CN85100433B - New process of hydrolyzing organochlorosilanes - Google Patents
New process of hydrolyzing organochlorosilanes Download PDFInfo
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- CN85100433B CN85100433B CN85100433A CN85100433A CN85100433B CN 85100433 B CN85100433 B CN 85100433B CN 85100433 A CN85100433 A CN 85100433A CN 85100433 A CN85100433 A CN 85100433A CN 85100433 B CN85100433 B CN 85100433B
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- organochlorosilane
- hydrochloric acid
- water
- hydrolysis
- acid
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Abstract
The present invention provides a novel technology for hydrolyzing organochlorosilane with equivalent water. The present invention is characterized in that a static mixer is used as a hydrolyzing reactor, saturated hydrochloric acid is used for cyclic operation, and the hydrolyzation is carried out under pressure; all chlorine hydride generated in the reaction is recovered in the gas state, and the recovery rate reaches 90 to 98%; the prepared hydrolyzate conforms to the requirements of all technologies in future.
Description
The present invention is a hydrolyzing organochlorosilanes, generates the processing method of polysiloxane and anhydrous hydrogen chloride.
The excessive water hydrolysis is arranged before the present invention, generate hydrolyzate and hydrochloric acid that cyclosiloxane and terminal hydroxy group wire polysiloxane two are partly formed.Because resultant hydrogenchloride is dissolved in water or the diluted acid, emits big calorimetric, remain within the processing condition requirement for making temperature of reaction, need heat is shifted out, and expend lot of energy, when synthesizing methyl chloride with this acid with methyl alcohol simultaneously, also to consume a lot of energy.
GB2112407A is with saturated salt acid hydrolysis dimethyldichlorosilane(DMCS), but because the water yield that adds consumption during greater than hydrolysis also has hydrochloric acid so pay to produce except that hydrogenchloride, need consume a lot of energy when utilizing this acid.
US4,382,145 usefulness concentration are minimum to be 35%(wt) water in the hydrochloric acid is as the water source, and its consumption is 10～30 times (mol ratios) of chlorosilane, is circulated in the reactor to be hydrolyzed; US4,497,942 usefulness concentration be water in 40～42% the hydrochloric acid as the water source, consumption is 10～50 times (mol ratios) of organochlorosilane, hydrochloric acid and organochlorosilane is imported static mixer together be hydrolyzed.The advantage of two patents is directly to obtain anhydrous hydrogen chloride, has therefore saved energy.But exist the incomplete shortcoming of hydrolysis, also do not report the yield of hydrolyzate and the data of hydrogenchloride yield and purity.
The object of the present invention is to provide a kind of stable operation, processing method that energy consumption is little, hydrolyzate yield 97.5%(wt), the yield 90～98%(wt) of hydrogenchloride.
The present invention realizes by following process steps:
1. saturated hydrochloric acid is cycle stock under a large amount of normalities, adds water or hydrochloric acid as the required water source of hydrolysis, and its water yield is normal 1.05～1.10 times an of chlorine in the organochlorosilane.
2. reactor adopts static mixer lengthening thrust-augmenting nozzle, pressure when reacting to strengthen mixing effect and increase, after this pressure can make the hydrogenchloride that generates after all organochlorosilane complete hydrolysis all be dissolved in the recycle acid, this hydrochloric acid still is in undersaturated condition, make whole system not have hydrogen chloride gas, avoid organochlorosilane to be diffused in the gas, take away with gas, cause hydrolyzate yield and hydrogenchloride yield low, hydrogenchloride purity is not high simultaneously.After hydrolysis reaction was finished, hydrolyzate and hydrochloric acid entered gas-liquid separator by long thrust-augmenting nozzle.Here pressure drops to normal pressure gradually, and hydrogenchloride parses with gaseous state from recycle acid.
3. the effect that increases recycle acid increases the organochlorosilane chance that contacts with water and the concentration and the little effect of temperature variation that keep reaction system acid in addition except in time dissolving the hydrogenchloride of generation.
Following processing condition all are suitable to the present invention:
(1). temperature of reaction 20～50(the best is 35 ± 5) ℃.
(2). the residence time 10～150(the best in reactor is 25 ± 2) second.
(3). the volume ratio of the organochlorosilane of recycle acid and input is 100: 1～60: 1(the best is 75: 1).
(4). the equivalence ratio of chlorine is 1.05～1.10 in water of input (or drop in the hydrochloric acid water) and the organochlorosilane: 1(refers to the mean value that per hour feeds intake).
(5). the working pressure of static mixer is 9.8～30 * 10
4(the best is 16.3～21 * 10
4) pascal.
Organochlorosilane among the present invention is expressed as with general formula
R
aH
bSiCl
(4-a-b)
R represents alkyl, the thiazolinyl of carbonatoms≤6.H represents hydrogen.A is smaller or equal to 3 positive integer more than or equal to 1.B can be 0; 1; 2.A+b is the positive integer more than or equal to 2, smaller or equal to 3.When a more than or equal to 2 the time, R can be identical group and different groups.
For better explanation characteristics of the present invention, figure is made description below:
Hydrolysis process carries out in a loop.Its major equipment is by (1). Suhl scholar formula static mixer; (2). thrust-augmenting nozzle; (3). gas-liquid separator; (4). phase separator; (5). neutralizer; (6). heat exchanger; (7). infusion pumps etc. are formed.Organochlorosilane after the metering and water (or hydrochloric acid) add in the static mixer ingress, pass through reactor with recycle acid, enter gas-liquid separator, the complete desorb of hydrogenchloride is also separated, liquid enters phase separator, the oil phase on upper strata is the acidic hydrolysis thing, enters neutralizer (or water scrubber), and the water of lower floor is that hydrochloric acid recycles by pump and heat exchanger.
For proving reliability of the present invention, lift following example with explanation, example is not the boundary of invention.
Example one
In above-mentioned cyclic system, carry out the dimethyldichlorosilane(DMCS) hydrolysis, 30 ± 2 ℃ of temperature of reaction, acid solution internal circulating load 3 ± 0.1m
3/ h; Total residence time in static mixer and thrust-augmenting nozzle 23.2～24.8 seconds; 40 jin of public affairs of the charging capacity of dimethyldichlorosilane(DMCS)/hour; 5.58 kilograms/hour of water charging capacitys.The feed ratio 1 of dimethyldichlorosilane(DMCS) and water: the 1.1(mol ratio) inlet pressure of static mixer is 2.1 * 10
5Pascal's top hole pressure is 16.3 * 10
4Pascal.The products therefrom index is as follows: acid content 3.0～3.8%(Wt) in the acidic hydrolysis thing; Viscosity 7.5～8.5 centistokes (20 ℃); In and the posthydrolysis thing be neutrality or subacidity, viscosity 18～25 centistokes (20 ℃) hydrolyzate yield 97.5%(Wt) cyclosiloxane content 30～35%(Wt) these hydrolyzates meet after each processing requirement, the productive rate of hydrogenchloride is 96～96.9%(Wt).
Example two
Other condition is identical with example one, as long as temperature of reaction is brought up to 35 ± 2 ℃ from 30 ℃, acid content is reduced to 2.53～2.87%(Wt) other indexs and do not become in the hydrolyzate.
Example three
Other condition such as example one, just the acidic hydrolysis thing is once washed.Calculate amount of water, make the acid in the hydrolyzate all enter water, generate 25 ± 2%(Wt) hydrochloric acid, after the washing, 1%(Wt is reduced in the acid in the hydrolyzate like this) below, neutralization is easily, the dilute hydrochloric acid sedimentation that obtains added in the response circuit after 48 hours, had improved the recovery of hydrogen chloride rate.The washed reaction device can be the reactor that band stirs, and also can be static mixer.
Characteristics of the present invention are
1. than excessive water hydrolysis and azeotropic acid hydrolysis, save a lot of energy.
2. technology stability is good, and the hydrogenchloride yield is up to 90～98%(Wt), improves the quality of 24～11%(Wt) gained hydrolyzates than the method for being talked among the English Patent GB211247A, remove cyclosiloxane lower with the hydrolyzate indistinction of excessive water hydrolysis.
3. there is not acid solution to discharge.
Claims (3)
1, a kind of hydrolyzing organochlorosilanes technology, it is to import static mixer together with saturated hydrochloric acid under the normality and organochlorosilane, 9.8～30 * 10
4Under the pascal pressure, reaction is hydrolyzed under 20～50 ℃ of temperature, material total residence time in reactor is 10～150 seconds, the consumption that the invention is characterized in the saturated hydrochloric acid under the normality is 60～100 times of organochlorosilane volume, adds the water yield in water or the hydrochloric acid and be in the organochlorosilane normal 1.05～1.10 times of chlorine.
2, as said hydrolysis process in the claim 1, the optimum amount that it is characterized in that the saturated hydrochloric acid under the normality is 75 times of organochlorosilane volume.
3,, it is characterized in that organochlorosilane is a dimethyldichlorosilane(DMCS) as claim 1,2 said hydrolysis processs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100433A CN85100433B (en) | 1985-04-01 | 1985-04-01 | New process of hydrolyzing organochlorosilanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100433A CN85100433B (en) | 1985-04-01 | 1985-04-01 | New process of hydrolyzing organochlorosilanes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100433A CN85100433A (en) | 1986-07-23 |
| CN85100433B true CN85100433B (en) | 1988-05-11 |
Family
ID=4791154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85100433A Expired CN85100433B (en) | 1985-04-01 | 1985-04-01 | New process of hydrolyzing organochlorosilanes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85100433B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20080276970A1 (en) * | 2007-05-09 | 2008-11-13 | John Christopher Cameron | Apparatus and method for treating materials with compositions |
| CN101619072B (en) * | 2009-08-13 | 2011-10-05 | 浙江大学 | Process for hydrolyzing dimethyl dichlorosilane by using concentrated hydrochloric acid loop |
| CN101921397B (en) * | 2010-08-24 | 2012-04-18 | 泸州北方化学工业有限公司 | Device and method for mixing and reacting halogenated silane with reaction medium |
| CN103183829B (en) * | 2013-03-28 | 2014-09-24 | 青岛科技大学 | Concentrated acid hydrolysis system used for organochlorosilane concentrated acid hydrolysis |
| CN106006557B (en) * | 2016-05-18 | 2018-06-15 | 昆明理工大学 | A kind of method of chlorosilane raffinate production hydrogen chloride gas |
| CN113620247A (en) * | 2021-08-26 | 2021-11-09 | 浙江新安化工集团股份有限公司 | Treatment process of organic silicon high-boiling residues |
| CN113996256B (en) * | 2021-11-12 | 2023-11-14 | 新疆晶硕新材料有限公司 | Method and device for treating dimethyl dichlorosilane hydrolysate |
| CN114085381B (en) * | 2021-11-29 | 2023-04-28 | 内蒙古恒星化学有限公司 | Gas phase dimethyl dichlorosilane hydrolysis process |
-
1985
- 1985-04-01 CN CN85100433A patent/CN85100433B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85100433A (en) | 1986-07-23 |
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