CN85100433A - New process of hydrolyzing organochlorosilanes - Google Patents
New process of hydrolyzing organochlorosilanes Download PDFInfo
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- CN85100433A CN85100433A CN 85100433 CN85100433A CN85100433A CN 85100433 A CN85100433 A CN 85100433A CN 85100433 CN85100433 CN 85100433 CN 85100433 A CN85100433 A CN 85100433A CN 85100433 A CN85100433 A CN 85100433A
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- organochlorosilane
- water
- static mixer
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- hydrochloric acid
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Abstract
The present invention proposes the novel process of equivalent water hydrolysis organochlorosilane, it is characterized in that adopting static mixer is hydrolysis reactor, and with saturated hydrochloric acid cyclical operation, hydrolysis is carried out under pressure; The hydrogenchloride that reaction generates all reclaims with gaseous form, and the rate of recovery reaches 90～98%; The requirement of each technology after the hydrolyzate that makes meets.
Description
The present invention is a hydrolyzing organochlorosilanes, generates a kind of new process of polysiloxane and anhydrous hydrogen chloride.
The excessive water hydrolysis is arranged before the present invention, and generating cyclosiloxane and end group is the wire polysiloxane hydrolyzate dimerous and the hydrochloric acid of hydroxyl.Because resultant hydrogenchloride is dissolved in water or the diluted acid, emits a large amount of heat, remain within the processing condition requirement for making temperature of reaction, need heat is shifted out, and expend lot of energy.
The concentration that generates hydrochloric acid is decided by amount of water, generally is to generate 32～34%(Wt) hydrochloric acid.Hydrochloric acid although it is so also can synthesize methyl chloride with methyl alcohol, no matter but be to adopt liquid phase method, or vapor phase process, all to consume a lot of energy.
In English Patent GB211247A, narrated saturated hydrochloric acid and reacted, generated the patent content of hydrolyzate and saturated hydrochloric acid and anhydrous hydrogen chloride with dimethyldichlorosilane(DMCS).
Its feed molar ratio is a dimethyldichlorosilane(DMCS): water=1: the 2(mol ratio).Its mol ratio is 1: 4 in example 3.The recovery of hydrogen chloride rate is 66～87%(Wt).34～13%(Wt) hydrogenchloride occurs with the form of saturated hydrochloric acid in addition.Such hydrochloric acid also need just can obtain hydrogenchloride through resolving, and increases equipment and energy consumption again.
According to the knowledge of generally acknowledging, we find that at work water as long as contact with chlorosilane hydrolysis reaction just takes place, and the hydrogenchloride of generation does not have excessive water dissolution to emit with gaseous state.Though the chlorosilane hydrolysis reaction is irreversible, not because the increase of hydrogen cloride concentration can not be carried out hydrolysis reaction.But under high hydrogen cloride concentration, the organochlorosilane particle surface forms one deck hydrogen chloride gas film, makes water molecules be difficult for contacting with the organochlorosilane molecule, thereby has reduced speed of response.Even more serious is reaction fully before, the organochlorosilane molecule will be diffused in the hydrogenchloride and be pulled away, and has therefore reduced the purity that yield has also influenced hydrogenchloride simultaneously, brings difficulty for the methyl chloride synthesizing section.One of key of the present invention is exactly to have adopted hydrolysis under certain pressure.Make hydrogenchloride under that pressure and temperature, be in undersaturated condition, therefore also not generating gas film had both accelerated speed of response, had also prevented the loss of organochlorosilane.
Adopting following processing step is principal feature of the present invention:
1. reactor adopts static mixer or Suhl scholar formula static mixer and long thrust-augmenting nozzle, the pressure during with reinforcement mixing effect and increase reaction.
2. hydrolysising reacting system is that a circulation loop (as shown in the figure) acid solution is the circulatory mediator in the loop, does not outflow.
3. the hydrolysis reaction section keeps certain pressure, after allowing the hydrogenchloride that produces after all organochlorosilane complete hydrolysis all be dissolved in the acid, the hydrochloric acid of whole system is under that pressure, also be in undersaturated condition, after hydrolysis reaction is finished, pressure is descended gradually, up to becoming normal pressure, hydrogenchloride is emitted with gaseous phase, reach the purpose of separating hydrogen chloride and hydrolyzate.
4. the ratio of recycle acid and organochlorosilane during augmenting response has two effects: the one, increased the touch opportunity of organochlorosilane and water, and the 2nd, before and after the reaction, the concentration of acid and the temperature variation of reaction system are little.
Following processing condition all are suitable to the present invention:
1. temperature of reaction 20～50(the best is 35 ± 5) ℃
2. 10～150 seconds residence time in reactor.(the best is 25 ± 2 seconds)
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 Tou Ruing (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) above pascal
Organochlorosilane among the present invention is expressed as RaHbSiCL(4-a-b with a general formula)
R is expressed as alkyl, thiazolinyl, the nitrile ethyl; 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 more than or equal to 2, the positive integer smaller or equal to 3.When a R more than or equal to 2 time can be identical group and different groups.
For better explanation characteristics of the present invention, diagram is made description below:
Hydrolysis process carries out in a loop.Its major equipment is by 1. Suhl scholar formula static mixer and 2. 3. gas-liquid separator and 4. phase separator of thrust-augmenting nozzle; 5. neutralizer; 6. 7. composition such as infusion pump of heat exchanger.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 enters neutralizer (or water scrubber) for the acidic hydrolysis thing, 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, like this after the washing, 1%(Wt is reduced in acid in the hydrolyzate) below, neutralization is very convenient, and the dilute hydrochloric acid sedimentation that obtains is after 48 hours, add in the response circuit, 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 hydrogen chloride yield is up to 90～98%(Wt), than the quality of method raising 24～11%(Wt) the gained hydrolysates of talking among the Britain patent GB211247A, the hydrolysate indistinction that is hydrolyzed with excessive water except cyclosiloxane hangs down some.
3. there is not acid solution to discharge.
Claims (3)
1, a kind of organochlorosilane continuous hydrolysis novel process.Its main equipment is reactor and phase separator [4].The invention is characterized in that reactor is a static mixer [1] with hydrochloric acid saturated solution cyclical operation under the normality of 60 to 100 times (the best is 75 times) of organochlorosilane volume, the required water of hydrolyzing organochlorosilanes adds with the water in water or the hydrochloric acid, the equivalence ratio of the chlorine in its amount and the organochlorosilane is 1.05～1.1: 1, and hydrolysis reaction is 9.8～30 * 10
4(the best is 16.3～21 * 10 to pascal
4Pascal) pressure, temperature are 20～50 ℃ (the best is 35 ± 5 ℃) reaction down, and the total residence time of material in reactor is 10～150 seconds (best 25 ± 2 seconds).
2,, it is characterized in that adopting Suhl formula static mixer as the said new process of hydrolyzing of claim 1.Add a gas-liquid separator (3) before being separated, add circulation fluid transferpump (7) and heat exchanger (6) behind the phase separator.To guarantee running steady in a long-term.
3, as claim 1 and 2 said new process of hydrolyzing, it is characterized in that the sour domestic animal hydrolyzate separated from phase separator, once wash again, (the also available static mixer of this equipment) improves the rate of recovery of chlorine to reduce the acid content in the hydrolyzate.
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 true CN85100433A (en) | 1986-07-23 |
| CN85100433B CN85100433B (en) | 1988-05-11 |
Family
ID=4791154
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85100433A Expired CN85100433B (en) | 1985-04-01 | 1985-04-01 | New process of hydrolyzing organochlorosilanes |
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| Country | Link |
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| CN (1) | CN85100433B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944492B (en) * | 2005-10-04 | 2010-05-26 | 瓦克化学有限公司 | Method for the preparation of organopolysiloxanes |
| CN101921397A (en) * | 2010-08-24 | 2010-12-22 | 泸州北方化学工业有限公司 | Halogenated silanes and reaction medium mixed reactor and method |
| CN101619072B (en) * | 2009-08-13 | 2011-10-05 | 浙江大学 | Process for hydrolyzing dimethyl dichlorosilane by using concentrated hydrochloric acid loop |
| CN103183829A (en) * | 2013-03-28 | 2013-07-03 | 青岛科技大学 | Concentrated acid hydrolysis system used for organochlorosilane concentrated acid hydrolysis |
| CN101743068B (en) * | 2007-05-09 | 2015-04-01 | 伍德控股环境公司 | Apparatus and method for treating materials with compositions |
| CN106006557A (en) * | 2016-05-18 | 2016-10-12 | 昆明理工大学 | Method for producing hydrogen chloride from chlorosilane raffinate |
| 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 |
| CN113996256A (en) * | 2021-11-12 | 2022-02-01 | 新疆晶硕新材料有限公司 | Method and device for treating dimethyl dichlorosilane hydrolysate |
| CN114085381A (en) * | 2021-11-29 | 2022-02-25 | 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
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944492B (en) * | 2005-10-04 | 2010-05-26 | 瓦克化学有限公司 | Method for the preparation of organopolysiloxanes |
| CN101743068B (en) * | 2007-05-09 | 2015-04-01 | 伍德控股环境公司 | 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 |
| CN101921397A (en) * | 2010-08-24 | 2010-12-22 | 泸州北方化学工业有限公司 | Halogenated silanes and reaction medium mixed reactor and method |
| CN103183829A (en) * | 2013-03-28 | 2013-07-03 | 青岛科技大学 | Concentrated acid hydrolysis system used for organochlorosilane concentrated acid hydrolysis |
| CN103183829B (en) * | 2013-03-28 | 2014-09-24 | 青岛科技大学 | Concentrated acid hydrolysis system used for organochlorosilane concentrated acid hydrolysis |
| CN106006557A (en) * | 2016-05-18 | 2016-10-12 | 昆明理工大学 | Method for producing hydrogen chloride from chlorosilane raffinate |
| 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 |
| CN113996256A (en) * | 2021-11-12 | 2022-02-01 | 新疆晶硕新材料有限公司 | Method and device for treating dimethyl dichlorosilane hydrolysate |
| 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 |
| CN114085381A (en) * | 2021-11-29 | 2022-02-25 | 内蒙古恒星化学有限公司 | Gas-phase dimethyl dichlorosilane hydrolysis process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85100433B (en) | 1988-05-11 |
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