CN100357298C - Continuous hydrolysis process of organic dichlorosilane - Google Patents
Continuous hydrolysis process of organic dichlorosilane Download PDFInfo
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- CN100357298C CN100357298C CNB031527175A CN03152717A CN100357298C CN 100357298 C CN100357298 C CN 100357298C CN B031527175 A CNB031527175 A CN B031527175A CN 03152717 A CN03152717 A CN 03152717A CN 100357298 C CN100357298 C CN 100357298C
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Abstract
The present invention relates to a continuous hydrolysis process for organic dichlorosilane. The process comprises at least three stages of cyclic hydrolysis reaction systems, and each cyclic hydrolysis reaction system comprises an internal circulation unit and an external circulation unit. A main product of the organic dichlorosilane is synthesized by organosilicon monomers, such as dimethyl dichlorosilane; low-viscosity linear or annular organosiloxane prepared by hydrolyzing the organic dichlorosilane is main raw materials of polyorganosiloxane; the organic dichlorosilane can be used for synthesizing silicon oil, silicon rubber, etc., and can be widely applied to electronic industry, daily chemical industry, electric power industry, construction material industry, etc.
Description
Technical field
The present invention relates to a kind of organic dichlorosilane continuous hydrolysis technology, this technology comprises at least three grades circulation hydrolysising reacting system, and every grade of circulation hydrolysising reacting system comprises two cycling elements again: internal recycle unit, outer circulation unit.Organic dichlorosilane is an organosilane monomer synthetic main products, dimethyldichlorosilane(DMCS) for example, and the low viscosity linearity or the cyclic organic siloxane of organic dichlorosilane hydrolysis preparation, it is the main raw material(s) of organopolysiloxane, it can be used for synthetic silicone oil, silicon rubber etc., is widely used in industry such as electronics, daily use chemicals, electric power, building materials.
Background technology
The hydrolysis process of organic dichlorosilane and technology can find in many disclosed technical information books, for example, W.Noll describes in " organosilicon chemistry and technology " (1968), the hydrolysis of dimethyldichlorosilane(DMCS) generally can be undertaken by two kinds of methods: a kind of is to adopt the excessive water hydrolysis, its hydrolysis process is to make the concentration of hydrochloric acid concentration (37%wt) that reaches capacity with azeotropic acid (about 21%wt) circulation and by hydrolyzing dimethyl dichlorosilane, obtain gas phase chlorination hydrogen by water distilling apparatus again, this method need consume lot of energy and possible a large amount of dilute hydrochloric acid; Another kind of hydrolysis process adopts hydrolysis under the lack of water condition, and hydrolysis process then can directly obtain gas phase chlorination hydrogen and need not the concentrated hydrochloric acid distillation, but thick hydrolyzate chlorinity height, and further neutralization causes the loss and the contaminated wastewater of chlorine.
The hydrolysis process of organic dichlorosilane also is disclosed in various countries' patent disclosure and the application.
USP4609751 has described the employing static mixer and has carried out the concentrated acid hydrolysis, promptly adopt the hydrolysis of equivalent water mode, alkyl halogen silanes does not have complete hydrolysis, and product contains the end capped alkylsiloxane of a spot of Cl, cause the post-processed difficulty, and because of producing a large amount of waste water with the alkali neutralization.
Chinese patent application 9311087 discloses the method for hydrolysis of organic radical silicane dichloride, when hydrolysis, add a spot of alkylsulphonic acid and alkali-metal anion surfactant thereof, when removing the residual HCl of siloxanes, do not improve the yield of ring body under the emulsive prerequisite, but can not obtain gasiform hydrogenchloride.
Chinese patent CN1108267A discloses the preparation method of polydimethyl silane, dimethyl dichloro silicon adopts poly-two radical siloxanes of two one-step hydrolysis preparations: the first step, dimethyldichlorosilane(DMCS) be present in thick hydrolysate and the gaseous hydrogen chloride that water reaction in the hydrochloric acid obtains comprising the chlorine end-blocking polydimethylsiloxane of ring-type and wire.Second step, with 110 ℃～160 ℃ the thick hydrolyzate of steam treatment,, and generate hydrochloric acid with the minimizing chlorinity, the hydrochloric acid that second step was generated is used for the first step simultaneously, though this method can obtain gas phase chlorination hydrogen, it adopts 25% hydrochloric acid as the water source, and the concentration of hydrochloric acid under this concentration is also unsaturated, in addition in second step, thick hydrolyzate was handled, the employing high-temperature water vapor is handled, and the viscosity of hydrolyzate finally is restive, and low viscous hydrolyzate is handled in following process easily.
Chinese patent CN1209823A discloses by the poly-method that siloxanes is arranged of organo-halogen-silane hydrolysis preparation, and having described general formula is RaRb
1The organo-halogen-silane of SiXc is at the continuous hydrolysis technology at least three steps, each hydrolysing step comprises hydrolysis reaction and gravity two steps that are separated, wherein reaction medium can be used in the hydrolysis masterpiece that improves on the organo-halogen-silane, wherein there is certain temperature and pressure in step (1), and last step adopts the alkaline matter neutralization.
Though above-mentioned patent is described the hydrogenchloride that can obtain gas phase, but the thick hydrolysate chlorinity of step (1) is higher, thereby the yield of the high pressure that produces, valuable gas phase chlorination hydrogen is on the low side, the directly not synthetic methyl chloride of hydrogenchloride that step (1) back discharges low pressure is worth, and the product cl content of per in addition step operation is wayward.And in the final step alkali and after can produce a certain amount of brine waste.
Chinese patent CN1268960 is on the basis of above-mentioned patent, and washing is adopted in final step.Overcome in the alkali and generation waste water, but still fail to solve every grade of low problem that reaches the quality control of operation after product of hydrolysis efficiency in the operational process.
United States Patent (USP) 6225490 discloses the hydrolysis process of successive organochlorosilane, and this hydrolysis process comprises at least three sections reactions, and every section reaction comprises reactor and is separated.Chlorosilane adds from the first step reactor,
The reaction water is all provided by the feed water of final step, and first section reaction produces gas phase chlorination hydrogen, and the hydrolyzate that back produces enters next step processing that is hydrolyzed, and the hydrochloric acid soln that one step of back produces adds to the reaction of back.
Can produce gas phase chlorination hydrogen though this patent is described, from embodiment, the gas phase chlorination hydrogen of this low pressure should not be directly used in synthetic chloroparaffin.Front patent such as CN1108267A emphasis have been described the importance of hydrogen chloride gas pressure.In addition, the reactor efficiency of stirring tank formula is low, in order to reach the enough reaction times, must amplify, and be unfavorable for the production of continuous processing, and technological operation elasticity is little, in case certain first order reaction product efficiency is not all right, will influence end product quality.
Comprehensive above-mentioned patent is commented, and must find the continuous hydrolysis technology of this organic dichlorosilane, and it must satisfy the requirement of following several respects:
1, this kind processing method must acquisition as much as possible has the anhydrous hydrogen chloride gas of enough pressure, and this gas phase chlorination hydrogen can be directly used in synthetic methyl chloride;
2, the production efficiency of every grade of this kind processing method wants high, and every order reaction is removed structure chlorine and the free chlorine in the organopolysiloxane as far as possible;
3, the viscosity of the final organopolysiloxane product of this kind processing method generation is low, and cl content is low;
4, this kind processing method does not have brine waste and few unnecessary diluted acid of trying one's best produces;
5, this kind processing method can very stably be operated and quality product can be stablized control.
Summary of the invention
The process program that the present invention proposes is for satisfying above-mentioned requirements, by being 30-60 ℃ in suitable reaction temperature, pressure is 0.2-0.6Mpa, make the HCl that produces that enough pressure be arranged, the present invention simultaneously adopts scum dredger, remove the impurity such as volatile siloxane that HCl gas is carried secretly, make HCl gas drying, pure, this synthetic just chloroparaffin is desired.
Interior external circulation process proposed by the invention is just in order to solve every grade the production efficiency and the problem of stable operation.Internal recycle solved mass transfer problem, solved the problem of reaction times and capacity of equipment.Make that this order reaction is able to fully improve the quality of every order reaction efficient and every grade of product; Outer circulation makes oleic acid fully separate, reduce the residence time of polysiloxane in acid, because organopolysiloxane can polycondensation in acid, particularly ought contain the end capped linear polysiloxane of Cl, and one-level in the end, when " cleaning " hydrolyzate with pure water, employing relatively-high temperature, lower concentration, short period of time, then the polysiloxane cl content is low, and viscosity can not change.
Technology provided by the present invention does not adopt the alkali neutralization, but directly adopts purified softening water washing, can avoid the saliniferous discharge of wastewater, meets environmental requirement, and the concentration of hydrochloric acid of each grade of appropriate design outer circulation can be eliminated unnecessary dilute hydrochloric acid output basically.
Every grade of relatively independent cyclical operation of technology provided by the present invention, it is relatively stable to pass in and out the unitary material of every order reaction, operation, and the constant product quality of final organopolysiloxane easily, and exsiccant anhydrous hydrogen chloride gas pressure is also stable, and chemical industry operation is desired just for this.
Because the inside and outside cyclical operation system of uniqueness of the present invention, make technological operation elasticity of the present invention very big, as long as adjust the value of inside and outside circulation volume flow ratio Rn, every section effusive polysiloxane fluid of reaction is met the requirements, and do not need to change time of reaction, make entire operation system stability and operation easily.Then obtain stay-in-grade organopolysiloxane and pressure-stabilisation, drying, purified hydrogen chloride gas thus at an easy rate.
In order to understand unique thinking proposed by the invention better, hydrolysis reaction at different levels among the present invention are described below in conjunction with accompanying drawing.
Fig. 1 is a dimethyldichlorosilane(DMCS) hydrolysis process schema.
In order to simplify understanding, be dimethyldichlorosilane(DMCS) at this specific organic dichlorosilane.
First step hydrolysis reaction described in the invention comprises the mixing tank (1a) that is used for internal circulation system, internal recycle reaction starting raw material Me
2SiCl
2Add from mixing tank, with inside and outside round-robin material C
1, C
1Constitute three phase materials that contain solution-air-liquid behind the ' thorough mixing, enter inner circulation reactor (1b), inner circulation reactor is a solution-air with pressure-liquid phase reactor, in first step hydrolysis reaction, also play simultaneously the function of gas-liquid separator, hydrogen chloride gas G is through HCl cleaner (1d), constitute by typical etch-proof scum dredger, remove harmful volatile siloxane and moisture content, to guarantee the purity of HCl gas.The preferred 0.2-0.4Mpa of the working pressure of inner circulation reactor, the preferred 25-60 of temperature of reaction ℃, through isolating organopolysiloxane of solution-air and saturated hydrochloric acid soln (F
1) entering outer circulation liquid liquid separator (1c), external circulating system is made of mixing tank, inner circulation reactor and liquid-liquid phase separation device.Purpose is with organopolysiloxane oil phase (L
1) and saturated hydrochloric acid water (C
1') separate, through the isolating L of liquid-liquid phase separation device (1c)
1Cl content＜5%wt, L1 contain cyclic polysiloxanes, α, the end capped linear polysiloxane of ω-chlorine, saturated hydrochloric acid water (C
1') titration concentration 40-60%, inside and outside circulation volume flow ratio R
1Be 2～3.While reaction water source (S as a supplement
1) come from the hydrochloric acid water (C of second stage hydrolysis reactor outer circulation
2'), the preferred 18-30% of concentration range.
Second stage reaction equally also comprises inside and outside cycling element, and this order reaction system inner circulation reactor (2b) pressure is normal pressure.Temperature of reaction is 10-40 ℃, inside and outside circulation volume flow ratio R
2Be 1～4, through the reacted oil-water mixture body of internal recycle (F
2) enter the phase separator (2C) of external circulating system, the hydrochloric acid soln water (C after being separated
2') concentration is 18～30%, and organopolysiloxane oil phase (L
2) viscosity＜7mpa.s, cl content＜1% is as second section required additional water source (S of reaction
2) concentration is 0.3-5%
By parity of reasoning;
The last step hydrolysis reaction is the soft water washing organopolysiloxane of " pure ", 60-90 ℃ of inner circulation reactor temperature, inside and outside circulation volume flow ratio R
n=2-5 with the reacted logistics of internal recycle (Fn), separates dilute hydrochloric acid solution water (C through phase separator (nc)
n'), concentration is 0.3-2%, the viscosity＜15mpa.s of organopolysiloxane oil phase (Ln '), cl content＜10ppm.
Embodiment
First step hydrolysis reaction:
System pressure control P=0.4mpa (absolute pressure) temperature of reaction T=50 ℃
Me
2SiCl
2Charging 400Kg/h internal recycle amount C
1=4m
3/ hr outer circulation amount C
1'=1.5m
3/ hr, R
1=2.67
C
1' concentration of hydrochloric acid 45.6% (titration measuring), the flow 198Kg/hr of gas phase HCl (G),
S
1Flow 70.0Kg/hr, concentration of hydrochloric acid 24.6%.
The flow of thick siloxanes (L1): 231.5Kg/hr, cl content 4.6%, viscosity 4.3mpa.s.Second stage hydrolysis reaction:
System pressure P=0.1mpa (absolute pressure), temperature of reaction T=30 ℃
L
1Charging internal recycle C
2=2.5m
3/ hr outer circulation amount C
2'=1.0m
3/ hr R
2=2.5
C
2' concentration of hydrochloric acid 24.6% (titration determination)
Thick siloxanes (L
2) flow 229.3Kg/hr cl content 0.8% viscosity 6.6mpa.s
S
2Flow 65.0Kg/hr titration concentration of hydrochloric acid 4.6%
Third stage hydrolysis reaction:
System pressure P=0.1mpa (absolute pressure), temperature of reaction T=40 ℃
L
2Charging internal recycle C
3=2.5m
3/ hr outer circulation amount C
3'=1.0m
3/ hr R
3=2.5
C
3' concentration of hydrochloric acid 4.6% (titration determination)
L
3Flow 228.0Kg/hr cl content 300ppm viscosity 8.5mpa.s
S
3Flow 62.8Kg/hr titration concentration of hydrochloric acid 0.6%
Fourth stage hydrolysis reaction:
System pressure P=0.1mpa (absolute pressure), temperature of reaction T=80 ℃
L
3Charging internal recycle C
4=5.0m
3/ hr outer circulation amount C
4'=1.5m
3/ hr R
4=3.33
C
3' concentration of hydrochloric acid 0.6% (titration determination)
S
4Flow 62.4Kg/hr " pure " softening water
L
4Flow 227.5Kg/hr cl content 9ppm viscosity 14mpa.s
Claims (6)
1. a general formula is RR ' SiCl
2Organic dichlorosilane continuous hydrolysis prepare organopolysiloxane, and produce the processing method of the hydrogenchloride of gas phase, R represent methylidene wherein, phenyl, ethyl or sec.-propyl, R ' represents hydrogen, methyl, phenyl, ethyl or sec.-propyl, R and R ' can be identical, also can be different, this method comprises the hydrolysis unit more than at least three grades, every grade of hydrolysis reaction unit all comprises two circulation routes: internal recycle and outer circulation, first step hydrolysis reaction unit is a compression system, every grade of hydrolysis unit comprises mixing reactor, inner circulation reactor, wherein inner circulation reactor also has the effect of solution-air phase separator in the first step hydrolysis reaction, the outer circulation phase separator is formed, every grade of hydrolysis reaction unit is relatively independent, but be to move continuously between the hydrolysis unit at different levels, it is the hydrolysis reaction unit that the hydrolysis organopolysiloxane of upper level enters next stage continuously, and the hydrolysis hydrochloric acid of next stage adds to upper level continuously, this method is included in the anhydrous hydrogen chloride that first step hydrolysis reaction unit produces gas phase, this hydrogenchloride can be directly used in synthetic chloroparaffin, and chloroparaffin is the starting raw material of synthetic organochlorosilane.
2. processing method according to claim 1, wherein every grade of hydrolysis reaction unit all comprises two circulation routes, internal recycle is guaranteed the sufficient reacting of this grade hydrolysis, wherein, in first step reaction, fully produce the hydrogenchloride of gas phase, outer circulation is to guarantee that organic phase behind this grade hydrolysis reaction is an organopolysiloxane with after water is effectively separating of hydrogen chloride solution, and water in time adds in the internal circulation system, and organic phase enters the hydrolysis reaction unit of next stage in time.
3. processing method according to claim 1, first step hydrolysis reaction unit is a pressurized systems, and it is the requirement of satisfying directly synthetic chloroparaffin that pressure requires, and pressure range is at 0.1～0.8mpa, 20～80 ℃ of temperature of reaction.
4. processing method according to claim 1, the ratio R of the internal recycle of first step hydrolysis reaction and outer circulation volumetric flow rate
1=VC
1/ VC
1'=1～10, the C of outer circulation
1' concentration of hydrochloric acid be 40～60%, cl content＜5% of thick organopolysiloxane.
5. processing method according to claim 1, the reaction pressure normal pressure of second stage hydrolysis, 0～50 ℃ of temperature of reaction, inside and outside recycle ratio R
2=1～6, outer circulation C
2' concentration of hydrochloric acid be 18～35%, cl content＜1% of thick organopolysiloxane.
6. processing method according to claim 1, the last step hydrolysis reaction adopts the soft water that replenishes " pure ", and temperature of reaction is 50～100 ℃, inside and outside recycle ratio R
n=2-10, outer circulation C
n' concentration of hydrochloric acid 0.3～5%, the cl content＜10PPm of organopolysiloxane, organopolysiloxane viscosity＜15mpa.s.
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| CNB031527175A CN100357298C (en) | 2003-08-10 | 2003-08-10 | Continuous hydrolysis process of organic dichlorosilane |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208617B2 (en) * | 2004-10-05 | 2007-04-24 | Dow Corning Corporation | Hydrolysis of chlorosilanes |
| DE102005047394A1 (en) * | 2005-10-04 | 2007-04-05 | Wacker Chemie Ag | Production of organopolysiloxane for use e.g. in buildings protection, involves reaction of chlorosilane with water and alcohol, continuous addition of water and immiscible solvent, and then phase separation |
| CN101148510B (en) * | 2006-09-21 | 2011-06-29 | 蓝星化工新材料股份有限公司 | Method for preparing polyorganosiloxane and gas phase hydrogen chloride by multi-stage continuously hydrolyzing dichlorosilane |
| CN101323666B (en) * | 2008-07-24 | 2011-04-27 | 北京石油化工设计院有限公司 | Method for continuous production of hydrolysate by methylchlorosilane concentrated acid hydrolyzing |
| CN101875726B (en) * | 2009-04-30 | 2012-05-30 | 中国石油天然气股份有限公司 | Method for preparing polysiloxane by hydrolyzing dimethyl dichlorosilane |
| CN102002163B (en) * | 2010-10-19 | 2012-05-09 | 江苏宏达新材料股份有限公司 | Dechlorinating process for polysiloxane |
| CN103011093B (en) * | 2012-12-25 | 2014-05-28 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Device and method for removing siloxane in dilute sulfuric acid |
| CN103183828B (en) * | 2013-03-28 | 2014-09-24 | 青岛科技大学 | Dechlorination washing system of hydrolysates in organochlorosilane concentrated acid hydrolysis process |
| CN104031084B (en) * | 2014-06-19 | 2016-09-07 | 鲁西化工集团股份有限公司硅化工分公司 | Organosilicon hydrolyzation thing loop wire separation method |
| CN106588583A (en) * | 2016-11-24 | 2017-04-26 | 大连东泰产业废弃物处理有限公司 | Harmless disposal method of waste organic solvent containing halogen silane polymer |
| CN109880119B (en) * | 2019-01-31 | 2021-08-10 | 山东东岳有机硅材料股份有限公司 | Method for eliminating phenomena of no delamination and equipment adhesion of organosilicon crude monomer hydrolysate |
| CN114752061B (en) * | 2022-05-27 | 2023-05-30 | 云南能投硅材科技发展有限公司 | Dimethyl dichlorosilane hydrolysis process with desorption function |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209823A (en) * | 1996-01-24 | 1999-03-03 | 罗狄亚化学公司 | Method for preparing polyorganosiloxanes by hydrolysing organchalosilanes |
| CN1268960A (en) * | 1997-07-24 | 2000-10-04 | 罗狄亚化学公司 | Method for preparing polyorganosiloxanes by hydrolysing organohalosilances |
| US6225490B1 (en) * | 1997-05-28 | 2001-05-01 | Shin-Etsu Chemical Co., Ltd. | Continuous hydrolysis of organochlorosilanes |
-
2003
- 2003-08-10 CN CNB031527175A patent/CN100357298C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209823A (en) * | 1996-01-24 | 1999-03-03 | 罗狄亚化学公司 | Method for preparing polyorganosiloxanes by hydrolysing organchalosilanes |
| US6225490B1 (en) * | 1997-05-28 | 2001-05-01 | Shin-Etsu Chemical Co., Ltd. | Continuous hydrolysis of organochlorosilanes |
| CN1268960A (en) * | 1997-07-24 | 2000-10-04 | 罗狄亚化学公司 | Method for preparing polyorganosiloxanes by hydrolysing organohalosilances |
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