CN104557446A - Method for preparing vinylidene fluoride monomer - Google Patents
Method for preparing vinylidene fluoride monomer Download PDFInfo
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- CN104557446A CN104557446A CN201410779274.5A CN201410779274A CN104557446A CN 104557446 A CN104557446 A CN 104557446A CN 201410779274 A CN201410779274 A CN 201410779274A CN 104557446 A CN104557446 A CN 104557446A
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- cracking tube
- vinylidene fluoride
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- monochloroethane
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Abstract
The invention relates to a method for preparing a vinylidene fluoride monomer. The method is characterized by comprising the following steps: preheating and mixing water and 1,1-difluoro-1-chloroethane and feeding the mixture into a cracking tube, quenching reacted cracking gas, removing HCl, drying and feeding the dried gas to a rectifying tower to obtain the high-purity vinylidene fluoride monomer. By the method, the problems of carbon deposition, clogging of a pipeline and the like can be decreased, the selectivity and reaction efficiency can be effectively improved, the reaction temperature is decreased and thus the energy consumption can be reduced, the energy consumption is substantially reduced and the pollution is decreased.
Description
Technical field
The present invention relates to a kind of preparation method of vinylidene, be specially the method that dilute with water method cracking technology prepares vinylidene.
Background technology
Vinylidene, be called for short VDF, its main application is homopolymerization or produces polyvinylidene difluoride (PVDF) with other monomer copolymerization.The preparation technology of current vinylidene fluoride monomers has carried out large quantifier elimination, adopt different technique to prepare according to different raw materials, industrially often adopt difluoromono-chloroethane (R142b) to be raw material, in the blank pipe of 700 ~ 1000 DEG C, carry out scission reaction obtain.Patent CN101003460 adopts nitrogen dilution reactant gases and U-shaped cascaded structure reaction tubes, is that 0.5:1.0 is input to cracking inner reaction tube by the volume ratio of high pure nitrogen and R142b.Although the transformation efficiency of VDF increases by 5% compared with before-improvement, productive rate and selectivity still have larger room for promotion, have the knot carbon not problem such as easy to clean simultaneously; It is the method that raw material scission reaction prepares VDF that Allied company of the U.S. it is also proposed with R142b, and in patent US 1458285, the said firm is by adding the Cl of 0.5 ~ 4wt%
2as promotor, make the transformation efficiency of R142b bring up to more than 85%, but selectivity only have 87.5%.Patent US 4053529 is front having on the basis of research and development, adds the CCl that molar fraction is 0.01 ~ 10% in cracking process simultaneously
4with 0.01 ~ 10% Cl
2, the transformation efficiency of VDF and selectivity are all improved to some extent, and transformation efficiency reaches 79%, and selectivity reaches 99%.
US Patent No. 3996301 utilizes the cracking of ptfe ring butane to prepare VDF.Ptfe ring butane reacts in the cracking tube of 500 ~ 900 DEG C, can pass into the rare gas elementes such as helium, nitrogen and tetrafluoro-methane, and low pressure is conducive to operation, and be preferably lower than 50Psig, the residence time is 1s ~ 10min.Main By product is tetrafluoroethylene and ethene, and this Patent design goes out a dimerization room, makes tetrafluoroethylene generate dimer with ethylene reaction and reach the object be separated.The temperature of dimerization room is 400 ~ 600 DEG C, and high pressure is conducive to dimerization reaction, therefore, indoor pressure is 50 ~ 500Psig, and gas was determined by temperature of reaction in the residence time of dimerization indoor, at high temperature stopped 1 ~ 20min, then need stay longer under low temperature, need 1 ~ 200h.The standby VDF purity of this legal system is high, and without in rectification process situation, generally can reach more than 95%, the highest reaches 98.7%, but its to there is by product many, selectivity is low, the high and easy knot carbon not problem such as easy to clean in cracking tube of energy consumption.
For above-mentioned each vinylidene fluoride monomers preparation method, easily produce knot carbon, the problem of easy blocking pipeline because scission reaction itself exists, the scission reaction energy consumption that simultaneously there is high temperature system is high, 1,1-bis-fluoro-1-monochloroethane low conversion rate, in splitting gas, foreign matter content is high, selectivity is low, unreacted 1, the shortcomings such as the cost recovery of 1-bis-fluoro-1-monochloroethane is high, this causes cracking low for vinylidene production efficiency, and needs often to stop maintenance facilities, coke cleaning de-carbon.Therefore its preparation method is optimized particularly important.
Summary of the invention
The present invention is directed to existing defects and deficiency in prior art, propose a kind of method that dilute with water method cracking technology prepares vinylidene.
Technical scheme of the present invention provides a kind of method preparing vinylidene fluoride monomers, comprise the following steps: water and 1, the fluoro-1-monochloroethane of 1-bis-enters cracking tube after preheating, mixing, reacted splitting gas passes through chilling, except after HCl, drying treatment, obtains highly purified vinylidene fluoride monomers through rectifying tower;
Described cracking tube is the U-shaped cracking tube of pure nickel material.
The mol ratio of described water and the fluoro-1-monochloroethane of 1,1-bis-is 1:0.3 ~ 1.1.
In certain embodiments of the present invention, cracking tube internal pressure is 0.05 ~ 0.5MPa.
In some embodiments of the present invention mode, during preheating, water preheat furnace temperature is 600 ~ 900 DEG C, and 1,1-bis-fluoro-1-monochloroethane preheating oven temperature is 250 ~ 450 DEG C.
In some embodiments of the present invention mode, described U-shaped cracking tube inner diameter is 17cm.
In some embodiments of the present invention mode, the temperature of reaction in cracking tube is 600 ~ 900 DEG C, 0.6 ~ 1.0s during reaction.
Unless explicitly stated otherwise in contrast, otherwise all scopes that the present invention quotes comprise end value.Such as, " 1,1-bis-fluoro-1-monochloroethane preheating oven temperature is 250 ~ 450 DEG C ", represents that the scope of temperature is 250 DEG C≤T≤450 DEG C.
Numeral in the present invention is approximation, no matter whether uses the wording such as " approximately " or " about ".The numerical value of numeral likely there will be the difference such as 1%, 2%, 5%, 7%, 8%, 10%.Whenever disclosing one and having N value digital, any have N+/-1%, N+/-2%, N+/-3%, N+/-5%, N+/-7%, the numeral of N+/-8% or N+/-10% value can be specifically disclosed, and wherein " +/-" refers to and add deduct, and the scope between N-10% to N+10% is also disclosed.Such as, for " cracking tube internal pressure is 0.05MPa ", then there is 0.05MPa+/-1%, 0.05MPa+/-2%, 0.05MPa+/-3%, 0.05MPa+/-5%, 0.05MPa+/-7%, the value of 0.05MPa+/-8% and 0.05MPa+/-10% is by simultaneously open, simultaneously, temperature range between 0.05MPa-10% to 0.05MPa+10% also belongs to scope of disclosure, that is the value between 0.045-0.055MPa, comprising in scope all at cracking tube overpressure.
Drying of the present invention, refers to and to make in material water or solvent gasification by means of energy, and take away the process of generated steam.The drying mode that embodiments more of the present invention adopt is bake drying.It should be pointed out that the drying means that can reach same effect also includes but not limited to oven dry, vacuum-drying, lyophilize, air stream drying, microwave drying, ultra red ray drying and dielectric dry etc.In certain embodiments of the present invention, drying temperature is 50 ~ 120 DEG C.
Beneficial effect of the present invention is:
1) method provided by the present invention can improve R142b cracking for vinylidene fluoride monomers transformation efficiency, selectivity and reduction energy consumption of reaction, the transformation efficiency of R142b can reach 97%, selectivity is up to 99%, prepared vinylidene fluoride monomers can reach 99.999% by purity after rectifying, along with high conversion improves the service efficiency of raw material, can recovery difficult be reduced, thus by a relatively large margin reduce production cost.；
2) the cracking tube material used in the present invention is pure nickel pipe, nickel has katalysis to reaction, reaction efficiency can be improved, reduce temperature of reaction, thus can energy consumption be lowered, save energy consumption by a relatively large margin, decreasing pollution, energy-saving and emission-reduction, make gas be heated evenly in pipe simultaneously, reduce knot carbon and generate.The effect reducing operating power consumption and extend the maintenance shut-downs cycle can be reached in the industrial production.
3) the present invention adopts water dilution method cracking for vinylidene, utilizes the feature that water vapour thermal capacitance is large, and in maintenance cracking tube, temperature is stable; Can cracking temperature be reduced, reduce knot carbon, be conducive to the raising of speed of reaction and fully carrying out of reaction; When operating pressure is constant, pass into the dividing potential drop that water vapour can reduce split product, promote that molecular balance moves to positive dirction.
Embodiment
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred implementation.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, the some distortion made and improvement, all belong to protection scope of the present invention.Raw material used in embodiment all can be obtained by commercial sources.
Embodiment 1
Displacement nitrogen 5 times will be vacuumized in cracker system, in detection still, oxygen level is lower than 20ppm, inflated with nitrogen makes system slightly malleation, deionized water and 1, the fluoro-1-monochloroethane of 1-bis-is mixed into cracking tube respectively through after preheating oven, and deionized water preheating oven temperature is 650 DEG C, and 1, the fluoro-1-monochloroethane of 1-bis-passes into preheating oven with the speed of 20L/s, H
2o feeding rate is 5ml/s, and preheating oven temperature is set to 300 DEG C, and cracking pressure-controlling is 0.05MPa, pyrolyzer temperature controls at 650 DEG C, after cracking tube, gas, respectively through surge chamber, condenser, sodium hydroxide deacidification tank, freezing de-watering apparatus, obtains splitting gas.The test result of selectivity and transformation efficiency is in table 1.
Embodiment 2
Displacement nitrogen 5 times will be vacuumized in cracker system, in detection still, oxygen level is lower than 20ppm, inflated with nitrogen makes system slightly malleation, deionized water and 1, the fluoro-1-monochloroethane of 1-bis-is mixed into cracking tube respectively through after preheating oven, and deionized water preheating oven temperature is 700 DEG C, and 1, the fluoro-1-monochloroethane of 1-bis-passes into preheating oven with the speed of 20L/s, H
2o feeding rate is 10ml/s, and preheating oven temperature is set to 350 DEG C, and cracking pressure-controlling is 0.05MPa, pyrolyzer temperature controls at 700 DEG C, after cracking tube, gas, respectively through surge chamber, condenser, sodium hydroxide deacidification tank, freezing de-watering apparatus, obtains splitting gas.The test result of selectivity and transformation efficiency is in table 1.
Embodiment 3
Displacement nitrogen 5 times will be vacuumized in cracker system, in detection still, oxygen level is lower than 20ppm, inflated with nitrogen makes system slightly malleation, deionized water and 1, the fluoro-1-monochloroethane of 1-bis-is mixed into cracking tube respectively through after preheating oven, and deionized water preheating oven temperature is 780 DEG C, and 1, the fluoro-1-monochloroethane of 1-bis-passes into preheating oven with the speed of 20L/s, H
2o feeding rate is 15ml/s, and preheating oven temperature is set to 350 DEG C, and cracking pressure-controlling is 0.10MPa, pyrolyzer temperature controls at 780 DEG C, after cracking tube, gas, respectively through surge chamber, condenser, sodium hydroxide deacidification tank, freezing de-watering apparatus, obtains splitting gas.The test result of selectivity and transformation efficiency is in table 1.
Embodiment 4
Displacement nitrogen 5 times will be vacuumized in cracker system, in detection still, oxygen level is lower than 20ppm, inflated with nitrogen makes system slightly malleation, deionized water and 1, the fluoro-1-monochloroethane of 1-bis-is mixed into cracking tube respectively through after preheating oven, and deionized water preheating oven temperature is 700 DEG C, and 1, the fluoro-1-monochloroethane of 1-bis-passes into preheating oven with the speed of 20L/s, H
2o feeding rate is 10ml/s, and preheating oven temperature is set to 450 DEG C, and cracking pressure-controlling is 0.15MPa, pyrolyzer temperature controls at 700 DEG C, after cracking tube, gas, respectively through surge chamber, condenser, sodium hydroxide deacidification tank, freezing de-watering apparatus, obtains splitting gas.The test result of selectivity and transformation efficiency is in table 1.
The VDF prepared by embodiment 1-4 makes transformation efficiency, selectivity test respectively by chromatography of gases, and concrete test result is as follows:
Vinylidene fluoride monomers splitting gas the performance test results prepared by table 1. embodiment of the present invention
| Experimental group | Transformation efficiency % | Selectivity % |
| Embodiment 1 | 95.24 | 99.40 |
| Embodiment 2 | 96.82 | 99.20 |
| Embodiment 3 | 97.14 | 99.03 |
| Embodiment 4 | 96.36 | 98.86 |
Claims (5)
1. prepare the method for vinylidene fluoride monomers for one kind, it is characterized in that, comprise the following steps: water and 1, the fluoro-1-monochloroethane of 1-bis-enters cracking tube after preheating, mixing, reacted splitting gas passes through chilling, except after HCl, drying treatment, obtains highly purified vinylidene fluoride monomers through rectifying tower;
Described cracking tube is the U-shaped cracking tube of pure nickel material;
The mol ratio of described water and the fluoro-1-monochloroethane of 1,1-bis-is 1:0.3 ~ 1.1.
2. preparation method according to claim 1, is characterized in that, cracking tube internal pressure is 0.05 ~ 0.5MPa.
3. preparation method according to claim 1, is characterized in that, during preheating, the temperature of water preheat stove is 600 ~ 900 DEG C, and 1,1-bis-fluoro-1-monochloroethane preheating oven temperature is 250 ~ 450 DEG C.
4. preparation method according to claim 1, is characterized in that, described U-shaped cracking tube inner diameter is 17cm.
5. preparation method according to claim 1, is characterized in that, the temperature of reaction in cracking tube is 600 ~ 900 DEG C, and the reaction times is 0.6 ~ 1.0s.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961622A (en) * | 2015-06-02 | 2015-10-07 | 江苏三美化工有限公司 | Method for high-selectivity R142b cracking preparation of vinylidene fluoride |
| CN105384596A (en) * | 2015-11-13 | 2016-03-09 | 巨化集团技术中心 | Preparation method of vinylidene fluoride (VDF) |
| CN106588563A (en) * | 2016-12-28 | 2017-04-26 | 浙江工业大学 | Preparation method of 1,1-difluoroethylene |
| CN107721813A (en) * | 2017-11-06 | 2018-02-23 | 常熟三爱富振氟新材料有限公司 | A kind of production method of vinylidene fluoride monomers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3830856A (en) * | 1970-09-08 | 1974-08-20 | Bayer Ag | Preparation of vinylidene fluoride |
| CN1428320A (en) * | 2001-12-25 | 2003-07-09 | 中昊晨光化工研究院 | Method for producing metafluoroethylene by pyrolysis of difluoro-chloroethane |
| CN101003460A (en) * | 2006-12-29 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Method and equipment for preparing bias fluoro ethylene by using R142b cracking |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1823419A1 (en) * | 1986-06-10 | 1996-06-10 | Научно-производственное объединение Государственного института прикладной химии | Method of synthesis of vinylidene fluoride |
-
2014
- 2014-12-15 CN CN201410779274.5A patent/CN104557446B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3830856A (en) * | 1970-09-08 | 1974-08-20 | Bayer Ag | Preparation of vinylidene fluoride |
| CN1428320A (en) * | 2001-12-25 | 2003-07-09 | 中昊晨光化工研究院 | Method for producing metafluoroethylene by pyrolysis of difluoro-chloroethane |
| CN101003460A (en) * | 2006-12-29 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Method and equipment for preparing bias fluoro ethylene by using R142b cracking |
Non-Patent Citations (1)
| Title |
|---|
| 郑海峰等: "1-氯-1，1-二氟乙烷裂解制备偏氟乙烯的研究进展", 《化工进展》, vol. 33, no. 1, 5 January 2014 (2014-01-05) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961622A (en) * | 2015-06-02 | 2015-10-07 | 江苏三美化工有限公司 | Method for high-selectivity R142b cracking preparation of vinylidene fluoride |
| CN105384596A (en) * | 2015-11-13 | 2016-03-09 | 巨化集团技术中心 | Preparation method of vinylidene fluoride (VDF) |
| CN106588563A (en) * | 2016-12-28 | 2017-04-26 | 浙江工业大学 | Preparation method of 1,1-difluoroethylene |
| CN106588563B (en) * | 2016-12-28 | 2019-02-05 | 浙江工业大学 | A kind of preparation method of 1,1- difluoroethylene |
| CN107721813A (en) * | 2017-11-06 | 2018-02-23 | 常熟三爱富振氟新材料有限公司 | A kind of production method of vinylidene fluoride monomers |
| WO2019084977A1 (en) * | 2017-11-06 | 2019-05-09 | 常熟三爱富振氟新材料有限公司 | Production method for vinylidene fluoride monomer |
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Effective date of registration: 20170516 Address after: 512799 chemical base of milk Town, Ruyuan County, Shaoguan, Guangdong Patentee after: Ruyuan East Sun fluorine resin Co., Ltd. Address before: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Patentee before: Dongyang, Dongguan City Chang'an light Aluminum research and development company limited |