CN106243145B - 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 PDFInfo
- Publication number
- CN106243145B CN106243145B CN201610626664.8A CN201610626664A CN106243145B CN 106243145 B CN106243145 B CN 106243145B CN 201610626664 A CN201610626664 A CN 201610626664A CN 106243145 B CN106243145 B CN 106243145B
- Authority
- CN
- China
- Prior art keywords
- silicon powder
- fixed bed
- catalyst
- trimethoxy silane
- reaction
- 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.)
- Active
Links
Classifications
-
- 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 for refering in particular to fixed bed reaction synthesizing trimethoxy silane.It is directly reacted and is obtained under Cu-series catalyst effect with methanol by silicon powder, it is characterized by: being pre-processed to silicon power raw material and catalyst, by stannous chloride, eliminate surface silica dioxide silicon powder and copper oxide mixed grinding, screening after carry out microwave treatment, by silicon powder-catalyst mixture tabletting, sieving after processing, silicon powder-catalyst mixture is obtained；Silicon powder-catalyst mixture is placed in fixed bed reactors and carries out gas phase catalytic reaction with methanol.Fixed bed reactors production capacity used by notable feature of the invention is big, easy to operate.Catalyst has good catalytic activity and stability during the reaction.
Description
Technical field
The present invention relates to trimethoxy silane synthesis technical fields, refer in particular to a kind of fixed bed reaction synthesizing trimethoxy silane
Method, belong to chemical organic catalysis field.
Background technique
Trimethoxy silane (abbreviation TMS) is the important source material for producing silane coupling agent etc., prepares organosilicon material
One of base stock.It had not only contained hydrolyzable siloxanes key, but also had active si-h bond, can carry out a series of anti-
It answers, such as combined polymerization, copolycondensation, disproportionation reaction, a series of downstream product of high added values is made.These products are widely used in
The starting material of coupling agent processed, textile fabric surface treatment agent, insulation agent etc..
At present industrially, trimethoxy silane is obtained, this complex process, yield by trichlorosilane and methanol reaction
It is low, in reaction process with a large amount of HCl generate, corrode equipment, pollute environment, higher cost, and product separating-purifying compared with
It is difficult.Research finds that trimethoxy silane can directly be reacted under copper catalyst effect by silicon powder with methanol and obtains, and reacts
Formula are as follows:
Si+CH3OH→HSi(OCH3)3+H2
The reaction biggest advantage is that molecule utilization rate is high, process route environmental protection.Existing research is essentially all use
The shortcomings that liquid phase reactor and intermittent reaction device, intermittent reaction device, is that production capacity is weak, is not suitable for continuously, and intermittent reaction
Middle reaction solution is too long with catalyst contact time, and target product selectivity is caused to decline.Therefore research and development are applied to the reaction
Successive reaction be of great significance.
Catalyst occupies especially important status, classical copper System Catalyst in Direct Synthesis of Trialkoxysilane
It is most effective most common catalyst in current all proof catalyst, in copper catalysts, the catalytic activity of CuCl
Highest.Currently, it when selecting catalyst system, is worth noting there are two trend: first is that using co-catalyst, second is that addition activity
Agent.Co-catalyst shows 3 aspects to the effect of catalyst: (1) reaction activity reduced, induction and reaction speed are accelerated,
To improve reaction spatiotemporal efficiency；(2) reaction selectivity is improved, side reaction is reduced and generates, obtain more purpose products；(3)
For currently used more CuCl, help to reduce its chlorinty.Further, since the silica on silicon power raw material surface
Layer can hinder reaction to carry out, and silicon power raw material has that solid affixed touching is bad with the cuprous chloride catalyst used, therefore
Silicon power raw material and catalyst are pre-processed, it is possible to reduce the pot-life of reaction increases reactivity.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of fixed bed reaction synthesizing trimethoxy silane, and this method is with silicon powder
It is raw material with methanol, using Cu-series catalyst, this method is suitable for atmospheric fixed bed reactor.
A kind of method of fixed bed reaction synthesizing trimethoxy silane is straight under Cu-series catalyst effect by silicon powder and methanol
Reversed answer obtains, it is characterised in that: pre-processes to silicon power raw material and catalyst, by stannous chloride, eliminates surface two
Microwave treatment is carried out after the silicon powder of silica and copper oxide mixed grinding, screening, by silicon powder-catalyst mixture pressure after processing
Piece, sieving obtain silicon powder-catalyst mixture；Silicon powder-catalyst mixture is placed in fixed bed reactors and is carried out with methanol
Gas phase catalytic reaction.
The present invention prepares silicon powder-catalyst mixture, silicon powder-catalyst mixture using polishing and Microwave Pretreatment
In contain silicon powder, copper oxide, stannous chloride, the quality of copper oxide and stannous chloride and silicon powder is respectively 1-3% and 1- than range
5%, preparation step is as follows:
(1) silicon powder is pre-processed first with hydrofluoric acid, removes the silica of silicon powder surface: taking a certain amount of silicon powder
As in plastic beaker, it is added and is stirred to react 5 minutes with the hydrofluoric acid of silicon powder same volume, reactant is first then used into deionization
Water uses ethanol washing again, and the silicon powder after washing is placed in the dry 12h of 60 DEG C of vacuum ovens and stand-by silicon powder is made.
(2) silicon powder, copper oxide, stannous chloride for weighing certain mass are placed in mortar and grind, and are sieved with the sieve of 180 mesh
Point, the silicon powder of sieving-catalyst mixture is moved into micro-wave oven, microwave treatment 5min, by pretreated silicon powder-catalyst
Mixture crosses 40-60 sieve, spare silicon powder-catalyst mixture is made in 12MPa tabletting.
(3) by methanol, (200 DEG C of gasification temperature) entrance is mounted with silicon powder-catalyst described in step (2) after overflash
Gas phase catalytic reaction is carried out 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 carries out under normal pressure, 220-260 DEG C of reaction temperature,
Continuous sampling l h under given temperature, ice-water bath condensation are collected product and are analyzed with gas-chromatography.
Fixed bed reactors production capacity used by notable feature of the invention is big, easy to operate.During the reaction
Catalyst has good catalytic activity and stability.For example, using catalyst of the invention, 240 DEG C of reaction items of reaction temperature
Under part, the conversion per pass of methanol can reach 73%, and the selection performance of trimethoxy silane reaches 85%.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described
Embodiment 1
(1) silicon powder is pre-processed first with hydrofluoric acid, removes the silica of silicon powder surface.Take the silicon powder of 10g extremely
In plastic beaker, it is added and is stirred to react 5min with the hydrofluoric acid of silicon powder same volume, reactant is first then used into deionized water
Ethanol washing is used again, and the silicon powder after washing is placed in the dry 12h of 60 DEG C of vacuum ovens and stand-by silicon powder is made.
(2) 5g silicon powder, 0.15g stannous chloride, 0.05g copper oxide are weighed to be placed in mortar and grind, is sieved with the sieve of 180 mesh
Point, the silicon powder of sieving-catalyst mixture is moved into micro-wave oven, microwave treatment 5min, by pretreated silicon powder-catalyst
Mixture tabletting crosses 40-60 sieve, spare silicon powder-catalyst mixture is made.
(3) by methanol, (200 DEG C of gasification temperature) entrance is mounted with silicon powder-catalyst described in step (2) after overflash
Gas phase catalytic reaction is carried out 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 carries out under normal pressure, 220-260 DEG C of reaction temperature, is being given
Determine continuous sampling l h at temperature, ice-water bath condensation is collected product and analyzed with gas-chromatography.It is catalyzed the result such as following table of reaction
It is shown:
The methanol conversion and TMS selectivity of 1. 3%CuCl-1%CuO of table catalysis reaction
Embodiment 2
With embodiment 1, the mass ratio of CuCl in catalyst and Si powder is only changed into 1%, the result for being catalyzed reaction is as follows
Shown in table:
The methanol conversion and TMS selectivity of 2. 1%CuCl-1%CuO of table catalysis reaction
Embodiment 3
With embodiment 1, the mass ratio of CuCl in catalyst and Si powder is only changed into 5%, the result for being catalyzed reaction is as follows
Shown in table:
The methanol conversion and TMS selectivity of 3. 5%CuCl-1%CuO of table catalysis reaction
Embodiment 4
With embodiment 1, the mass ratio of CuO in catalyst and Si powder is only changed into 2%, is catalyzed the result such as following table of reaction
It is shown:
The methanol conversion and TMS selectivity of 4. 3%CuCl-2%CuO of table catalysis reaction
Embodiment 5
With embodiment 1, the mass ratio of CuO in catalyst and Si powder is only changed into 3%, is catalyzed the result such as following table of reaction
It is shown:
The methanol conversion and TMS selectivity of 5. 3%CuCl-3%CuO of table catalysis reaction
Embodiment 6
With embodiment 1, the sample introduction flow of methanol is only changed into 4mL/h, the result for being catalyzed reaction is as shown in the table:
The methanol conversion and TMS selectivity of 6. 3%CuCl-1%CuO of table catalysis reaction
Claims (7)
1. a kind of method of fixed bed reaction synthesizing trimethoxy silane, using silicon powder and methanol as raw material, using Cu-series catalyst,
Suitable for atmospheric fixed bed reactor, is directly reacted and obtained under Cu-series catalyst effect with methanol by silicon powder, feature exists
In: silicon power raw material and catalyst are pre-processed, by stannous chloride, eliminate the silicon powder of surface silica dioxide and copper oxide mixes
Microwave treatment is carried out after closing grinding, screening, by silicon powder-catalyst mixture tabletting, sieving after processing, obtains silicon powder-catalyst
Mixture；Silicon powder-catalyst mixture is placed in fixed bed reactors and carries out gas phase catalytic reaction with methanol；Using polishing
Silicon powder-catalyst mixture is prepared with Microwave Pretreatment, contains silicon powder, copper oxide, protochloride in silicon powder-catalyst mixture
The quality of copper, copper oxide and stannous chloride and silicon powder is respectively 1-3% and 1-5% than range.
2. a kind of method of fixed bed reaction synthesizing trimethoxy silane as described in claim 1, it is characterised in that: copper oxide
It than range is respectively 1% and 5% with the quality of stannous chloride and silicon powder.
3. a kind of method of fixed bed reaction synthesizing trimethoxy silane as described in claim 1, it is characterised in that specific system
It is standby that steps are as follows:
(1) silicon powder is pre-processed first with hydrofluoric acid, removes the silica of silicon powder surface: take a certain amount of silicon powder as
In plastic beaker, be added and be stirred to react 5 minutes with the hydrofluoric acid of silicon powder same volume, then by reactant first with deionized water again
With ethanol washing, the silicon powder after washing is placed in the dry 12h of 60 DEG C of vacuum ovens and stand-by silicon powder is made；
(2) weigh pretreated silicon powder, the copper oxide of silicon powder quality 1-3%, silicon powder quality 1-5% stannous chloride be placed in and grind
It is ground in alms bowl, is sieved, the silicon powder of sieving-catalyst mixture is moved into micro-wave oven, microwave treatment with the sieve of 180 mesh
5min crosses 40-60 sieve, spare silicon powder-catalysis is made by pretreated silicon powder-catalyst mixture in 12MPa tabletting
Agent composition.
4. a kind of method of fixed bed reaction synthesizing trimethoxy silane as described in claim 1, it is characterised in that: by methanol
Enter in the fixed bed reactors for being mounted with the silicon powder-catalyst mixture after gasification and carry out gas phase catalytic reaction,
Middle loaded catalyst is 2g, sample introduction flow velocity 4-8mL/h, carrier gas N2Flow velocity is 20ml/min, and reaction carries out under normal pressure, is reacted
220-260 DEG C of temperature, continuous sampling l h, ice-water bath condensation are collected product and are analyzed with gas-chromatography at a given temperature.
5. a kind of method of fixed bed reaction synthesizing trimethoxy silane as claimed in claim 4, it is characterised in that: methanol
Gasification temperature is 200 DEG C.
6. a kind of method of fixed bed reaction synthesizing trimethoxy silane as claimed in claim 4, it is characterised in that: fixed bed
Reactor long 20cm, internal diameter 0.5cm.
7. a kind of method of fixed bed reaction synthesizing trimethoxy silane as claimed in claim 4, it is characterised in that: reaction temperature
240 DEG C of degree, sample introduction flow velocity 4mL/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610626664.8A CN106243145B (en) | 2016-08-03 | 2016-08-03 | A kind of method of fixed bed reaction synthesizing trimethoxy silane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610626664.8A CN106243145B (en) | 2016-08-03 | 2016-08-03 | A kind of method of fixed bed reaction synthesizing trimethoxy silane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106243145A CN106243145A (en) | 2016-12-21 |
| CN106243145B true CN106243145B (en) | 2019-10-01 |
Family
ID=57607112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610626664.8A Active CN106243145B (en) | 2016-08-03 | 2016-08-03 | A kind of method of fixed bed reaction synthesizing trimethoxy silane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106243145B (en) |
Families Citing this family (3)
| 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 |
| CN114505084B (en) * | 2022-01-18 | 2023-09-12 | 石河子大学 | Pretreatment method of cuprous chloride catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2653700B2 (en) * | 1989-07-12 | 1997-09-17 | 東燃化学株式会社 | Method for producing trimethoxysilane |
| CN101353356A (en) * | 2008-09-22 | 2009-01-28 | 哈尔滨工业大学 | Method for directly synthesizing trialkoxysilane |
-
2016
- 2016-08-03 CN CN201610626664.8A patent/CN106243145B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Mechanism of Active-Site Formation in Copper-Catalyzed Synthesis of Trimethoxysilane by the Reaction of Silicon with Methanol;Suzuki et al.;《JOURNAL OF CATALYSIS》;19910111;摘要 * |
| 直接法合成三烷氧基硅烷的研究;冀鸽;《中国优秀硕士学位论文全文数据库工程科技I辑》;20111215;第13-14页2.2.2节实验步骤、第36页第4.1.1.1节，第42页最后一段、第6页1.3.1节实验装置、第8页1.3.3.3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106243145A (en) | 2016-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243145B (en) | A kind of method of fixed bed reaction synthesizing trimethoxy silane | |
| Zhou et al. | Functionalized IRMOF-3 as efficient heterogeneous catalyst for the synthesis of cyclic carbonates | |
| CN105268463B (en) | A kind of nitrogen-doped carbon/carbon nitride photocatalyst material and its one-step method for synthesizing | |
| CN105664952B (en) | Copper oxide-zinc oxide composite catalyst, preparation method and purposes | |
| CN105944722B (en) | A kind of Cu-Cu2O-CuO ternary copper catalyst and its preparation method and application | |
| Dai et al. | Coexistence of Cu (ii) and Cu (i) in Cu ion-doped zeolitic imidazolate frameworks (ZIF-8) for the dehydrogenative coupling of silanes with alcohols | |
| CN104693224B (en) | There is cadmium metal complex of catalysis light degradation dye property and preparation method thereof | |
| CN102225947A (en) | Preparation method of polyether modified siloxane | |
| CN103288865B (en) | A kind of method utilizing organic silicon azeotrope to produce tetraethoxy | |
| CN103224511A (en) | Hydrophobic-surface treatment agent and preparation method thereof | |
| CN101817723A (en) | Method for preparing chloroethylene by catalytic reforming | |
| CN103846101B (en) | A kind of C-SiC catalyst and Synthesis and applications thereof | |
| CN109453762A (en) | A kind of preparation method and application of modified clay mine loaded palladium catalyst | |
| Marciniec et al. | Synthesis, Characterization, and Catalytic Activity of a Well‐Defined Rhodium Siloxide Complex Immobilized on Silica | |
| Su et al. | Approach to generating the right active phase in the “Direct” synthesis of trimethoxysilanes using the CuCl-Cu2O catalyst | |
| CN105906659A (en) | Dimethyldichlorosilance purification process and system | |
| CN101671356B (en) | Hydrosilylation of rhodium complex catalyzed alkene in room-temperature ion liquid/super-critical CO2 medium | |
| Vivien et al. | Mn 2 (CO) 10 and UV light: a promising combination for regioselective alkene hydrosilylation at low temperature | |
| CN104387413A (en) | Production method for preparing trialkoxysilane by adopting direct method | |
| CN106349273A (en) | Trimethoxysilane synthesis method | |
| CN112456500A (en) | Preparation method of trichlorosilane | |
| CN105668605B (en) | A kind of nest like has the preparation method of high specific surface area and mesoporous ceria | |
| CN101703929A (en) | Synthesis and characterization of MCM loaded Pt catalyst and microwave catalytic hydrosilylation of octene | |
| CN102924497A (en) | Method for preparing saturated hydrocarbyl alkoxy silane | |
| CN104689841A (en) | Synthesis and characterization of MCM loaded Pt catalyst and microwave catalytic hydrosilylation of octene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200601 Address after: 215500 No.13, Caotang Road, Changshu, Suzhou, Jiangsu Province Patentee after: Changshu intellectual property operation center Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: JIANGSU University |
|
| TR01 | Transfer of patent right | ||
| CP02 | Change in the address of a patent holder |
Address after: 215500 5th floor, building 4, 68 Lianfeng Road, Changfu street, Changshu City, Suzhou City, Jiangsu Province Patentee after: Changshu intellectual property operation center Co.,Ltd. Address before: No.13 caodang Road, Changshu City, Suzhou City, Jiangsu Province Patentee before: Changshu intellectual property operation center Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211125 Address after: 215500 Jiangsu fluorine chemical industrial park, Changshu City, Suzhou City, Jiangsu Province (No.16 Haifeng Road, Haiyu town Fluorine Chemical Industrial Park) Patentee after: CHANGSHU 3F ZHENFU NEW MATERIALS Co.,Ltd. Address before: 215500 5th floor, building 4, 68 Lianfeng Road, Changfu street, Changshu City, Suzhou City, Jiangsu Province Patentee before: Changshu intellectual property operation center Co.,Ltd. |
|
| TR01 | Transfer of patent right |