CN113956275B - Method for preparing alkoxy silane from organic silicon byproducts - Google Patents
Method for preparing alkoxy silane from organic silicon byproducts Download PDFInfo
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- CN113956275B CN113956275B CN202111172255.2A CN202111172255A CN113956275B CN 113956275 B CN113956275 B CN 113956275B CN 202111172255 A CN202111172255 A CN 202111172255A CN 113956275 B CN113956275 B CN 113956275B
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- alkoxy silane
- organic silicon
- hydrolysate
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- 239000006227 byproduct Substances 0.000 title claims abstract description 53
- -1 alkoxy silane Chemical compound 0.000 title claims abstract description 40
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000012043 crude product Substances 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000413 hydrolysate Substances 0.000 claims description 37
- 239000000919 ceramic Substances 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000005048 methyldichlorosilane Substances 0.000 claims description 10
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 9
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 9
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 9
- 239000005049 silicon tetrachloride Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005052 trichlorosilane Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000012784 inorganic fiber Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 30
- 235000019441 ethanol Nutrition 0.000 description 26
- 238000000605 extraction Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000005046 Chlorosilane Substances 0.000 description 9
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- 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
- C07F7/04—Esters of silicic acids
Abstract
The invention relates to the technical field of utilization of organic silicon byproducts, and discloses a method for preparing alkoxy silane from organic silicon byproducts, which aims to solve the problems that the organic silicon byproducts are high in treatment cost and cannot be effectively utilized in the prior art, and comprises the following steps: adding the organic silicon by-product and the vaporized alcohol into a reaction tower, and enabling the organic silicon by-product and the alcohol to react under the catalysis of a filler loaded with a dehydrogenation catalyst; under the action of a condenser at the top of the reaction tower and a kettle-type reboiler at the bottom of the reaction tower, unreacted raw materials circularly react in the reaction tower; and rectifying the crude product of the alkoxy silane collected in the kettle-type reboiler to obtain the finished product of the alkoxy silane. The invention prepares single alkoxy silane through the organic silicon byproduct and alcohol, solves the problem that the organic silicon byproduct is difficult to be utilized, has higher economic benefit and social benefit, realizes continuous production of the alkoxy silane prepared by the organic silicon byproduct, and has low energy consumption and high purity of the product.
Description
Technical Field
The invention relates to the technical field of utilization of organic silicon byproducts, in particular to a method for preparing alkoxy silane from organic silicon byproducts.
Background
In recent years, the domestic organosilicon industry rapidly develops, and China becomes the largest organosilicon production country worldwide, and the domestic organosilicon monomer yield accounts for more than 70% of the global yield. With the rapid expansion of the production scale of silicones, a large amount of chlorosilane by-products are produced. Some high-purity chlorosilane byproducts, such as methyltrichlorosilane, silicon tetrachloride and the like, have wide application and large downstream market, but other chlorosilane byproducts, such as methyldichlorosilane, are limited by the downstream market, and a new application needs to be developed to avoid a large backlog of the chlorosilane byproducts and the silicon tetrachloride, so that large treatment cost is generated. In the production and processing process of the organic silicon, a mixture of methyl dichlorosilane and methyl trichlorosilane, a mixture of trichlorosilane and silicon tetrachloride and the like are also generated, and if the mixtures are not treated, the mixtures cannot be reasonably utilized; if these mixtures are subjected to a rectification treatment, high purity chlorosilanes can be obtained which are usable, but the rectification treatment method has high process requirements, high energy consumption and high environmental pollution.
At present, a process technology for preparing methyltrimethoxysilane and methyltriethoxysilane by using methyltrichlorosilane and a process technology for preparing tetramethoxysilane and tetraethoxysilane by using silicon tetrachloride are widely reported, but a technology for preparing a single substance by using a chlorosilane mixture or preparing alkoxysilane without containing silicon hydrogen bonds by using chlorosilane containing silicon hydrogen bonds is rarely reported. The alkoxysilane without the silicon-hydrogen bond has huge market in the industries of room temperature curing silicon rubber, paint, coating, waterproof material, surface treatment and the like, so the technology for preparing the alkoxysilane without the silicon-hydrogen bond from the hydrogen-containing chlorosilane is developed, and the technology has good economic and social benefits for solving the treatment difficulty of the organosilicon byproduct chlorosilane.
For example, "a method for preparing methyltriethoxysilane", disclosed in chinese patent literature, has the publication number CN105131028B, and the steps are as follows: (1) Adding methyldichlorosilane and a catalyst into a reaction kettle, heating to reflux, and dropwise adding absolute ethyl alcohol from the bottom of the reaction kettle under the stirring condition; (2) After the absolute ethyl alcohol is completely dripped, controlling the reaction temperature to be 60+/-1 ℃, continuously reacting for more than 2 hours, refluxing for deacidification, neutralizing sodium ethoxide, and rectifying to obtain the methyltriethoxysilane with the content of more than 99.0 percent. The reaction involved in the preparation method is intermittent reaction, the production efficiency is low, and hydrogen chloride generated in the reaction process is easy to generate side reaction with alcohol in a reaction system.
Disclosure of Invention
The invention provides a method for preparing alkoxy silane by using organosilicon byproducts, which aims to solve the problems of high organosilicon byproduct treatment cost and incapability of effective utilization in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing alkoxysilane from organosilicon byproducts, comprising the steps of:
(A) Adding the organic silicon by-product and the vaporized alcohol into a reaction tower, and keeping a certain temperature in the reaction tower to enable the organic silicon by-product and the alcohol to react under the catalysis of a filler loaded with a dehydrogenation catalyst;
(B) Unreacted vaporization raw materials are subjected to heat exchange through a condenser positioned at the top of the reaction tower and then flow back to the middle part of the reaction tower, crude products of alkoxy silane obtained by reaction are collected into a kettle type reboiler positioned at the bottom of the reaction tower, and the raw materials which are not fully reacted in the kettle type reboiler are vaporized and enter the reaction tower again for reaction;
(C) And rectifying the crude product of the alkoxy silane in the kettle-type reboiler to obtain the finished product of the alkoxy silane.
The invention enables the organic silicon by-product and the alcohol to generate single alkoxy silane under the catalysis of the filler loaded with the dehydrogenation catalyst, the organic silicon by-product and the alcohol fall into a kettle type reboiler at the bottom of the reaction tower after reaction, wherein unreacted raw materials are vaporized and then mixed with newly added organic silicon by-product and alcohol raw materials for reaction again, and hydrogen chloride and hydrogen mixed gas generated by reaction escapes from the top of the reaction tower and is discharged after being treated by a spray absorption system. When the liquid level of the kettle type reboiler is 30-70%, the crude product of the alkoxy silane can be extracted for subsequent rectification treatment. The method can prepare a single organic silicon product with higher use value by taking the organic silicon byproduct as the raw material, the organic silicon product is thoroughly dehydrogenated, the raw material is continuously added in the production process, the product is continuously extracted, the operation is simple, the energy consumption is low, and the yield is high.
Preferably, in the step (a), the organosilicon byproduct is one or two of methyldichlorosilane and methyltrichlorosilane, or one or two of silicon tetrachloride and trichlorosilane, and the alcohol is methanol or ethanol.
In the production process of the organic silicon, the organic silicon byproducts obtained according to different products are respectively a mixture of methyl dichlorosilane and methyl trichlorosilane and a mixture of silicon tetrachloride and trichlorosilane, and the two types of organic silicon byproducts can respectively obtain single organic silicon products through the following four reactions
①CH 3 -SiCl 3 +3ROHCH 3 -Si(OR) 3 +3HCl
②
③SiCl 4 +4ROHSi(OR) 4 +4HCl
④
Preferably, in the step (A), the ratio of the organosilicon by-product to the alcohol is 1 (1-1.3) based on the total number of hydrogen and chlorine atoms directly connected with silicon atoms.
In the reaction of the organosilicon by-product with the alcohol to form the alkoxysilane, RO-groups replace the silicon-bonded hydrogen and chlorine, and thus an alcohol excess of 0-30% is preferred during the preparation. When the reaction raw material is a mixture of methyl dichlorosilane and methyl trichlorosilane, the molar ratio of the organic silicon by-product to alcohol is 1 (3-3.9); when the reaction raw material is a mixture of silicon tetrachloride and trichlorosilane, the molar ratio of the organic silicon byproduct to the alcohol is 1 (4-5.2).
Preferably, in the step (A) and the step (B), the temperature of the reaction tower is 50-100 ℃, and the temperature of the kettle-type reboiler is 50-100 ℃.
Preferably, the filler for supporting the dehydrogenation catalyst used in the step (a) is prepared by the steps of:
(1) Mixing alcohol with water, and then dropwise adding alkoxy silane for hydrolysis reaction to obtain alkoxy silane hydrolysate;
(2) Mixing the alkoxy silane hydrolysate with the dehydrogenation catalyst, adding the filler for impregnation, and drying the impregnated filler to obtain the filler for loading the dehydrogenation catalyst.
The alkoxysilane can be hydrolyzed to generate sticky substances, the alkoxysilane hydrolysate is mixed with the dehydrogenation catalyst, the dehydrogenation catalyst can be loaded on the filler by soaking the alkoxysilane hydrolysate in the filler, and the dehydrogenation catalyst can be fixed on the filler after the alkoxysilane hydrolysate is dried and solidified, so that the dehydrogenation catalyst cannot flow out of the reactor along with raw materials in the process of preparing the alkoxysilane by catalyzing the organosilicon byproducts. Hydroxyl is generated after the alkoxy silane is hydrolyzed, and alkoxy silane hydrolysate is crosslinked by self-polycondensation among the hydroxyl; the rate of the silanol generated by the hydrolysis of the alkoxysilane under the acidic or alkaline condition is high, the alkoxysilane is thoroughly hydrolyzed, the generated silanol contains a plurality of hydroxyl groups, the alkoxysilane hydrolysate forms gel due to the high crosslinking degree, the gel-like alkoxysilane hydrolysate can influence the uniform mixing state of the dehydrogenation catalyst and the alkoxysilane hydrolysate, and the dispersion condition of the dehydrogenation catalyst in the filler is influenced, so that the catalytic efficiency of the filler loaded with the dehydrogenation catalyst in the production process is reduced. The hydrolysis speed of the alkoxy silane in a neutral medium is low, and the hydrolysis degree of the alkoxy silane can be controlled by adding alcohol into a hydrolysis system, so that the condition that the alkoxy silane hydrolysate is condensed into gel is reduced. The alkoxysilane hydrolysate with low crosslinking degree has a micropore structure with larger pore diameter after being dried, so that the influence on the contact between the dehydrogenation catalyst and reactants can be reduced, and the alkoxysilane hydrolysate has good compatibility with the organosilicon byproducts, which is beneficial to the contact between the organosilicon byproducts and the dehydrogenation catalyst on the surface of the alkoxysilane hydrolysate. The alkoxysilane hydrolysate is high temperature resistant and insoluble in ethanol after being dried and cured, and can prolong the service life of the filler loaded with the dehydrogenation catalyst in preparation and production.
Preferably, in the step (1), the mass ratio of the alcohol, the water and the alkoxy silane is 1 (0.02-1): 1, the hydrolysis reaction temperature is 10-100 ℃, and the reaction time is 1-24 hours.
The lower water content in the alkoxysilane hydrolysis reaction system is beneficial to reducing the gel formation condition of silanol condensation.
Preferably, the alkoxysilane hydrolysate obtained in the step (1) includes methyltrialkoxysilane hydrolysate, vinyltrialkoxysilane hydrolysate, phenyltrialkoxysilane hydrolysate and tetraalkoxysilane hydrolysate.
Preferably, in the step (2), the dehydrogenation catalyst is one of nickel sulfate, nickel chloride, nickel carbonate and nickel nitrate, and the filler is one of ceramic filler with holes, metal oxide filler, filler obtained by pressing inorganic fibers and filler obtained by pressing organic fibers.
The nickel-based dehydrogenation catalyst has a good catalytic effect on the reaction related to the invention, wherein the nickel chloride has the best effect. The filler is in a porous shape, and the reaction raw material contacts with the dehydrogenation catalyst fixed in the pore canal when passing through the pore canal.
Preferably, in the step (2), the soaking time is 1-24 hours, the drying temperature is 50-200 ℃, and the drying time is 3-12 hours.
Preferably, in the filler carrying the dehydrogenation catalyst obtained in the step (2), the mass of the dehydrogenation catalyst and the alkoxysilane hydrolysate is 1-20% of that of the filler.
Therefore, the invention has the following beneficial effects: (1) The single alkoxy silane is prepared by the organic silicon byproducts and the alcohol under the action of the catalyst, so that the problem that the organic silicon byproducts are difficult to use is solved, and the economic benefit and the social benefit are higher; (2) Realizes continuous production of the alkoxysilane prepared from the organosilicon byproducts, and has low energy consumption and high purity of the product.
Drawings
FIG. 1 is a schematic view showing a structure of a reaction apparatus used in the present invention, wherein a 1-reaction column, a 2-tank reboiler, a 3-condenser, and a 4-vaporizer are provided.
Detailed Description
The invention is further described with reference to the drawings and the detailed description.
General example the reaction apparatus used in the following example was a reaction tower 1 with a condenser 3, a kettle-type reboiler 2 and a vaporizer 4, the structure of which is shown in fig. 1, the diameter of the reaction tower 1 is four hundred millimeters and sixteen meters high, and the middle of the reaction tower 1 is filled with a filler carrying a dehydrogenation catalyst; the kettle-type reboiler 2 is positioned at the bottom of the reaction tower 1, and the volume of the kettle-type reboiler is one kiloliter; the condenser 3 is positioned at the top of the reaction tower 1, the cooling area is forty square, and the temperature of the cooling liquid is-40 ℃; the feed inlet of the organic silicon byproduct is positioned at the position lower than the tower top by two meters, alcohol enters the reaction tower 1 through the vaporizer 4, the feed inlet of the alcohol is positioned at the position higher than the kettle type reboiler 2 by three meters, and the gas leaving the condenser 3 is discharged after being treated by the spray absorption system.
Example 1
Preparation of a dehydrogenation catalyst-supporting filler: adding 300kg of methanol and 40kg of water into a 1000L hydrolysis kettle, keeping the temperature in the kettle at 50 ℃, dropwise adding 300kg of methyltrimethoxysilane, and keeping the temperature in the kettle at 50 ℃ for continuous stirring reaction for 8 hours after the dropwise adding is finished to obtain an alkoxy silane hydrolysate; adding 30kg of nickel chloride into the hydrolysate, stirring uniformly, then placing the hydrolysate of the alkoxy silane into an impregnating tank, placing the ceramic filler with holes into the impregnating tank to completely impregnate the ceramic filler with the ceramic filler for 16 hours, taking out the filler, and placing the filler into a dryer to dry for 4 hours at 100 ℃ to obtain the filler for loading the dehydrogenation catalyst.
Preparation of methyltrimethoxysilane: methyl dichlorosilane enters a reaction tower at a flow rate of 300k/kg, methanol enters the reaction tower after being gasified, and the flow rate is 300k/kg; maintaining the temperature of the kettle type reboiler at 100 ℃ and the temperature of the middle part of the reaction tower at 70 ℃; when the liquid level in the kettle-type reboiler exceeds 30%, crude product extraction is started, and the liquid level of the kettle-type reboiler is kept at 50% during extraction.
Crude products at the beginning of extraction are detected: 86.4% of methyltrimethoxysilane, 0.4% of methyldimethoxyhydrosilane, 12.1% of methanol and 1.1% of other components; the crude product is rectified to obtain the methyltrimethoxysilane with the purity of 99 percent.
The crude product 50 hours after the start of extraction was detected: 86.5% of methyltrimethoxysilane, 0.3% of methyldimethoxyhydrosilane, 12.2% of methanol and 1.0% of other components; the crude product is rectified to obtain the methyltrimethoxysilane with the purity of 99 percent.
Example 2
Preparation of a dehydrogenation catalyst-supporting filler: adding 300kg of methanol and 40kg of water into a 1000L hydrolysis kettle, keeping the temperature in the kettle at 50 ℃, dropwise adding 300kg of methyltrimethoxysilane, and keeping the temperature in the kettle at 50 ℃ for continuous stirring reaction for 8 hours after the dropwise adding is finished to obtain an alkoxy silane hydrolysate; adding 30kg of nickel chloride into the hydrolysate, stirring uniformly, then placing the hydrolysate of the alkoxy silane into an impregnating tank, placing the ceramic filler with holes into the impregnating tank to completely impregnate the ceramic filler with the ceramic filler for 16 hours, taking out the filler, and placing the filler into a dryer to dry for 4 hours at 100 ℃ to obtain the filler for loading the dehydrogenation catalyst.
Preparation of methyltrimethoxysilane: 30% of methyl trichlorosilane and 70% of methyl trichlorosilane enter a reaction tower at a flow rate of 300k/kg, methanol enters the reaction tower after being gasified, and the flow rate is 260kg; maintaining the temperature of the kettle type reboiler at 100 ℃ and the temperature of the middle part of the reaction tower at 70 ℃; when the liquid level in the kettle-type reboiler exceeds 30%, crude product extraction is started, and the liquid level of the kettle-type reboiler is kept at 50% during extraction.
Crude products at the beginning of extraction are detected: 84.2% of methyltrimethoxysilane, 0.2% of methyldimethoxyhydrosilane, 14.2% of methanol and 1.4% of other components; the crude product is rectified to obtain the methyltrimethoxysilane with the purity of 99 percent.
The crude product 50 hours after the start of extraction was detected: 84.1% of methyltrimethoxysilane, 0.2% of methyldimethoxyhydrosilane, 14.3% of methanol and 1.4% of other components; the crude product is rectified to obtain the methyltrimethoxysilane with the purity of 99 percent.
Example 3
Preparation of a dehydrogenation catalyst-supporting filler: adding 300kg of methanol and 40kg of water into a 1000L hydrolysis kettle, keeping the temperature in the kettle at 50 ℃, dropwise adding 300kg of methyltrimethoxysilane, and keeping the temperature in the kettle at 50 ℃ for continuous stirring reaction for 8 hours after the dropwise adding is finished to obtain an alkoxy silane hydrolysate; adding 30kg of nickel nitrate into the hydrolysate, stirring uniformly, then placing the hydrolysate of the alkoxy silane into an impregnating tank, placing the ceramic filler with holes into the impregnating tank to completely impregnate the ceramic filler with the ceramic filler for 16 hours, taking out the filler, and placing the filler into a dryer to dry for 4 hours at 100 ℃ to obtain the filler for loading the dehydrogenation catalyst.
Preparation of tetraethoxysilane: the mixture of 40% of trichlorosilane and 60% of silicon tetrachloride enters a reaction tower at a flow rate of 300k/kg, ethanol enters the reaction tower after being vaporized, and the flow rate is 460kg; maintaining the temperature of the kettle type reboiler at 100 ℃ and the temperature of the middle part of the reaction tower at 80 ℃; when the liquid level in the kettle-type reboiler exceeds 30%, crude product extraction is started, and the liquid level of the kettle-type reboiler is kept at 50% during extraction.
Crude products at the beginning of extraction are detected: 83.5% of tetraethoxysilane, 0.2% of triethoxyhydrosilane, 14.9% of ethanol and 1.4% of other components; the crude product is rectified to obtain tetraethoxysilane with purity of 98 percent.
The crude product 50 hours after the start of extraction was detected: 83.3% of tetraethoxysilane, 0.3% of triethoxyhydrosilane, 15.1% of ethanol and 1.3% of other components; the crude product is rectified to obtain tetraethoxysilane with purity of 98 percent.
Comparative example 1
Preparation of a dehydrogenation catalyst-supporting filler: adding 300kg of N, N-dimethylformamide and 40kg of water into a 1000L hydrolysis kettle, keeping the temperature in the kettle at 50 ℃, dropwise adding 300kg of methyltrimethoxysilane, and keeping the temperature in the kettle at 50 ℃ after dropwise adding, and continuously stirring and reacting for 8 hours to obtain an alkoxysilane hydrolysate; adding 30kg of nickel chloride into the hydrolysate, stirring uniformly, then placing the hydrolysate of the alkoxy silane into an impregnating tank, placing the ceramic filler with holes into the impregnating tank to completely impregnate the ceramic filler with the ceramic filler for 16 hours, taking out the filler, and placing the filler into a dryer to dry for 4 hours at 100 ℃ to obtain the filler for loading the dehydrogenation catalyst.
Preparation of methyltrimethoxysilane: methyl dichlorosilane enters a reaction tower at a flow rate of 300k/kg, methanol enters the reaction tower after being gasified, and the flow rate is 300kg; maintaining the temperature of the kettle type reboiler at 100 ℃ and the temperature of the middle part of the reaction tower at 70 ℃; when the liquid level in the kettle-type reboiler exceeds 30%, crude product extraction is started, and the liquid level of the kettle-type reboiler is kept at 50% during extraction.
Crude products at the beginning of extraction are detected: 62.8% of methyltrimethoxysilane, 6.7% of methyldimethoxyhydrosilane, 28.9% of methanol and 1.6% of other components; the crude product is rectified to obtain methyltrimethoxysilane with the purity of 98 percent.
The crude product 50 hours after the start of extraction was detected: 63.1% of methyltrimethoxysilane, 6.8% of methyldimethoxyhydrosilane, 28.2% of methanol and 1.9% of other components; the crude product is rectified to obtain methyltrimethoxysilane with the purity of 98 percent.
Comparative example 2
Preparation of a dehydrogenation catalyst-supporting filler: mixing 300kg of ethanol, 300kg of phenolic resin and 30kg of nickel chloride, uniformly stirring, then placing into an impregnating tank, placing ceramic filler with holes into the impregnating tank, completely immersing for 16 hours, taking out the filler, and placing into a dryer for drying at 100 ℃ for 4 hours to obtain the filler loaded with the dehydrogenation catalyst.
Preparation of methyltrimethoxysilane: methyl dichlorosilane enters a reaction tower at a flow rate of 300k/kg, methanol enters the reaction tower after being gasified, and the flow rate is 300kg; maintaining the temperature of the kettle type reboiler at 100 ℃ and the temperature of the middle part of the reaction tower at 70 ℃; when the liquid level in the kettle-type reboiler exceeds 30%, crude product extraction is started, and the liquid level of the kettle-type reboiler is kept at 50% during extraction.
Crude products at the beginning of extraction are detected: 75.4% of methyltrimethoxysilane, 1.5% of methyldimethoxyhydrosilane, 21.8% of methanol and 1.3% of other components; the crude product is rectified to obtain the methyltrimethoxysilane with the purity of 99 percent.
The crude product 50 hours after the start of extraction was detected: 76.8% of methyltrimethoxysilane, 1.3% of methyldimethoxyhydrosilane, 19.4% of methanol and 1.7% of other components; the crude product is rectified to obtain methyltrimethoxysilane with the purity of 98 percent.
According to the invention, the organic silicon byproduct and alcohol can be reacted to generate the alkoxy silane, the product yield is high, the purity is good, the catalytic effect of the prepared filler of the supported dehydrogenation catalyst is stable, and the service life is long.
In the preparation process of the filler loaded with the dehydrogenation catalyst in comparative example 1, alcohol is not used for controlling the hydrolysis process of methyltrimethoxysilane, so that the hydrolysate of methyltrimethoxysilane is polycondensed and crosslinked into gel, the precipitated gel can influence the mixing condition of the dehydrogenation catalyst and the hydrolysate of methyltrimethoxysilane, further influence the loading and dispersion condition of the dehydrogenation catalyst in the filler after impregnation, and the catalyst loaded with the filler can reduce the catalytic efficiency of the filler loaded with the dehydrogenation catalyst in the production process less. At the same time, compared with the methyltrimethoxysilane hydrolysate with lower crosslinking degree, the gel methyltrimethoxysilane hydrolysate has no great improvement on the fixation capacity of the dehydrogenation catalyst, but has great blocking effect on the contact of reactants with the dehydrogenation catalyst, so the catalytic efficiency of comparative example 1 and the yield of the target product in the obtained crude product are lower than those of example 2.
In comparative example 2, phenolic resin was used instead of alkoxysilane hydrolysate to fix dehydrogenation catalyst, but the phenolic resin had good adhesiveness but did not have good permeability and compatibility with organosilane by-products, so after the dehydrogenation catalyst was fixed on the filler by the phenolic resin, the phenolic resin could obstruct contact between the reactant and the dehydrogenation catalyst, resulting in lower yield of the product, and thus the effect of using alkoxysilane hydrolysate in the filler was better.
Claims (7)
1. A method for preparing alkoxy silane by using organosilicon byproducts, which is characterized by comprising the following steps:
(A) Adding the organic silicon by-product and the vaporized alcohol into a reaction tower, and keeping a certain temperature in the reaction tower to enable the organic silicon by-product and the alcohol to react under the catalysis of a filler loaded with a dehydrogenation catalyst;
(B) Unreacted vaporization raw materials are subjected to heat exchange through a condenser positioned at the top of the reaction tower and then flow back to the middle part of the reaction tower, crude products of alkoxy silane obtained by reaction are collected into a kettle type reboiler positioned at the bottom of the reaction tower, and the raw materials which are not fully reacted in the kettle type reboiler are vaporized and enter the reaction tower again for reaction;
(C) Rectifying the crude product of the alkoxy silane in the kettle-type reboiler to obtain the finished product of the alkoxy silane;
in the step (A), the organic silicon byproduct is one or two of methyl dichlorosilane and methyl trichlorosilane or one or two of silicon tetrachloride and trichlorosilane, and the alcohol is methanol or ethanol;
the filler for supporting the dehydrogenation catalyst used in the step (A) is prepared by the following steps:
(1) Mixing alcohol with water, and then dropwise adding alkoxy silane for hydrolysis reaction to obtain alkoxy silane hydrolysate;
(2) Mixing the alkoxy silane hydrolysate with the dehydrogenation catalyst, adding the filler for impregnation, and drying the impregnated filler to obtain the filler for loading the dehydrogenation catalyst;
in the step (1), the mass ratio of the alcohol to the water to the alkoxy silane is 1 (0.02-1): 1, the hydrolysis reaction temperature is 10-100 ℃, and the reaction time is 1-24h.
2. The method for producing an alkoxysilane by using an organosilicon by-product according to claim 1, wherein in said step (A), the molar ratio of the organosilicon by-product to the alcohol is 1 (1) to 1.3 based on the total number of hydrogen and chlorine atoms directly bonded to the silicon atom.
3. The method for preparing alkoxysilane by using organosilicon by-products according to claim 1, wherein in step (a) and step (B), the temperature of the reaction column is 50-100 ℃, and the temperature of the kettle reboiler is 50-100 ℃.
4. The method of preparing an alkoxysilane by-product according to claim 1, wherein the alkoxysilane hydrolysate obtained in step (1) comprises methyltrialkoxysilane hydrolysate, vinyltrialkoxysilane hydrolysate, phenyltrialkoxysilane hydrolysate and tetraalkoxysilane hydrolysate.
5. The method for preparing alkoxysilane by using an organosilicon byproduct according to claim 1, wherein in the step (2), the dehydrogenation catalyst is one of nickel sulfate, nickel chloride, nickel carbonate and nickel nitrate, and the filler is one of a ceramic filler with holes, a metal oxide filler, a filler obtained by pressing inorganic fibers, and a filler obtained by pressing organic fibers.
6. The method for preparing alkoxysilane by using an organosilicon byproduct according to claim 1, wherein in the step (2), the dipping time is 1-24 hours, the drying temperature is 50-200 ℃, and the drying time is 3-12 hours.
7. The method for preparing alkoxysilane by using an organosilicon byproduct according to claim 1 or 6, wherein the mass of the dehydrogenation catalyst and alkoxysilane hydrolysate in the filler loaded with the dehydrogenation catalyst obtained in the step (2) is 1-20% of that of the filler.
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| US4228092A (en) * | 1978-01-02 | 1980-10-14 | Dynamit Nobel Aktiengesellschaft | Process for the preparation of organoalkoxysilanes |
| US4471133A (en) * | 1983-05-31 | 1984-09-11 | General Electric Company | Continuous method for making methyldimethoxysilane |
| US4851558A (en) * | 1987-06-12 | 1989-07-25 | Toshiba Silicone Co., Ltd. | Process for producing alkoxysilanes |
| CN105131028A (en) * | 2015-09-06 | 2015-12-09 | 浙江衢州硅宝化工有限公司 | Preparation method of methyl triethoxysilane |
| CN111303198A (en) * | 2020-01-14 | 2020-06-19 | 浙江衢州硅宝化工有限公司 | Method for preparing organosilane by using organic silicon byproduct |
| KR20210018566A (en) * | 2019-08-05 | 2021-02-18 | 효성화학 주식회사 | Preparation method of propane dehydrogenation catalyst |
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| US4228092A (en) * | 1978-01-02 | 1980-10-14 | Dynamit Nobel Aktiengesellschaft | Process for the preparation of organoalkoxysilanes |
| US4471133A (en) * | 1983-05-31 | 1984-09-11 | General Electric Company | Continuous method for making methyldimethoxysilane |
| US4851558A (en) * | 1987-06-12 | 1989-07-25 | Toshiba Silicone Co., Ltd. | Process for producing alkoxysilanes |
| CN105131028A (en) * | 2015-09-06 | 2015-12-09 | 浙江衢州硅宝化工有限公司 | Preparation method of methyl triethoxysilane |
| KR20210018566A (en) * | 2019-08-05 | 2021-02-18 | 효성화학 주식회사 | Preparation method of propane dehydrogenation catalyst |
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