CN102219760A - Method for preparing epichlorohydrin and white carbon black by coupling process - Google Patents
Method for preparing epichlorohydrin and white carbon black by coupling process Download PDFInfo
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- CN102219760A CN102219760A CN201110105190XA CN201110105190A CN102219760A CN 102219760 A CN102219760 A CN 102219760A CN 201110105190X A CN201110105190X A CN 201110105190XA CN 201110105190 A CN201110105190 A CN 201110105190A CN 102219760 A CN102219760 A CN 102219760A
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- carbon black
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- epoxy chloropropane
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Abstract
The invention discloses a method for preparing epichlorohydrin and white carbon black by a coupling process. The method comprises the steps as follows: hydrolyzing silicon tetrachloride to obtain silica gel and a byproduct, namely, HCl (chlorine hydride); chlorinating the byproduct-HCl with glycerol under the participation of a catalyst to obtain glycerindichlorohydrin and a by-product, namely, water; hydrolyzing the silicon tetrachloride with the byproduct-water; and carrying out thermal treatment on the silica gel to obtain the white carbon black, and saponifying the glycerindichlorohydrin to obtain epoxy chloropropane. In the invention, through coupling of glycerol chlorination and SiCl4 hydrolysis process, the byproduct water during chlorination and the byproduct HCl during hydrolysis process are both utilized, thus being beneficial to energy conservation and emission reduction as well as clean production during the production processes of the epoxy chloropropane and the white carbon black. In addition, due to mutual utilization of the byproducts during the two processes, the cost of the products obtained from the coupling production process is greatly lowered; furthermore, the coupling production process is beneficial to popularization and application of glycerol epoxy chloropropane technology, as well as health development of polycrystalline silicon industry.
Description
Technical field
The invention belongs to a kind of method for preparing epoxy chloropropane and white carbon black.Specifically relating to a kind of is the method for feedstock production epoxy chloropropane and white carbon black by glycerine and silicon tetrachloride with coupling technique.
Background technology
Epoxy chloropropane is a kind of important Essential Chemistry product, is widely used in to make Resins, epoxy and multiple fine chemicals.The main production method of epoxy chloropropane is based on the propylene high-temperature chlorination process of Shell company exploitation in 1948.Be that propylene earlier generates propenyl chloride with chlorine reaction about 500 ℃, the propenyl chloride of generation generates dichlorohydrine with the chlorine water reaction about 5 ℃, and the dichlorohydrine of generation obtains epoxy chloropropane with caustic soda or liming generation saponification cyclization again.Such production process energy consumption is very high, production process danger, and produce a large amount of brine wastes (producing 40 ~ 50 tons of waste water/ton epoxy chloropropane).Reaction process is as follows:
In the last few years, the technology of utilizing by-product glycerol of biological diesel oil to prepare epoxy chloropropane received very big concern.Its reaction process is that biological glycerol and HCl react the generation glycerin dichlorohydrin under catalyst action, and glycerin dichlorohydrin that is generated and alkali reaction generate epoxy chloropropane, and reaction process is as follows:
Such reaction can be carried out (CN1882522A) in stirring tank, also can carry out (CN100509726C) in tubular reactor.
Relative propylene method, the glycerine method has remarkable advantages.Be embodied in: utilize renewable resources, technology is simple, energy consumption low (be about propylene method 1/3), wastewater flow rate very little (be about propylene method 1/30).Yet for the glycerine method, the subject matter of existence is that the source of reaction raw materials HCl is unlike Cl in the propylene method
2Be easy to get like that, the accumulating of HCl can not show a candle to Cl
2Convenient, this is the major obstacle that restriction glycerine method technology is applied.
White carbon black is a kind of multifunction additive, is widely used in industries such as rubber, tire, coating, printing ink, medicine, machinery.The method that generates white carbon black at present mainly contains vapor phase process and liquid phase method.Vapor phase process is to use the chlorosilane hydrolysis, and liquid phase method is to use the water glass acid-hydrolysis method.Vapor phase process can produce large quantity of exhaust gas, and liquid phase method can produce a large amount of brine wastes.The vapor phase process quality is better, generally adopts vapor phase process to produce high-quality white carbon black.
Along with the photovoltaic industry comes into one's own in the whole world, the polysilicon industry of China develops rapidly.To 2011, Chinese polysilicon production capacity reached about 200,000 tons.Yet produce polysilicon per ton can by-product about 15 tons silicon tetrachloride, the scientific and reasonable utilization of silicon tetrachloride has been become the main difficult problem of polysilicon industry development, demand urgently solving.
The method of processing silicon chloride mainly contains two kinds at present: a kind of is to be translated into trichlorosilane (CN101941702), lacks the market competitiveness but such technology cost is very high; Another kind method is to prepare white carbon black (CN101798088) with it.Utilize silicon tetrachloride to prepare 1 ton of white carbon black of the every theoretically production of white carbon black and want 2.43 tons of HCl dry gas of by-product, use H
2O then produces 7.6 tons of hydrochloric acid (32%) after absorbing.Though can obtain high-quality white carbon black with silicon tetrachloride, because of by-product a large amount of hydrochloric acid like this makes the application of this processing method be suppressed.
The content of invention:
The objective of the invention is that glycerin chlorination is prepared epoxy chloropropane process and silicon tetrachloride hydrolysis prepares the white carbon black process and is coupled, utilize the water of glycerin chlorination by-product to come hydrolysis of silicon tetrachloride, the HCl that utilizes the silicon tetrachloride hydrolysis to produce again comes chlorination glycerine, obtain two products simultaneously, by product is utilized mutually.Reactional equation is as follows:
Technical scheme of the present invention is:
A kind of method for preparing epoxy chloropropane and white carbon black, carry out according to following step:
(1) with catalyst dissolution in glycerine, with in the volume pump input reactor, and with SiCl
4Slowly input contains in the glycerine of catalyzer, and control certain reaction temperature, time and pressure react;
(2) the control certain reaction is carried out filtering separation with reaction mixture after the time;
(3) step (2) is separated refilter after silicon gel filter cake that the hydrolysis obtain produces washs with rare glycerine of about 30%; Silicon gel after washing is made into 20 ~ 50% slurries with deionized water, and slurries are carried out spraying drying under 400 ~ 1000 ℃ of conditions, can obtain white carbon black;
(4) filtrate of washing generation merges the back, obtains glycerin dichlorohydrin, a glycerin chlorohydrin, glycerine and tar through rectification under vacuum with the reaction filtered liquid; Wherein glycerin dichlorohydrin and alkali further react, and generate epoxy chloropropane; One glycerin chlorohydrin and glycerine loop back feed system, continue reaction; Tar carries out harmless treatment.
Wherein the described catalyzer of step (1) is lipid acid and/or mineral acid, and wherein said lipid acid is meant C
2~ C
12Monoprotic acid and polyprotonic acid, C preferably
6~ C
8Diprotic acid.
Wherein the described temperature of reaction of step (1) is 60 ~ 160 ℃, and preferably 70 ~ 120 ℃, preferably early stage is controlled 70 ~ 90 ℃ in reaction, 100 ~ 120 ℃ of reaction later stage controls.
The described SiCl of step (1) wherein
4Can be and the glycerine cocurrent adding material, also can be that the form that multichannel is distributed adds, and preferably the form of multichannel distribution adds SiCl
4, can control reacting balance ground like this and carry out, realize safety operation.
Wherein the raw materials components mole ratio of described glycerine of step (1) and silicon tetrachloride is 2.5 ~ 1.8:1, and preferred mol ratio is 2.3 ~ 1.8:1.
Wherein the described reaction times of step (1) is 2.5 ~ 8 hours, preferably 3 ~ 6 hours.
Wherein the described working pressure of step (1) is 0.03 ~ 1.0MPa, preferably 0.35 ~ 0.85 MPa.Pressurization helps improving speed of reaction and product yield, but too high pressure is unfavorable for safety operation.
Reaction mixture after wherein chlorination described in the step (2) and hydrolysis coupling reaction finish can be by press filtration, also can pass through suction filtration.
Concentration of slurry preferably in mass 30 ~ 40% in the step (3) wherein; Preferably 550 ~ 700 ℃ of drying temperatures.
Wherein the alkali described in the step (4) is NaOH or milk of lime or KOH, and resulting glycerin dichlorohydrin and described alkali are carried out saponification reaction and obtain epoxy chloropropane.
Above-mentioned a kind of procedure for preparing epoxy chloropropane and white carbon black can be intermittently, also can be successive, and preferred scheme is the operate continuously process.Used reactor types can be a tubular type, also can be the still formula, can also be tower.
The effect of invention:
The present invention is with glycerin chlorination and SiCl
4Hydrolytic process is coupled, and makes the water of chlorination process by-product and the HCl of hydrolytic process by-product all obtain utilizing, and is beneficial to epoxy chloropropane production process and carbon white production process energy-saving and emission-reduction, cleaner production.Utilize the other side's byproduct again mutually owing to two processes, the product cost that makes coupling connection production process obtain declines to a great extent; Say that further the coupling connection production process that the present invention proposes helps applying of glycerine method epoxy chloropropane technology, also helps the sound development of polysilicon industry.
Embodiment
Among the present invention in the used Industrial products glycerine glycerol content can be 80% ~ 99%(mass ratio), preferably contain the glycerine of quality amount 2 ~ 8%.
For used Industrial products SiCl
4Middle SiCl
4Content has no special requirements, and content is greater than the 90%(mass ratio) get final product.
Operate continuously in example 1. tubular reactors
It is in 95% the industry glycerol (mass ratio) that hexanodioic acid (catalyzer) is dissolved in content, is made into the 5%(mass ratio) industry glycerol solution.The industry glycerol that will contain catalyzer with volume pump is pressed in the tubular reactor that cumulative volume is 50L with the speed of 11.75kg/h, two portions before and after tubular reactor is divided into, fore portion tubular reactor volume is that 30L(DN40mm pipe 24m is long), control reaction temperature is 70 ℃; Rear section tubular reactor volume is 20L(DN40mm pipe 16m), control reaction temperature is 130 ℃.
Is the 98.5%(mass ratio with another volume pump with content) SiCl
4Speed with 8.5kg/h is pressed into above-mentioned reactor.SiCl
4With the mol ratio of glycerine be 2.3:1.0, SiCl
4Be to enter reactor in the mode that multichannel is distributed.Wherein 50% is that form with three tunnel uniformly distributings enters the fore portion reactor, and 50% is that form with two tunnel uniformly distributings enters the rear section reactor in addition.The control residence time of material in reactor is about 3h.Reactor pressure 0.45 ~ 0.55MPa.
Effusive material pumps into the pressure filter in tubular reactor, and filtrate is thick chlorination glycerine, and filter cake is the silicon gel.Filter cake is made into the 40%(mass ratio with glycerine washing back with deionized water) slurry to send into gas flow temperature be to dewater in 700 ℃ the spray-drying tower, obtain white carbon black product 2.88kg/h, its specific surface area is 167m
2/ g, median size is 185nm, yield about 98%.
After merging, the glycerine of thick chlorination glycerine and washing leaching cake sends into chlorination glycerine knockout tower.Glycerin dichlorohydrin of telling and milk of lime are mixed into the saponification column reaction, and the epoxy chloropropane of generation finally obtains the epoxy chloropropane finished product from the cat head extraction through further making with extra care.
The heavy constituent of telling from chlorination glycerine knockout tower (glycerin chlorohydrin) loop back feed system, gently turn to glycerin dichlorohydrin with further chlorination, and tar is discharged from the tower still.Through 8 hours continuous operation, make entire reaction system equilibrium establishment, can finally obtain content from the epoxy chloropropane rectifying tower is 99.5% epoxy chloropropane 8.8 7kg/h, its yield is 79.4%.
Example 2. tank reactor periodical operation
At volume is 0.5 m
3The outside circulation reactor in to add content be 99% smart glycerine 186kg, add Glacial acetic acid 10 kg, close charging opening, start recycle pump, be pressed into SiCl with the speed of 35kg/h by feed pipe earlier with volume pump
4, be 90 ℃ by chuck water-cooled control reaction temperature.React after 2 hours, with SiCl
4The speed that pumps into change 50kg/h into, control reaction temperature is 120 ℃, continues such operation 2 hours, pumps into SiCl altogether
4170kg, glycerine and SiCl
4Mol ratio is 2:1, and working pressure is at 0.3 ~ 0.8MPa, and total reaction time is 4 hours.
Reaction is sent into reaction product in the rotary drum suction filter by the outer circulation pump after finishing, the rare glycerine washing filter residue with 30%.
Filter residue is made into the slurry of siliceous gel 50% with deionized water, and this slurry obtains white carbon black product 58.0 kg with being pumped in 550 ℃ the spray-drying tower, and yield is 96.7%, and its specific surface area is 148 m
2/ g, median size is 206 nm.
To carry out rectifying after filtrate and the merging of residue washing liquid, obtaining glycerin dichlorohydrin, is that 20% NaOH carries out saponification reaction with the glycerin dichlorohydrin of gained and concentration, obtains the epoxy chloropropane crude product, through the refining content that obtains is 99.8% epoxy chloropropane 164.6 kg, yield 88.5%.
Example 3. tower reactor operate continuouslys
It is to be made into 3% solution in 82% the raw glycerine that silicomolybdic acid is dissolved in content.The raw glycerine that will contain catalyzer with volume pump is pressed in the tower reactor with the speed of 217kg/h.Tower reactor is composed in series by two portions of band outer circulation pump, and first tower body is long-pending to be 0.4m
3, second tower body is long-pending to be 0.6m
3
With the SiCl of volume pump with content 98.5%
4Speed with 170kg/h is pressed in the above-mentioned tower reactor.Glycerine and SiCl
4Mol ratio be 1.8:1.SiCl
4Be to enter tower reactor in the mode that two-way distributes, wherein one the tunnel with 40% SiCl
4Send in first tower reactor, 60% SiCl will be left in another road
4Send in second tower reactor.Service temperature control 60 ℃, the working pressure 0.25 ~ 0.35MPa of first tower, service temperature control 110 ℃, the working pressure 0.5 ~ 0.6MPa of second tower.Material total residence time in tower is about 3.5 hours.
Effusive reaction solution pumps in the pressure filter, and with rare glycerine washing leaching cake of 30%.After merging, washings and reactant filtrate separates and circulation.
After the continuously feeding reaction 6 hours, the reactive system operation is stable gradually, and filter cake is made into 20% slurry with deionized water, sends in 950 ℃ the spray-drying tower dryly, obtains white carbon black 57.1kg/h, yield 95.2%.Its specific surface area is 219 m
2/ g, median size is 147 nm.
Filtrate is through rectifying separation, heavy constituent (glycerin chlorohydrin and glycerine) circulating reaction, and light constituent is a glycerin dichlorohydrin.The KOH of gained glycerin dichlorohydrin and 25% concentration is reacted the thick epoxy chloropropane of generation at saponification column, obtain the epoxy chloropropane 153.5kg/h of purity 99.8% again through rectifying, yield is 91.7%.
Claims (8)
1. method for preparing epoxy chloropropane and white carbon black is characterized in that carrying out according to following step:
(1) with catalyst dissolution in glycerine, with in the volume pump input reactor, and with SiCl
4Slowly input contains in the glycerine of catalyzer, and control certain reaction temperature, time and pressure react;
(2) the control certain reaction is carried out filtering separation with reaction mixture after the time;
(3) step (2) is separated refilter after silicon gel filter cake that the hydrolysis obtain produces washs with rare glycerine of about 30%; Silicon gel after washing is made into 20 ~ 50% slurries with deionized water, and slurries are carried out spraying drying under 400 ~ 1000 ℃ of conditions, can obtain white carbon black;
(4) filtrate of washing generation merges the back, obtains glycerin dichlorohydrin, a glycerin chlorohydrin, glycerine and tar through rectification under vacuum with the reaction filtered liquid; Wherein glycerin dichlorohydrin and alkali further react, and generate epoxy chloropropane; One glycerin chlorohydrin and glycerine loop back feed system, continue reaction; Tar carries out harmless treatment.
2. a kind of method for preparing epoxy chloropropane and white carbon black according to claim 1 is characterized in that wherein the described catalyzer of step (1) is lipid acid and/or mineral acid, and wherein said lipid acid is meant C
2~ C
12Monoprotic acid and polyprotonic acid, 60 ~ 160 ℃ of described temperature of reaction, described SiCl
4Can be and the glycerine cocurrent adding material, also can be that the form that multichannel is distributed adds, and the raw materials components mole ratio of described glycerine and silicon tetrachloride is 2.5 ~ 1.8:1, and the described reaction times is 2.5 ~ 8 hours, and described working pressure is 0.03 ~ 1.0MPa.
3. a kind of method for preparing epoxy chloropropane and white carbon black according to claim 1 is characterized in that the reaction mixture after wherein chlorination described in the step (2) and hydrolysis coupling reaction finish can be by press filtration, also can carry out filtering separation by suction filtration.
4. a kind of method for preparing epoxy chloropropane and white carbon black according to claim 1 is characterized in that wherein the middle concentration of slurry of step (3) is 30 ~ 40% in mass; Drying temperature is 550 ~ 700 ℃.
5. a kind of method for preparing epoxy chloropropane and white carbon black according to claim 1, it is characterized in that wherein the alkali described in the step (4) is NaOH or milk of lime or KOH, resulting glycerin dichlorohydrin and described alkali are carried out saponification reaction and obtain epoxy chloropropane.
6. a kind of method for preparing epoxy chloropropane and white carbon black according to claim 1, it is characterized in that described procedure can be intermittently, also can be successive, and used reactor types can be a tubular type, also can be the still formula, can also be tower.
7. a kind of method for preparing epoxy chloropropane and white carbon black according to claim 2 is characterized in that wherein the described catalyzer of step (1) is C
6~ C
8Diprotic acid, described temperature of reaction is 70 ~ 120 ℃, reaction the early stage is controlled 70 ~ 90 ℃, 100 ~ 120 ℃ of reaction later stage controls; Described SiCl
4The form of distributing with multichannel adds SiCl
4, the raw materials components mole ratio of described glycerine and silicon tetrachloride is 2.3 ~ 1.8:1, and the described reaction times is 3 ~ 6 hours, and described working pressure is 0.35 ~ 0.85 MPa.
8. a kind of method for preparing epoxy chloropropane and white carbon black according to claim 6 is characterized in that described procedure is the operate continuously process.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584745A (en) * | 2012-02-09 | 2012-07-18 | 常州大学 | Method using glycerol and silicon tetrachloride to prepare epichlorohydrin and white carbon black |
| CN106831860A (en) * | 2017-01-10 | 2017-06-13 | 肇庆市稳固化工有限公司 | A kind of Gemini phosphate ester surfactants and preparation method thereof |
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|---|---|---|---|---|
| CN1208016A (en) * | 1998-08-27 | 1999-02-17 | 沈阳化工股份有限公司 | Gas phase process preparing white carbon |
| CN1882522A (en) * | 2003-11-20 | 2006-12-20 | 索尔维公司 | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
| CN101007751A (en) * | 2007-01-26 | 2007-08-01 | 江苏工业学院 | Preparation method of dichloro propanol from glycerin |
| US20080015370A1 (en) * | 2004-07-21 | 2008-01-17 | Hook Bruce D | Process for the conversion of a crude glycerol, crude mixtures of naturally derived multicomponent aliphatic hydrocarbons or esters thereof to a chlorohydrin |
-
2011
- 2011-04-26 CN CN 201110105190 patent/CN102219760B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208016A (en) * | 1998-08-27 | 1999-02-17 | 沈阳化工股份有限公司 | Gas phase process preparing white carbon |
| CN1882522A (en) * | 2003-11-20 | 2006-12-20 | 索尔维公司 | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
| US20080015370A1 (en) * | 2004-07-21 | 2008-01-17 | Hook Bruce D | Process for the conversion of a crude glycerol, crude mixtures of naturally derived multicomponent aliphatic hydrocarbons or esters thereof to a chlorohydrin |
| CN101007751A (en) * | 2007-01-26 | 2007-08-01 | 江苏工业学院 | Preparation method of dichloro propanol from glycerin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584745A (en) * | 2012-02-09 | 2012-07-18 | 常州大学 | Method using glycerol and silicon tetrachloride to prepare epichlorohydrin and white carbon black |
| CN106831860A (en) * | 2017-01-10 | 2017-06-13 | 肇庆市稳固化工有限公司 | A kind of Gemini phosphate ester surfactants and preparation method thereof |
| CN106831860B (en) * | 2017-01-10 | 2018-12-07 | 肇庆市稳固化工有限公司 | A kind of Gemini phosphate ester surfactants and preparation method thereof |
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Effective date of registration: 20150925 Address after: Daitou town of Liyang City Ferry Street 213311 Jiangsu city of Changzhou province 8-2 No. 7 Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |