CN1454883A - Hexafluoropropylene production method - Google Patents
Hexafluoropropylene production method Download PDFInfo
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- CN1454883A CN1454883A CN 03117869 CN03117869A CN1454883A CN 1454883 A CN1454883 A CN 1454883A CN 03117869 CN03117869 CN 03117869 CN 03117869 A CN03117869 A CN 03117869A CN 1454883 A CN1454883 A CN 1454883A
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Abstract
The production method of hexafluoropropylene includes the following steps: uniformly mixing raw material gas tetrafluoroethylene and octafluorocyclobutane according to a certain proportion, preheating and feeding them into stage heated tubular reactor for making cracking reaction, quenching reaction product, removing acid, drying and finally rectifying separation to obtain the invented hexafluoropylene whose purity is greater than or equal to 99.98%. Said invention adopts the octafluorocyclobutane as diluting agent and as reactant, at the same time adopts stage heated cracking process, so that it not only improves the thermal conductivity of cracking gas, but also can make the whole reaction process be implemented in optimum temp. range to inhibite the production of poor side reaction.
Description
Technical field
The invention belongs to the method for a kind of production R 1216 (HFP) in the Chemical Manufacture.Particularly a kind of employing tetrafluoroethylene (TFE) and the method for Perfluorocyclobutane (C-318) mixed pyrolysis with the production R 1216.
Background technology
R 1216 (also claiming perfluoro propylene) is one of basic material of organic fluorine industry, is widely used in the production of viton, fluoroplastics, perfluoro propene oxid, heptafluoro-propane, fluorine surfactant etc.But the pure tetrafluoroethylene of traditional employing is a raw material, method by tubular reactor heating Pintsch process production R 1216, owing to easily tie carbon at the easy autohemagglutination in inlet pipe oral area position, going out to manage the position, and at high temperature disproportionation reaction can take place in long reaction time, generate carbon and tetrafluoro-methane, temperature control also can induce reaction simultaneously.Thereby this method exists raw material consumption height, by product many, and the autopolymer of generation and carbon easily stop up reactor, and productive rate is lower, the more high defective of production cost.In order to overcome above-mentioned defective, in application number is 87104471 patent documentation disclosed " preparation method of perfluoro propylene ", at first will in a tank reactor, carry out reversible reaction as the tetrafluoroethylene of reactant or tetrafluoroethylene and Perfluorocyclobutane, after the amount for the treatment of Perfluorocyclobutane wherein increases, with this mixture input tubular reactor, also finally be translated into perfluoro propylene again in the hope of the autohemagglutination phenomenon that is reduced in inlet pipe oral area position.This processing method is owing to adopt same Heating temperature in cracking process, thereby ingress is because of being in thermo-negative reaction, and its temperature of reaction is lower, about 600 ℃, just be heated in high temperature reaction zone more than 700 ℃, near the invert point the exit is then up to 800-950 ℃.Thereby still exist tetrafluoroethylene easily at the entrance end autohemagglutination, cause the temperature runaway phenomenon at exit end, carbonization takes place and generate the disadvantages such as raising of a large amount of by products, overslaugh productive rate.
Summary of the invention
The objective of the invention is defective at the existence of above-mentioned background technology, improve the production method of a kind of R 1216 of design, to reach the generation that prevents tetrafluoroethylene autohemagglutination and knot carbon in the reaction process, suppresses bad side reaction, prolong tubular reactor work-ing life, effectively improve productive rate, purpose such as reduce production costs.
Solution of the present invention is at first tetrafluoroethylene to be mixed by a certain percentage with Perfluorocyclobutane, enter the tubular reactor scission reaction again after the preheating, and to improve the heat transfer condition of splitting gas, wherein Perfluorocyclobutane is a reactant, also is thinner; While is according to the ultimate principle of tetrafluoroethylene and Perfluorocyclobutane mixed pyrolysis, tubular reactor is taked zone heating, so that effectively reduce the axial thermograde of tubular reactor, the temperature of entire reaction course is controlled within the generation R 1216 optimum range, effectively preventing tetrafluoroethylene autohemagglutination and knot carbon and to suppress the generation etc. of bad side reaction, thereby realize its purpose.Therefore, the inventive method comprises:
A. mixed gas compounding: with tetrafluoroethylene and Perfluorocyclobutane is 0.1-10 in molar ratio: 1 ratio is to mix under the condition of 10-60KPa at pressure;
B. preheating: with above-mentioned gas mixture input primary heater unit, be preheated to 300-700 ℃ after direct input tubular reactor;
C. heating pyrolyze: after the gas mixture of input enters reactor, by the required Heating temperature of reaction process, the zone heating cracking; Each section Heating temperature is 650-900 ℃, temperature of reaction is controlled in 750 ± 30 ℃ of scopes; Each temperature section boiler tube is long to be 0.5-16.0m;
D. chilling, deacidification, drying: will be chilled to 25-60 ℃ through the input of the product after C scission reaction refrigerating unit, and adopt sorbent material to remove micro-hydrogen fluoride and the moisture content that wherein generates;
E. rectifying separation: will be through the input of the split product after above-mentioned processing rectifier unit, rectifying separation under 0.1-0.8MPa pressure, the R 1216 of purity 〉=99.98%; And isolated Perfluorocyclobutane and tetrafluoroethylene backspace mixing tank enter next circulation.
Above-mentioned primary heater unit can be tubular preheater.And described zone heating cracking can be divided into tubular reactor 2-7 relatively independent heating zone; Each heating zone is established 1-4 monitoring temperature point respectively, to regulate and to control the Heating temperature of this section.And described each heating zone both can adopt indirect heating, also can adopt direct heating, and when each heating zone established temperature control point was 2-4 point, its input was regulated, the temperature parameter of control heating unit is the mean value of each control point temperature.And described sorbent material is silica gel (SiO
2) or calcium oxide (CaO), aluminum oxide (Al
2O
3), calcium chloride (CaCl
2).
The present invention since with Perfluorocyclobutane not only as reactant, but also mix, import again after the preheating scission reaction in the tubular reactor of zone heating with tetrafluoroethylene as attenuant, not only improved the thermal conduction of splitting gas, and reduced the axial thermograde of tubular reactor effectively, thereby whole scission reaction process all can be carried out in the optimum temperature range that generates R 1216, tetrafluoroethylene autohemagglutination and the generation of tying carbon and temperature runaway phenomenon in the reaction process have been prevented, suppress the generation of bad side reaction, the productive rate of R 1216 can be brought up to 87.0-92.5%.Thereby the present invention has technology advanced person, reliable, and temperature of reaction is regulated accurately, by product is few, productive rate height, tubular reactor (cracking tube) long service life, characteristics such as production cost is low.
Embodiment 1
The present embodiment tubular reactor adopts 3 sections heating, tetrafluoroethylene in the gas mixture (TFE) 73.67%, Perfluorocyclobutane (C-318) 26.33% (wherein containing perfluorobuttene 6.1%).Tubular reactor is the stainless steel tube of φ 32 * 3mm, long 13.0m.; Each section all adopts indirect heating, and first and second segment length is 1.5m, respectively establishes monitoring temperature point; The 3rd segment length 11.5m establishes three monitoring temperature points.Its production method is:
A. at first with TFE with 25.0Nm
3/ h, C-318 are with 7.1Nm
3The flow input mixer of/h mixes under 15KPa pressure;
B. the splitting gas input tubular preheater that mixes above-mentioned, be preheated to 450 ℃ after direct input tubular reactor;
C. Shu Ru the mixed pyrolysis gas after preheating, first section Heating temperature is 851 ℃ (reactor outer tube wall temperature, as follows), second section 660 ℃, the 3rd section 3 monitoring temperature point temperature are respectively scission reaction under the condition of 706 ℃, 684 ℃ and 777 ℃, reaction time 0.9 second;
D. above-mentioned reactant input shell and tube cooler is chilled to 40 ℃, and adopts silica gel adsorption to remove hydrogen fluoride and moisture content wherein;
E. with split product after D handles input high efficiency packing formula rectifying tower, rectifying separation under 0.6MPa pressure, purity is 99.99% R 1216, isolated TFE and C-318 return mixing tank and enter next circulation, residual matter is made burning disposal.
The present embodiment reaction result is after testing: TFE37.20%, HFP31.16%, C-318:25.41%, perfluorobuttene 3.07%, residue perfluoroisobutylene 3.16%.TFE+C-318 transformation efficiency 36.35%, HFP (R 1216) productive rate 87.05%.
Embodiment 2
TFE70.92% in the present embodiment gas mixture, C-318 were 29.08% (wherein containing perfluorobuttene 12.0%); Tubular reactor divides 6 sections direct heating, and the every segment length of 1-5 heating zone is 3.0m, respectively establishes monitoring temperature point, and the 6th segment length 11.5m establishes 3 monitoring temperature points.The present embodiment method is:
A.TFE is with 25.1Nm
3/ h, C-318 are with 7.6Nm
3The flow input mixer of/h mixes under 11.0KPa pressure;
B. after being preheated to 550 ℃ in the above-mentioned gas mixture input tubular preheater, directly import tubular reactor;
C. heating pyrolyze reaction under 776 ℃ the condition with the gas mixture after the preheating in 741 ℃ of first section Heating temperatures, second section 754 ℃, the 3rd section 760 ℃, the 4th section 767 ℃, the 5th section 760 ℃, the 6th section three control point medial temperature, reaction time 1.5 seconds.
All the other operations and embodiment 1 are together.
The present embodiment reaction result is after testing: TFE38.88%, C-318:22.84%, HFP31.95%, perfluorobuttene 4.91%, perfluoroisobutylene 1.14%; TFE+C-318 transformation efficiency 35.89%, the productive rate 92.47% of HFP, purity 99.99%.
Claims (5)
1, a kind of production method of R 1216 is characterized in that this method comprises:
A. mixed gas compounding: with tetrafluoroethylene and Perfluorocyclobutane is 0.1-10 in molar ratio: 1 ratio is to mix under the 10-60KPa condition at pressure;
B. preheating: with above-mentioned gas mixture input primary heater unit, be preheated to 300 °-700 ℃ after direct input tubular reactor;
C. heating pyrolyze: after the gas mixture of input enters reactor, by the required Heating temperature of reaction process, the zone heating cracking; Each section Heating temperature is 650-900 ℃, temperature of reaction is controlled in 750 ° ± 30 ° scopes; And each temperature section boiler tube length is 0.5-16.0m;
D. chilling, deacidification, drying: will be chilled to 25 °-60 ℃ through the input of the product after C scission reaction refrigerating unit, and adopt sorbent material to remove micro-hydrogen fluoride and the moisture content that wherein generates;
E. rectifying separation: will be through the input of the split product after above-mentioned processing rectifier unit, rectifying separation under 0.1-0.8MPa pressure, the R 1216 of purity 〉=99.98%; And isolated Perfluorocyclobutane and tetrafluoroethylene backspace mixing tank enter next circulation.
2, press the production method of the described R 1216 of claim 1; It is characterized in that described primary heater unit is a tubular preheater.
3, press the production method of the described R 1216 of claim 1; It is characterized in that described zone heating cracking, tubular reactor can be divided into 2-7 relatively independent heating zone; Each heating zone is established 1-4 monitoring temperature point respectively, to regulate and to control the Heating temperature of this section.
4, press the production method of claim 1 or 3 described R 1216s; It is characterized in that described each heating zone both can adopt indirect heating, also can adopt direct heating; And when each heating zone established temperature control point was the 2-4 point, its input was regulated, the temperature parameter of control heating unit is the mean value of each control point temperature.
5, press the production method of the described R 1216 of claim 1; It is characterized in that described sorbent material is silica gel or calcium oxide, aluminum oxide, calcium chloride.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117869 CN1273427C (en) | 2003-05-16 | 2003-05-16 | Hexafluoropropylene production method |
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|---|---|---|---|
| CN 03117869 CN1273427C (en) | 2003-05-16 | 2003-05-16 | Hexafluoropropylene production method |
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| CN1273427C CN1273427C (en) | 2006-09-06 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558538A (en) * | 2011-12-28 | 2012-07-11 | 湖南大学 | Deep purification method of hexafluropropylene oxide |
| CN103922889A (en) * | 2014-04-01 | 2014-07-16 | 江苏梅兰化工有限公司 | Temperature runaway-preventing control method of hexafluoropropylene cracking reactor |
| CN104557447A (en) * | 2015-01-30 | 2015-04-29 | 福建三农化学农药有限责任公司 | Jointly recycling method for production residual liquid of tetrafluoroethylene and hexafluoropropylene |
| CN104788283A (en) * | 2015-03-12 | 2015-07-22 | 福建三农化学农药有限责任公司 | Double line rectification method of hexafluoropropene production cracking gas, and rectification apparatus thereof |
| CN110078586A (en) * | 2019-05-06 | 2019-08-02 | 聊城氟尔新材料科技有限公司 | The device and technique of a kind of tetrafluoroethene coproduction hexafluoropropene and application |
| CN110818528A (en) * | 2019-10-05 | 2020-02-21 | 泰兴梅兰新材料有限公司 | Novel method for removing acid in hexafluoropropylene production |
| CN111905668A (en) * | 2020-09-04 | 2020-11-10 | 南京工业大学 | Reaction device and application thereof in continuous preparation of vegetable oil polyalcohol |
| CN114956953A (en) * | 2022-06-21 | 2022-08-30 | 常熟三爱富氟化工有限责任公司 | Process for preparing hexafluoropropene |
| CN115651184A (en) * | 2022-09-28 | 2023-01-31 | 四川弘氟新材料有限公司 | Fluorine-containing polyether carboxylic acid type surfactant and preparation method thereof |
-
2003
- 2003-05-16 CN CN 03117869 patent/CN1273427C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558538A (en) * | 2011-12-28 | 2012-07-11 | 湖南大学 | Deep purification method of hexafluropropylene oxide |
| CN103922889A (en) * | 2014-04-01 | 2014-07-16 | 江苏梅兰化工有限公司 | Temperature runaway-preventing control method of hexafluoropropylene cracking reactor |
| CN103922889B (en) * | 2014-04-01 | 2016-08-17 | 江苏梅兰化工有限公司 | A kind of hexafluoropropene cracking reactor anti-temperature runaway control method |
| CN104557447A (en) * | 2015-01-30 | 2015-04-29 | 福建三农化学农药有限责任公司 | Jointly recycling method for production residual liquid of tetrafluoroethylene and hexafluoropropylene |
| CN104788283A (en) * | 2015-03-12 | 2015-07-22 | 福建三农化学农药有限责任公司 | Double line rectification method of hexafluoropropene production cracking gas, and rectification apparatus thereof |
| CN110078586A (en) * | 2019-05-06 | 2019-08-02 | 聊城氟尔新材料科技有限公司 | The device and technique of a kind of tetrafluoroethene coproduction hexafluoropropene and application |
| CN110078586B (en) * | 2019-05-06 | 2022-05-27 | 聊城氟尔新材料科技有限公司 | Device and process for co-production of hexafluoropropylene from tetrafluoroethylene and application of device |
| CN110818528A (en) * | 2019-10-05 | 2020-02-21 | 泰兴梅兰新材料有限公司 | Novel method for removing acid in hexafluoropropylene production |
| CN111905668A (en) * | 2020-09-04 | 2020-11-10 | 南京工业大学 | Reaction device and application thereof in continuous preparation of vegetable oil polyalcohol |
| CN114956953A (en) * | 2022-06-21 | 2022-08-30 | 常熟三爱富氟化工有限责任公司 | Process for preparing hexafluoropropene |
| CN115651184A (en) * | 2022-09-28 | 2023-01-31 | 四川弘氟新材料有限公司 | Fluorine-containing polyether carboxylic acid type surfactant and preparation method thereof |
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| CN1273427C (en) | 2006-09-06 |
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Address after: 643201 Zigong County, Sichuan Province, Chenguang Road, No. 135, Fushun Patentee after: Zhonghao Chenguang Chemical Institute Co., Ltd. Address before: 643000 Chenguang Chemical Research Institute, Zigong, Sichuan, Fushun Patentee before: Zhonghao Chenguang Chemical Research Inst. |
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