CN102408568B - Method for continuously preparing high boiling silicone oil - Google Patents
Method for continuously preparing high boiling silicone oil Download PDFInfo
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- CN102408568B CN102408568B CN 201110356133 CN201110356133A CN102408568B CN 102408568 B CN102408568 B CN 102408568B CN 201110356133 CN201110356133 CN 201110356133 CN 201110356133 A CN201110356133 A CN 201110356133A CN 102408568 B CN102408568 B CN 102408568B
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Abstract
The invention relates to a method for continuously preparing high boiling silicone oil, which comprises the following steps of: continuously adding an organic silicon high boiling substance and methanol in a ratio into an alcoholysis reaction kettle from the bottom, performing alcoholysis, and ensuring that an upper-layer material overflows and enters a falling film reactor to deepen alcoholysis and desorb HCl gas; and neutralizing the material subjected to alcoholysis, demixing, and neutralizing a neutralization bottom material to obtain the high boiling silicone oil. By the process, continuous production and automatic process control can be realized in the process of preparing the high boiling silicone oil, the aims of improving efficiency, increasing product stability and the like are fulfilled, and oil yield is over 85 percent.
Description
Technical field
The present invention relates to the synthetic production technical field of methyl chlorosilane monomer, be specifically related to a kind of continuous production method of high boiling point silicon oil.
Background technology
In the methyl chlorosilane monomer building-up process, produce a large amount of high boiling organosilicon point by products, the organosilicon high-boiling product complicated components contains the silicon chlorine key that a large amount of facile hydrolysiss produce hydrogen-chloride etching gas, therefore storage and use difficulty have hindered further developing of methyl chlorosilane monomer scale.
At present domestic and international processing to organosilicon high-boiling product has following several mode: catalytic pyrolysis prepares silane, alcoholysis prepares high boiling point silicon oil, hydrolysis preparation water-resisting agent and silicone resin etc.Wherein to prepare high boiling point silicon oil be one of its important treatment process in alcoholysis, and technique is simple, and secondary pollution is few, recycling economy, and end-use is extensive, is the focus method that organosilicon high-boiling product utilizes, and is worth giving priority to.
Chinese patent ZL200410013358.4 discloses a kind of preparation method with the synthetic high boiling point silicon oil of organosilicon high-boiling product, at normal temperatures, in organosilicon high-boiling product, drip the methyl alcohol alcoholysis, then with in urea, fusing assistant and the bicarbonate of ammonia and the hydrogenchloride that dissolves in the system, standing demix, filter, obtain the high boiling point silicon oil product.After this, Chinese patent ZL200710168925.7, ZL200710055283.X, 200910019645.9,201010581672.8 etc. all the oil yield for above-mentioned patent is low, the problems such as the neutralizing agent consumption is large, adopting rising alcoholysis temperature, using tower instead is that the means such as alcoholysis device are carried out process modification, obtains relatively better effect.And Chinese patent 201110091829.3,201110091851.8,201110091854.1 etc., then adopt the means such as ethanol alcoholysis, catalytic pyrolysis rearrangement, neutralization, obtain high boiling point silicon oil, and reclaim its by product, realized resource recycling, eco-friendly friendly process.
Above-mentioned disclosed patented technology, all can obtain up-to-standard high boiling point silicon oil product, but preparation technology has all adopted mode intermittently, the inherent characteristics of this mode brings in the high boiling point silicon oil preparation process, inefficiency, all drawbacks such as oil yield is low, and can't realize automatic control, and product batches is unstable.
Summary of the invention
Problem to be solved by this invention is to provide a kind of continuous production method of high boiling point silicon oil, and this technique can realize that in the high boiling point silicon oil preparation process serialization production, process control automatically.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: a kind of continuous production method of high boiling point silicon oil, it is characterized in that, and comprise the steps:
⑴ alcoholysis step: organosilicon high-boiling product, methyl alcohol in mass ratio 0.2 ~ 5:1 add respectively from alcoholysis reaction still bottom, continues in the adition process to stir, and alcoholysis 60min ~ 150min, temperature of reaction is controlled at 30 ℃ ~ 65 ℃, and removes HCl gas;
⑵ in-depth alcoholysis step: the upper materials automatic overflow of alcoholysis reaction still imports in the falling film reactor, in-depth alcoholysis and desorb HCl gas 2min ~ 20min, and temperature is 65 ℃ ~ 150 ℃;
⑶ neutralization procedure: above-mentioned alcoholysis material is pumped in the neutralization reaction still, and with neutralizing agent generation neutralization reaction 10min ~ 30min, pH value reaches 6 ~ 7;
⑷ stratification step: in the material of becoming reconciled import quantizer, standing demix 150min ~ 500min, the upper strata is high boiling point silicon oil, lower floor be in and bed material, in and bed material enter the further neutralizing treatment of Calcified pond.
Preferably, machine silicon high boiling material, the methanol quality in the described alcoholysis step is preferably 1 ~ 2:1 than ratio.The total consumption of methyl alcohol considers that not only the alcoholysis of organosilicon high-boiling product own is required, and it is required that solid salt is dissolved into solution after also will considering to neutralize.
Preferably, the temperature in the alcoholysis reaction still is preferably 40 ℃ ~ 50 ℃, because alcoholysis reaction is relatively fiercer at the beginning, the suitable temperature of control reactor is so that reaction is carried out more gently.
Preferably, the falling film reactor temperature is preferably 70 ℃ ~ 130 ℃.Preliminary alcoholysis in the alcoholysis reaction still, the chlorine element is partly replaced in the material, but the alcoholysis reaction degree is limited, therefore material need enter the HCl desorption of gases that carries out dissolving in alcoholysis in-depth and the system in the falling film reactor, thereby greatly improve oil yield, and reduce later stage neutralizing agent consumption.
Preferably, neutralizing agent specifically can be selected potassium hydroxide, sodium hydroxide, urea, calcium carbonate.Because steric hindrance, in the alcoholysis process, the chlorine element in the organosilicon high-boiling product can't be substituted fully, therefore need after the alcoholysis to adopt neutralizing agent further to neutralize, its add-on is as the criterion so that the rear high boiling point silicon oil pH value of neutralization reaches 6 ~ 7.
Preferably, according to the speed conditions of alcoholysis and neutralization reaction, material mean residence time in the alcoholysis reaction still is preferably 80min ~ 120min; Mean residence time is preferably 3min ~ 10min in falling film reactor; Mean residence time is preferably 15min ~ 25min in the neutralization reaction still; Mean residence time is preferably 200min ~ 350min in quantizer.
Delamination process of the present invention can adopt ordinary method to carry out.High boiling point silicon oil of the present invention is the mixture that comprises multiple alkylakoxysiloxanes.
The continuous production method of high boiling point silicon oil of the present invention is owing to the HCl desorption of gases that adopts dissolving in falling film reactor in-depth alcoholysis reaction and the system, thus the raising oil yield, and reduce later stage neutralizing agent consumption.And realized serialization production, reached purposes such as raising the efficiency, increase product stability.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples:
Fig. 1 is the schema of high boiling point silicon oil continuous production method.
1 is the organosilicon high-boiling product storage tank; 2 is the methyl alcohol storage tank; 3,4,9 is under meter; 5 is the alcoholysis reaction still; 6,7 is condenser; 8 is falling film reactor; 10 is the neutralization reaction still; 11 is quantizer; 12 is product storage tank.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Describe the present invention in detail below in conjunction with embodiment, should be appreciated that described herein giving an example only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1:
In the 1.5:1 ratio, with impeller pump organosilicon high-boiling product, methyl alcohol are squeezed into alcoholysis reaction still bottom continuously, temperature is controlled at 40 ℃, alcoholysis, mean residence time 90min, the hydrogen chloride gas that alcoholysis produces enters hydrochloric acid absorption tower by overhead condenser and reclaims concentrate.The upper materials overflow enters in the falling film reactor, in-depth alcoholysis and HCl desorption of gases, and temperature is controlled at 100 ℃, mean residence time 4min.The material that alcoholysis is good is continuously pumped in the neutralization reaction still, carries out neutralization reaction, mean residence time 20min with the urea of raw material total amount 15%.Material enters quantizer again, layering, mean residence time 240min, the upper strata is high boiling point silicon oil, lower floor be in and bed material, in and bed material enter the further neutralizing treatment of Calcified pond.
The preparation the high boiling point silicon oil product: viscosity be (25 ℃, mm2/s) 32, pH value is 7.5, oil yield is 87.5%.
Embodiment 2:
In the 1.5:1 ratio, with impeller pump organosilicon high-boiling product, methyl alcohol are squeezed into alcoholysis reaction still bottom continuously, temperature is controlled at 50 ℃, alcoholysis, mean residence time 90min.The upper materials overflow enters in the falling film reactor, in-depth alcoholysis and HCl desorption of gases, and temperature is controlled at 110 ℃, mean residence time 4min.The material that alcoholysis is good is continuously pumped in the neutralization reaction still, carries out neutralization reaction, mean residence time 20min with the urea of raw material total amount 11%.Material enters quantizer again, layering, mean residence time 240min, the upper strata is high boiling point silicon oil, lower floor be in and bed material, in and bed material enter the further neutralizing treatment of Calcified pond.
The preparation the high boiling point silicon oil product: viscosity be (25 ℃, mm2/s) 36, pH value is 7.0, oil yield is 91.2%.
Embodiment 3:
In the 1.2:1 ratio, with impeller pump organosilicon high-boiling product, methyl alcohol are squeezed into alcoholysis reaction still bottom continuously, temperature is controlled at 50 ℃, alcoholysis, mean residence time 90min.The upper materials overflow enters in the falling film reactor, in-depth alcoholysis and HCl desorption of gases, and temperature is controlled at 110 ℃, mean residence time 4min.The material that alcoholysis is good is continuously pumped in the neutralization reaction still, carries out neutralization reaction, mean residence time 20min with the urea of raw material total amount 8%.Material enters quantizer again, layering, mean residence time 240min, the upper strata is high boiling point silicon oil, lower floor be in and bed material, in and bed material enter the further neutralizing treatment of Calcified pond.
The preparation the high boiling point silicon oil product: viscosity be (25 ℃, mm2/s) 21, pH value is 7.0, oil yield is 85.2%.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with technique can understand content of the present invention and according to this enforcement, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (9)
1.
The continuous production method of high boiling point silicon oil is characterized in that, comprises the steps:
⑴ alcoholysis step: organosilicon high-boiling product, methyl alcohol in mass ratio 0.2 ~ 5:1 add respectively from alcoholysis reaction still bottom, continues in the adition process to stir, and alcoholysis 60min ~ 150min, temperature of reaction is controlled at 30 ℃ ~ 65 ℃, and removes HCl gas;
⑵ in-depth alcoholysis step: the upper materials automatic overflow of alcoholysis reaction still imports in the falling film reactor, in-depth alcoholysis and desorb HCl gas 2min ~ 20min, and temperature is 65 ℃ ~ 150 ℃;
⑶ neutralization procedure: above-mentioned alcoholysis material is pumped in the neutralization reaction still, and with neutralizing agent generation neutralization reaction 10min ~ 30min, the pH value reaches 6 ~ 7;
⑷ stratification step: in the material of becoming reconciled import quantizer, standing demix 150min ~ 500min, the upper strata is high boiling point silicon oil, lower floor be in and bed material, in and bed material enter the further neutralizing treatment of Calcified pond.
2.
The continuous production method of high boiling point silicon oil according to claim 1 is characterized in that, organosilicon high-boiling product, methyl alcohol ratio in the described alcoholysis step are preferably 1 ~ 2:1.
3.
The continuous production method of high boiling point silicon oil according to claim 1 is characterized in that, the temperature in the alcoholysis reaction still is preferably 40 ℃ ~ 50 ℃.
4.
The continuous production method of high boiling point silicon oil according to claim 1 is characterized in that, the control of falling film reactor temperature is preferably at 70 ℃ ~ 130 ℃ in the in-depth alcoholysis step.
5.
The continuous production method of high boiling point silicon oil according to claim 1 is characterized in that described neutralizing agent is selected from potassium hydroxide, sodium hydroxide, urea, calcium carbonate.
6.
According to claim 1, the continuous production method of each described high boiling point silicon oil is characterized in that-5, and material mean residence time in the alcoholysis reaction still is preferably 80min ~ 120min.
7.
According to claim 1, the continuous production method of each described high boiling point silicon oil is characterized in that-5, and mean residence time is preferably 3min ~ 10min in falling film reactor.
8.
According to claim 1, the continuous production method of each described high boiling point silicon oil is characterized in that-5, and mean residence time is preferably 15min ~ 25min in the neutralization reaction still.
9.
According to claim 1, the continuous production method of each described high boiling point silicon oil is characterized in that-5, and mean residence time is preferably 200min ~ 350min in quantizer.
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| CN105061766B (en) * | 2015-09-16 | 2017-08-25 | 浙江新安化工集团股份有限公司 | The processing unit and method of a kind of organic silicon waste liquid |
| CN106589376B (en) * | 2016-11-30 | 2019-05-03 | 江西蓝星星火有机硅有限公司 | A kind of high-quality high boiling point silicon oil and preparation method thereof |
| CN108503836A (en) * | 2018-05-28 | 2018-09-07 | 宜昌兴越新材料有限公司 | High boiling point silicon oil hydrolyzes working system |
| CN113441101B (en) * | 2020-03-26 | 2023-02-10 | 上海汇友消防技术有限公司 | Disposal method for easily-fogging chlorine-containing compound leakage |
| CN112048065B (en) * | 2020-09-16 | 2022-04-29 | 江西蓝星星火有机硅有限公司 | Continuous production method of methyl ethyl silicone oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5374761A (en) * | 1994-04-29 | 1994-12-20 | Corning Corporation | Process for preparation of organooxysilanes |
| CN101016383A (en) * | 2007-01-24 | 2007-08-15 | 吉林市凇泰化工有限责任公司 | Method of producing high boiling point silicon oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5374761A (en) * | 1994-04-29 | 1994-12-20 | Corning Corporation | Process for preparation of organooxysilanes |
| CN101016383A (en) * | 2007-01-24 | 2007-08-15 | 吉林市凇泰化工有限责任公司 | Method of producing high boiling point silicon oil |
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Owner name: ZHEJIANG CHUANGJI ORGANIC SILICON MATERIAL CO., LT Free format text: FORMER OWNER: JIANGSU CHUANGJI RENEWABLE ENERGY CO., LTD. Effective date: 20130502 |
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Effective date of registration: 20130502 Address after: 324000 No. 26 Huayang Road, Quzhou hi tech Industrial Park, Zhejiang Patentee after: ZHEJIANG CHANGE ORGANIC SILICON MATERIAL CO., LTD. Address before: 215123 second teaching building B218, room 150, 220 benevolence Road, Suzhou Industrial Park, Jiangsu, China Patentee before: Jiangsu Chuangji Renewable Energy Co., Ltd. |
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