour-catalyst mixture sieved is moved in microwave oven, microwave treatment 5min, by pretreated silica flour-catalyst Mixture tabletting, crosses 40-60 sieve, prepares standby silica flour-catalyst mixture.
(3) by methanol, after overflash, (gasification temperature 200 DEG C) entrance is mounted with silica flour-catalyst described in step (2) Carrying out gas phase catalytic reaction in the fixed bed reactors (long 20cm, internal diameter 0.5cm) of mixture, wherein loaded catalyst is 2g, sample introduction flow velocity 8mL/h, carrier gas N2Flow velocity is 20ml/min, and reaction is carried out at ambient pressure, and reaction temperature 220-260 DEG C is being given Continuous sampling l h under fixed temperature, ice-water bath condensation is collected product gas chromatogram and is analyzed.The result of catalytic reaction such as following table Shown in:
The methanol conversion of table 1. 3%CuCl-1%CuO catalytic reaction and TMS selectivity
Embodiment 2
With embodiment 1, only the mass ratio of CuCl Yu Si powder in catalyst being changed into 1%, the result of catalytic reaction is as follows Shown in table:
The methanol conversion of table 2. 1%CuCl-1%CuO catalytic reaction and TMS selectivity
Embodiment 3
With embodiment 1, only the mass ratio of CuCl Yu Si powder in catalyst being changed into 5%, the result of catalytic reaction is as follows Shown in table:
The methanol conversion of table 3. 5%CuCl-1%CuO catalytic reaction and TMS selectivity
Embodiment 4
With embodiment 1, only the mass ratio of CuO Yu Si powder in catalyst is changed into 2%, the result of catalytic reaction such as following table Shown in:
The methanol conversion of table 4. 3%CuCl-2%CuO catalytic reaction and TMS selectivity
Embodiment 5
With embodiment 1, only the mass ratio of CuO Yu Si powder in catalyst is changed into 3%, the result of catalytic reaction such as following table Shown in:
The methanol conversion of table 5. 3%CuCl-3%CuO catalytic reaction and TMS selectivity
Embodiment 6
With embodiment 1, only the sample introduction flow of methanol being changed into 4mL/h, the result of catalytic reaction is as shown in the table:
The methanol conversion of table 6. 3%CuCl-1%CuO catalytic reaction and TMS selectivity

Claims (8)

1. a method for fixed bed reaction synthesizing trimethoxy silane, with silica flour and methanol as raw material, uses Cu-series catalyst, Be applicable to atmospheric fixed bed reactor, by silica flour and methanol under Cu-series catalyst effect direct reaction and obtain, its feature exists In: silicon power raw material and catalyst are carried out pretreatment, and the silica flour and the copper oxide that by Cu-lyt., eliminate surface silica dioxide mix Close grind, screening after carry out microwave treatment, after process by silica flour-catalyst mixture tabletting, sieve, obtain silica flour-catalyst Mixture；Silica flour-catalyst mixture is placed in fixed bed reactors and carries out gas phase catalytic reaction with methanol.
The method of a kind of fixed bed reaction synthesizing trimethoxy silane the most as claimed in claim 1, it is characterised in that: use and grind Mill method and microwave pretreatment prepare silica flour-catalyst mixture, containing silica flour, copper oxide, chlorine in silica flour-catalyst mixture Changing cuprous, copper oxide and Cu-lyt. are respectively 1-3% and 1-5% with the quality of silica flour than scope.
The method of a kind of fixed bed reaction synthesizing trimethoxy silane the most as claimed in claim 2, it is characterised in that: copper oxide It is respectively 1% and 5% than scope with the quality of Cu-lyt. with silica flour.
The method of a kind of fixed bed reaction synthesizing trimethoxy silane the most as claimed in claim 2, it is characterised in that specifically make Standby step is as follows:
(1) first silica flour Fluohydric acid. is carried out pretreatment, remove silicon powder surface silicon dioxide: take a certain amount of silica flour as In plastic beaker, add the Fluohydric acid. with silica flour same volume and stir reaction 5 minutes, then by reactant first with deionized water again By washing with alcohol, the silica flour after washing is placed in 60 DEG C of vacuum drying ovens and is dried 12h and prepares stand-by silica flour；
(2) weigh the silica flour of certain mass, copper oxide, Cu-lyt. are placed in mortar grinding, sieve with the sieve of 180 mesh, will The silica flour sieved-catalyst mixture moves in microwave oven, microwave treatment 5min, by pretreated silica flour-catalyst mixing Thing, in 12MPa tabletting, crosses 40-60 sieve, prepares standby silica flour-catalyst mixture.
The method of a kind of fixed bed reaction synthesizing trimethoxy silane the most as claimed in claim 1, it is characterised in that: by methanol Enter to be mounted with in the fixed bed reactors of described silica flour-catalyst mixture after gasification and carry out gas phase catalytic reaction, its Middle loaded catalyst is 2g, sample introduction flow velocity 4-8mL/h, carrier gas N2Flow velocity is 20ml/min, and reaction is carried out at ambient pressure, reaction Temperature 220-260 DEG C, at a given temperature continuous sampling lh, ice-water bath condensation is collected product gas chromatogram and is analyzed.
The method of a kind of fixed bed reaction synthesizing trimethoxy silane the most as claimed in claim 5, it is characterised in that: methanol Gasification temperature is 200 DEG C.
The method of a kind of fixed bed reaction synthesizing trimethoxy silane the most as claimed in claim 5, it is characterised in that: fixed bed The long 20cm of reactor, internal diameter 0.5cm.
The method of a kind of fixed bed reaction synthesizing trimethoxy silane the most as claimed in claim 5, it is characterised in that: reaction temperature Spend 240 DEG C, sample introduction flow velocity 4mL/h.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107011373A (en) * 2017-05-16 2017-08-04 江苏大学 A kind of CuCl/Cu composite catalysts catalysis methanol reacts the method that direct method prepares trimethoxy silane with silica flour
CN107216348A (en) * 2017-05-16 2017-09-29 江苏大学 A kind of method that direct method prepares tetramethoxy-silicane
CN114505084A (en) * 2022-01-18 2022-05-17 石河子大学 Pretreatment method of cuprous chloride catalyst

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Publication number Priority date Publication date Assignee Title
JPH0344393A (en) * 1989-07-12 1991-02-26 Tonen Chem Corp Production of trimethoxysilane
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CN101501044A (en) * 2006-06-09 2009-08-05 莫门蒂夫性能材料股份有限公司 Process for the direct synthesis of trialkoxysilane
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CN104387413A (en) * 2014-11-03 2015-03-04 湖北武大有机硅新材料股份有限公司 Production method for preparing trialkoxysilane by adopting direct method

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JPH0344393A (en) * 1989-07-12 1991-02-26 Tonen Chem Corp Production of trimethoxysilane
CN101501044A (en) * 2006-06-09 2009-08-05 莫门蒂夫性能材料股份有限公司 Process for the direct synthesis of trialkoxysilane
CN101541814A (en) * 2006-12-01 2009-09-23 罗斯顿家族有限责任公司 Process for preparation of alkoxysilanes
CN101353356A (en) * 2008-09-22 2009-01-28 哈尔滨工业大学 Method for directly synthesizing trialkoxysilane
CN104387413A (en) * 2014-11-03 2015-03-04 湖北武大有机硅新材料股份有限公司 Production method for preparing trialkoxysilane by adopting direct method

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Title
SUZUKI ET AL.: "Mechanism of Active-Site Formation in Copper-Catalyzed Synthesis of Trimethoxysilane by the Reaction of Silicon with Methanol", 《JOURNAL OF CATALYSIS》 *
冀鸽: "直接法合成三烷氧基硅烷的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107011373A (en) * 2017-05-16 2017-08-04 江苏大学 A kind of CuCl/Cu composite catalysts catalysis methanol reacts the method that direct method prepares trimethoxy silane with silica flour
CN107216348A (en) * 2017-05-16 2017-09-29 江苏大学 A kind of method that direct method prepares tetramethoxy-silicane
CN114505084A (en) * 2022-01-18 2022-05-17 石河子大学 Pretreatment method of cuprous chloride catalyst
CN114505084B (en) * 2022-01-18 2023-09-12 石河子大学 Pretreatment method of cuprous chloride catalyst

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