CN101003460A - Method and equipment for preparing bias fluoro ethylene by using R142b cracking - Google Patents
Method and equipment for preparing bias fluoro ethylene by using R142b cracking Download PDFInfo
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- CN101003460A CN101003460A CN 200610171018 CN200610171018A CN101003460A CN 101003460 A CN101003460 A CN 101003460A CN 200610171018 CN200610171018 CN 200610171018 CN 200610171018 A CN200610171018 A CN 200610171018A CN 101003460 A CN101003460 A CN 101003460A
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Abstract
This invention discloses method and apparatus for preparing vinylidene fluoride by pyrolyzing R142b. The method comprises: mixing R142b and high-purity nitrogen, sending into a pyrolysis furnace, pyrolyzing at 600-900 deg.C to obtain vinylidene fluoride, rapidly cooling to 30-80 deg.C, removing HCl and water, rectifying to obtain high-purity vinylidene fluoride, and returning unreacted R142b to the pyrolysis furnace. The pyrolysis furnace has large metal pipe diameter (76*40), U-shaped structure, small pressure drop, no carbon accumulation, and convenient maintenance.
Description
Technical field
The invention belongs to fluorine chemical fluorochemical monomer production field, relate to the preparation method and the equipment and technology of vinylidene (VDF).
Background technology:
The vinylidene molecular structural formula is:
Molecular weight 64,
Main application is: polyvinylidene difluoride (PVDF) is produced in homopolymerization, produces viton with other olefin-copolymerizations, as industrial chemicals, produces fluorine-containing fine chemicals.
The main route of producing:
(1) with 1,1-C2H4F2 C2H4F2 (R152a) is a raw material, with chlorine (CL
2) be dehydrogenating agent, Pintsch process is produced vinylidene.This is the method that China just adopted since the sixties in last century, and it has mainly experienced following three developmental stage:
A, dilute cracking (or R12) with carbonic acid gas;
CF
2HCH
3+ CL
2+ CO
2→ CF
2=CH
2+ HCL+CO
2Reaction conditions: (heating)
B, improve and remove thinner CO after operational condition improves the material linear velocity
2, simplify technology.
C, two-step approach:
I, CF
2HCH
3+ CL
2→ CF
2=CH
2+ HCL reaction conditions: (light)
II, photochemical chlorination product do not separate and directly go cracking.
CF
2ClCH
3+ HCl+CF
2HCH
3+ Cl
2→ CF
2=CH
2+ HCl reaction conditions: (heating)
(2) vinylidene chloride catalytic chlorination:
CCl
2=CH
2+ 2HF → CF
2=CH
2+ 2HCl reaction conditions: (heating)
It is many that above production method has a byproduct of reaction, the unit consumption height; The pipe reaction boiler tube is easily tied carbon, and life cycle is not long, and reactor amplifies than shortcomings such as difficulties.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of method for preparing vinylidene with the R142b thermo-cracking is provided.
The present invention also provides a kind of pyrocrack furnace that is used for aforesaid method.
Technical scheme of the present invention is as follows:
Prepare vinylidene with 1.1.1-difluoro monochlorethane (R142b) thermo-cracking, reaction formula is as follows:
CF
2ClCH
3→ CF
2=CH
2600～900 ℃ of+HCl temperature of reaction
Preparation method's step is as follows:
R142b is heated to 600～900 ℃ in pyrolyzer, Pintsch process generates vinylidene, and the gas mixture after the cracking is chilled to 30～80 ℃ through quencher, carries out dehydrochlorination and dehydration thereupon, obtains highly purified vinylidene through rectifying again; Again return pyrolyzer after unreacted R142b reclaims and carry out cracking.
The present invention is preferably as follows:
Adopt the R142b thermo-cracking to prepare vinylidene, as thinner, be mixed into pyrolyzer with R142b with high pure nitrogen.High pure nitrogen simultaneously makes the material thermally equivalent reaction in the pyrolyzer, prevents the local superheating carbon distribution, can reduce the R142b dividing potential drop again simultaneously, helps scission reaction and carries out and effectively control side reaction, and the R142b transformation efficiency is improved, and the vinylidene yield increases.
Preferably, the volume ratio of high pure nitrogen and R142b is 0.5: 1.0.Pressure is 0.5～1.5Mpa.
Preferably, with the flow of R142b with 150-200Kg/h, high pure nitrogen is with 50-100m
3The flow of/h is mixed into pyrolyzer and carries out scission reaction.
Preferably, R142b scission reaction temperature is 700 ℃.
The key point that above-mentioned R142b cracking prepares the method for vinylidene also is to react the chilling of high-temperature gas afterwards, and the gas mixture after the cracking is chilled to 30～80 ℃ through quencher.
The present invention is the pyrolyzer that adopts φ 76 * 4.0 larger caliber metal boiler tubes with the preferred equipment that the R142b thermo-cracking prepares the method for vinylidene, and boiler tube adopts the novel cascaded structure of " U " type.
Cracking furnace tube adopts φ 76 * 4.0 larger caliber metal tubes, has broken through the limitation that domestic production vinylidene reaction tube diameter is not more than φ 40, and boiler tube adopts the novel cascaded structure of " U " type, and pressure drop is little, is difficult for carbon distribution, and inspection operation is convenient.
The pyrolyzer structure is as follows:
Pyrolyzer mainly is made up of heating muff, reaction boiler tube, conductive copper plate, refractory materials etc., and wherein the boiler tube in the pyrolyzer adopts φ 76 * 4.0 larger caliber metal tubes, and boiler tube adopts the novel cascaded structure of " U " type.As shown in Figure 1.
The product that the chemical reaction that carries out under differing temps obtains also is different, because the flow velocity of gas is very fast, 600 ~ 900 ℃ of temperature when guaranteeing that gas can reach cracking, therefore the design of the boiler tube of heating is also longer, 30 ~ 40 meters length generally will be arranged, the platform of corresponding operation and peripheral capital construction also will reach corresponding height, and pipeline takes mostly is the pipeline of φ 32 * 2, cracked output is difficult for improving, the cost of product and maintenance cost are high, are difficult to realize fairly large production.Can reduce production cost as the crooking of the tubes is connected, but be difficult to solution because the type selecting of material and bend pipe connection exist problems.Subject matter is: hydrocarbon compound cracking at high temperature easily generates knot carbon, causes line clogging.We adopt " U " type cascaded structure with the reaction boiler tube of φ 76 * 4.0 now, and bend pipe directly welds connection, has solved the reaction tubes carbon distribution, and easy fracture damages, the problem of local superheating.
The present invention adopts the R142b thermo-cracking to prepare vinylidene, and when using the pyrolyzer of novel texture to obtain vinylidene, by product is a hydrochloric acid.This processing unit has the product yield height, unit consumption is low, and few and fast cooling device life-span of pyrolyzer carbon deposit such as grows at advantage.
Description of drawings
Fig. 1 is the structural representation of pyrocrack furnace, wherein 1, heating muff, and 2, reaction boiler tube, 3, conductive copper plate, 4, bend pipe.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited thereto.Pyrolyzer described in the embodiment 1-3 all adopts φ 76 * 4.0 " U " type boiler tube.
Embodiment 1
With the flow of R142b with 150Kg/h, high pure nitrogen (99.99%) is with 50m
3The flow of/h is mixed into pyrolyzer and carries out scission reaction, and high pure nitrogen and R142b volume ratio are 0.5: 1.0, and pressure is 1.0Mpa, 700 ℃ of temperature of reaction, and from pyrolyzer outlet sampling analysis, splitting gas consists of: R142b:21%, vinylidene: 71%.The vinylidene transformation efficiency increases by 5 percentage points than before, illustrates with the high pure nitrogen to be the transformation efficiency that thinner and employing φ 76 * 4.0 " U " type boiler tube have increased vinylidene.
Gas mixture after the cracking is chilled to 30～80 ℃ through quencher, carries out dehydrochlorination and dehydration thereupon, obtains highly purified vinylidene through rectifying again.
Again return pyrolyzer after unreacted R142b reclaims and carry out cracking.
As described in embodiment 1, different is:
With the flow of R142b with 200Kg/h, high pure nitrogen is with 70m
3The flow of/h is mixed into pyrolyzer and carries out scission reaction, 800 ℃ of temperature of reaction, from pyrolyzer outlet sampling analysis, splitting gas consists of: R142b:18%, vinylidene: 70%, the vinylidene transformation efficiency increases by 4 percentage points than before, illustrates with the high pure nitrogen to be the transformation efficiency that thinner and employing φ 76 * 4.0 " U " type boiler tube have increased vinylidene.
As described in embodiment 1, different is:
With the flow of R142b with 250Kg/h, high pure nitrogen is with 100m
3The flow of/h is mixed into pyrolyzer and carries out scission reaction, 900 ℃ of temperature of reaction, from pyrolyzer outlet sampling analysis, splitting gas consists of: R142b:16%, vinylidene: 69%, the vinylidene transformation efficiency increases by 3 percentage points than before, illustrates with the high pure nitrogen to be the transformation efficiency that thinner and employing φ 76 * 4.0 " U " type boiler tube have increased vinylidene.
The pyrolyzer structure as shown in Figure 1, pyrolyzer is made up of heating muff, reaction boiler tube, conductive copper plate, refractory materials etc., wherein cracking furnace tube adopts φ 76 * 4.0 larger caliber metal tubes, boiler tube adopts the novel cascaded structure of " U " type, elbow directly welds the connection boiler tube, fracture damage, carbon distribution parking accident did not appear in three months in pyrolyzer operation continuously.Pyrolyzer moves the cycle stretch-out of two months parking maintenances than before.
Claims (6)
1, prepare the method for vinylidene with 1.1.1-difluoro monochlorethane (R142b) thermo-cracking, reaction formula is as follows:
CF
2ClCH
3→CF
2＝CH
2+HCl
R142b is heated to 600～900 ℃ in pyrolyzer, Pintsch process generates vinylidene, and the gas mixture after the cracking is chilled to 30～80 ℃ through quencher, carries out dehydrochlorination and dehydration thereupon, obtains highly purified vinylidene through rectifying again; Again return pyrolyzer after unreacted R142b reclaims and carry out cracking.
2, as claimed in claim 1ly prepare the method for vinylidene, it is characterized in that as thinner, high pure nitrogen and R142b are mixed into pyrolyzer and carry out scission reaction with high pure nitrogen with 1.1.1-difluoro monochlorethane (R142b) thermo-cracking.
3, as claimed in claim 2ly prepare the method for vinylidene, it is characterized in that the volume ratio of high pure nitrogen and R142b is 0.5: 1.0 with 1.1.1-difluoro monochlorethane (R142b) thermo-cracking.
4, as claimed in claim 2ly prepare the method for vinylidene, it is characterized in that with the flow of R142b with 150～200Kg/h, high pure nitrogen is with 50～100m with 1.1.1-difluoro monochlorethane (R142b) thermo-cracking
3The flow of/h is mixed into pyrolyzer and carries out scission reaction.
5, as claimed in claim 1 or 2ly prepare the method for vinylidene, it is characterized in that 700 ℃ of R142b scission reaction temperature with 1.1.1-difluoro monochlorethane (R142b) thermo-cracking.
6, be used for the pyrolyzer that claim 1-5 either party legal system is equipped with vinylidene, mainly form by heating muff, reaction tubes, conductive copper plate, refractory materials, wherein cracking furnace tube is adopted φ 76 * 4.0 larger caliber metal tube, and boiler tube adopts " U " type cascaded structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101710183A CN101003460B (en) | 2006-12-29 | 2006-12-29 | Method and equipment for preparing bias fluoro ethylene by using R142b cracking |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101710183A CN101003460B (en) | 2006-12-29 | 2006-12-29 | Method and equipment for preparing bias fluoro ethylene by using R142b cracking |
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| Publication Number | Publication Date |
|---|---|
| CN101003460A true CN101003460A (en) | 2007-07-25 |
| CN101003460B CN101003460B (en) | 2010-09-15 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664507A (en) * | 2013-12-18 | 2014-03-26 | 常熟振氟新材料有限公司 | Production method of vinylidene fluoride |
| CN103664508A (en) * | 2013-12-18 | 2014-03-26 | 常熟振氟新材料有限公司 | Production method of vinylidene fluoride monomer |
| CN103708993A (en) * | 2013-12-30 | 2014-04-09 | 江苏梅兰化工有限公司 | Alkali washing and dehydrating process for crude cracked gas in vinylidene fluoride production |
| CN104557446A (en) * | 2014-12-15 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | Method for preparing vinylidene fluoride monomer |
| CN107638852A (en) * | 2017-10-17 | 2018-01-30 | 龙星化工股份有限公司 | One kind fluorination work pyrolysis furnace |
| CN107652161A (en) * | 2017-11-06 | 2018-02-02 | 常熟三爱富振氟新材料有限公司 | A kind of production system of vinylidene |
| CN110642667A (en) * | 2019-10-19 | 2020-01-03 | 湘潭大学 | Method for co-production of methyl chloropropene and chloro tert-butane by chlorination of isobutene |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2044370C3 (en) * | 1970-09-08 | 1978-11-02 | Bayer Ag, 5090 Leverkusen | Process for the production of 1,1-difluoroethylene |
| CN1223560C (en) * | 2001-12-25 | 2005-10-19 | 中昊晨光化工研究院 | Method for producing metafluoroethylene by pyrolysis of difluoro-chloroethane |
| DE60328725D1 (en) * | 2003-10-17 | 2009-09-17 | Arkema France | METHOD OF PREPARING 1,1-DIFLUORETHANE AND USE IN THE PREPARATION OF 1,1-DIFLUORETHYLENE |
-
2006
- 2006-12-29 CN CN2006101710183A patent/CN101003460B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664507A (en) * | 2013-12-18 | 2014-03-26 | 常熟振氟新材料有限公司 | Production method of vinylidene fluoride |
| CN103664508A (en) * | 2013-12-18 | 2014-03-26 | 常熟振氟新材料有限公司 | Production method of vinylidene fluoride monomer |
| CN103708993A (en) * | 2013-12-30 | 2014-04-09 | 江苏梅兰化工有限公司 | Alkali washing and dehydrating process for crude cracked gas in vinylidene fluoride production |
| CN103708993B (en) * | 2013-12-30 | 2016-06-29 | 江苏梅兰化工有限公司 | A kind of vinylidene is thick cracking gas alkali cleaning and dehydrating process in producing |
| CN104557446A (en) * | 2014-12-15 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | Method for preparing vinylidene fluoride monomer |
| CN104557446B (en) * | 2014-12-15 | 2016-06-01 | 东莞市长安东阳光铝业研发有限公司 | A kind of method preparing vinylidene fluoride monomers |
| CN107638852A (en) * | 2017-10-17 | 2018-01-30 | 龙星化工股份有限公司 | One kind fluorination work pyrolysis furnace |
| CN107652161A (en) * | 2017-11-06 | 2018-02-02 | 常熟三爱富振氟新材料有限公司 | A kind of production system of vinylidene |
| CN110642667A (en) * | 2019-10-19 | 2020-01-03 | 湘潭大学 | Method for co-production of methyl chloropropene and chloro tert-butane by chlorination of isobutene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101003460B (en) | 2010-09-15 |
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Owner name: SHANDONG HUAXIA SHENZHOU NEW MATERIAL CO., LTD. Free format text: FORMER NAME: DONGGUE SHENZHOU NEW MATERIAL CO., LTD., SHANDONG |
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Address after: 256401 Tangshan Town, Huantai County, Shandong Province Patentee after: Shandong Dongyue Shenzhou New Material Co., Ltd. Address before: 256401 Tangshan Town, Huantai County, Shandong Province Patentee before: Donggue Shenzhou New Material Co., Ltd., Shandong |