CN1044803C - 1,1,1-trifluoroethane preparation by gas-phase fluorization of 1,1,1-dichlorofluoroethane - Google Patents

1,1,1-trifluoroethane preparation by gas-phase fluorization of 1,1,1-dichlorofluoroethane Download PDF

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CN1044803C
CN1044803C CN94101618A CN94101618A CN1044803C CN 1044803 C CN1044803 C CN 1044803C CN 94101618 A CN94101618 A CN 94101618A CN 94101618 A CN94101618 A CN 94101618A CN 1044803 C CN1044803 C CN 1044803C
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reaction
hcfc141b
alf
hfc143a
catalyst
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CN1106780A (en
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郭心正
赵璇
郑承武
叶朝珲
汪民
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Zhejiang Lantian Environmental Protection Hi Tech Co Ltd
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Zhejiang Chemical Industry Research Institute Co Ltd
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Abstract

The present invention relates to a method for preparing 1, 1, 1-trifluoroethane (HFC143a) by gas phase catalysis and fluorination of 1, 1, 1-dichlorofluoroethane (HCFC141b) and anhydrous HF. A catalyst adopts activated carbon AlF3 or activated Al2O3 as a carrier which is subsidiarily carried with 5 to 10 wt% of metal of oxides of Fe<3+>, Be<3+>, B<3+>, Cr<3+>, Ni<3+>, Co<3+>, Mn<2+>, Bi<2+>, Cu<2+> or Ag<+> or halogenide or carrier-free Cr2O3 or AlF3-Cr2O3, the mole proportion of HF to HCFC141b is from 2.0 to 2.5, the reaction temperature is from 160 to 350 DEG C, and the reaction pressure is from 0.1 to 1.5MPa. The method provides a novel method for preparing an HCFC22 substitute HFC143a and solves the defect after HCFC141b limited use or forbidden use, and both the reaction conversion rate and the selectivity are larger than 99%.

Description

1.1.1-chloro fluoroethane gas phase fluorination system 1.1.1-Halothane
The present invention relates to the method that 1.1.1-chloro fluoroethane and anhydrous hydrogen fluoride gas phase fluorination prepare the 1.1.1-Halothane.
Discovering in recent years, HCFC22 (CF 2CLH), HCFC141b (1.1.1-chloro fluoroethane), HCFC142b (1.1.1-two chlorofluoroethanes) though etc. HCFC class chemical serious unlike CFC class chemical; but the ozone to earth atmospheric advection layer also has destruction; be the more effective ozonosphere of preserving our planet, increasing people also advocates to limit as early as possible and even forbid at last the use of these chemical.HCFC22 uses extensively at present, world's annual production reaches the hundreds of thousands of ton, and HCFC141b, HCFC142b are as the transition surrogate of CFC series products, built up at present the about 100,000 tons production equipment of annual production in the world already, how to substitute HCFC22, the production equipment that how to make the HCFC141b, the HCFC142b that had built up is already changed the line of production behind its forbidding and earth's ozone layer is not produced the HFC series products of destruction, is a problem that need are considered in advance and solved
1.1.1-Halothane belongs to the HFC series products, be called for short HFC143a, boiling point-48 ℃, AEL is 1000ppm, its ozone layer destroying potential value (ODP) is zero, it is as cooling agent, the volume refrigerating capacity is greater than HCFC22, and exhaust temperature is lower than HCFC22, so the substitute that HFC143a or its azeotrope, nearly azeotropic mixture just are being used as HCFC22 is carried out extensive studies, and arrived achievement
About the preparation method of HFC143a, existing many patent documentation reports with regard to its starting raw material, have added up to three kinds, i.e. vinylidene chloride (CH 2=CCL 2), trichloroethane (CH 3CCl a) and CFC114a (CCl 2FCF 3),
The objective of the invention is to be to provide a kind of preparation method who is different from the new HFC143a of existing raw material route, it promptly is the novel method that starting raw material prepares HFC143a with HCFC141b, like this, both having can be in the future, changing the line of production of HCFC141b production equipment provides method, provide effective substitute for HCFC22 again
By the inventive method, prepare HFC143a by realizing by HCFC141b with anhydrous hydrogen fluoride gas phase fluorination in the presence of solid catalyst, there is the following halogen exchange reaction in the reaction,
According to the inventive method, suitable as long as catalyzer is selected, processing condition control is correct, just can obtain very high HCFC141b transformation efficiency and HFC143a selectivity.
The technical process of the inventive method as shown in drawings.
Raw material HCFC141b and anhydrous hydrogen fluoride enter preheater (3) with volume pump from storage tank (1) and (2) with selected speed, entering fluorination reactor (4) after the gasification reacts, reaction product enters condensation separator (5) condensation separation, gas-phase product HCL, CH after the separation from the bottom of fluorination reactor (4) 3CF 3Draw from condenser overhead and to enter water wash column (6), soda-wash tower (7) is removed HCL, enters gas holder (8), and then drying device (9) (10) drying is after compressor (11) is pressed into thick product groove (12).The CH that condensation is got off in the condensation separator (5) 3CCL 2F, CH 3CCLF 2Preheater (3) and unstripped gas HF, CH are returned in overflow with HF etc. 3CCL 2F enters together and continues reaction in the fluorination reactor (4).
Selection of catalysts is one of key problem in technology of the present invention, and the solid acid catalyst of numerous species all is suitable for the present invention, comprising with gac, ALF 3Or activated alumina carries the metal Fe of attached 0.5-10 weight % as carrier 3+, Be 2+, B 3+, Cr 3+, Ni 3+, Co 3+, Mn 2+, Bi 3+, Cu 2+Or Ag +Oxide compound or halide catalyst.The full genus in the halogenide, bromide and iodide can use, but best with fluorochemical, secondly are muriate or fluorochemical and muriatic mixture.In addition, carrier-free Cr 2O 3Or AlF 3-Cr 2O 3Also can be used as process catalyzer of the present invention, but the most suitable of the present invention be to contain 0.5-10 weight %Co 3+, Mn 2+Or Bi 3+Oxide compound or halogenide be attached to AlF 3Or Al 2O 3Supported catalyst or contain 2-25%Cr 2O 3AlF 3-Cr 2O 3Composite catalyst.At AlF 3Or Al 2O 3Contained Bi in the carrier 3+, Mn 2+, Co 3+Halogenide in best with fluorochemical, secondly be muriate.
Catalyzer can adopt fixed bed, also can adopt thermopnore.
The mole proportioning of raw material HF and HCFC141b can have influence on the transformation efficiency of HCFC141b and the selectivity that HCFC141b is converted into HFC143a.Mole proportioning＜2 of HF and HCFC141b, by product CH 3CCLF 2And CH 3CCL 3Increase, the selectivity of purpose product HFC143a reduces; If HF and HCF141b mole proportioning are greater than 2.5, HCFC141b is converted into the selectivity height of HFC143a, but the utilization ratio of HF is low, and unnecessary HF can increase the recovery burden of HF undoubtedly, therefore, HF that relatively suits and the mole proportioning of HCFC141b are 2.0～2.5, are preferably 2.1～2.3.
Temperature control of the present invention is also very important.Temperature of reaction is high more, and it is fast more that HCFC141b is converted into the speed of response of HFC143a, but the increase of catalyst carbon deposit speed is faster, causes catalyst life to shorten significantly.On the contrary, temperature of reaction reduces, and the carbon deposit speed of catalyzer reduces, and helps prolonging life of catalyst, but CH 3CCl 2F is converted into CH 3CF 3Also corresponding the slowing down of speed.Take all factors into consideration speed of response and catalyst life, temperature of reaction of the present invention generally is controlled at 160～350 ℃, preferably is controlled at 200～280 ℃.
Reaction pressure of the present invention can be a normal pressure, also can pressurize.Synthesis under normal pressure, equipment requirements are not high, and compressive reaction helps fast reaction speed, help CH 3CF 3Generation, also helps HF and reclaim, but pressure increases, also certainly will increase the requirement of equipment and entire reaction system.Therefore, reaction pressure is controlled at 0.1～1.5mpa and is advisable, and preferably is controlled at 0.5～1.0mpa.
By the inventive method, prepare HFC143a by the HCFC141b gas phase fluorination, transformation efficiency and the HCFC141b of HCFC141b are converted into HFC143 aSelectivity all reach more than 99%, every gram catalyzer per hour can prepare HFC143 a0.7 gram.The catalyst surface coking amount is little, and catalyst life obtains significantly and prolongs.The inventive method both provided the substitute HFC143 of a preparation HCFC22 aNovel method, the fine outlet after a HCFC141b limits the use of or forbids is provided again.
Specify the inventive method below for example, the catalyzer component content is weight percentage in each example
Embodiment: one
200 grams are contained Bi 2O 3, M nCl 2AlF 3(Bi content 3%, M nContent 2%) add gas phase fluorination device (4) (carbon steel system, 25 millimeters of calibers, catalyzer are piled high 90 centimetres),, feed nitrogen simultaneously and drive moisture content per hour to heat up 50 ℃ speed heating.Kept after rising to 250 ° five hours, wherein last hour feeds anhydrous hydrogen fluoride 60 grams.Be cooled to 220 ℃ of beginning fluoridations then.Control HF feed rate is 85 Grams Per Hours, and the feed rate of HCFC141b is 200 Grams Per Hours, and 3 seconds residence time, reaction pressure is a normal pressure, and reaction product is through washing (6), and alkali cleaning enters gas holder after (7).Form at the preceding gas chromatography analysis for sampling material of gas holder (8) simultaneously.Reaction continues 250 hours.The results are shown in Table one: table one
Reaction times (accumulative total) Temperature of reaction ℃ The alkali cleaning after product is formed M% HFC143a output gram/gram. hour HCFC141b
HFC 143a HCFC 142b HCFC 141b Transformation efficiency % Selectivity %
50 220 94.1 1.5 0.3 0.68 99.7 94.4
100 220 98.0 1.1 0.5 0.89 99.5 96.5
150 220 98.1 1.1 0.3 0.69 99.7 96.8
200 220 94.3 3.0 0.4 0.68 98.6 94.7
250 220 98.1 0.9 0.4 0.89 99.6 96.5
Embodiment two～nine
The dissimilar catalyzer of 400 grams are added gas phase fluorination device (4) (carbon steel system, caliber are 35 millimeters, and catalyzer is piled high 90 centimetres),, feed nitrogen simultaneously and drive moisture content per hour to heat up 50 ℃ speed heating.Rise to and kept five hours after giving fixed temperature of reaction.Wherein last hour feeds the HF120 gram, begins fluoridation then.Press the given reaction conditions control of table two.The heat transfer area of condensation separator (5) is 0.2 meter 2, number of actual plates is 5, control condenser (5) top material temperature＜-10 ℃, after treating that fluorination reactor pressure liter reaches 0.9MPa, emit reaction product by condenser (5) top, after washing (6), alkali cleaning (7), enter gas holder before gas chromatography analysis for sampling product composition.The anhydrous hydrogen fluoride that the interior condensation of condensation separator (5) is got off, CH 3CCl 2Be back to fluorination reactor (4) continuation reaction Deng overflow to preheater (14). react the 20th hour sampling analysis.The results are shown in Table three.
Table two
Sequence number Catalyzer and prescription thereof Reaction conditions
Temperature of reaction (℃) HF add-on (g/h) HCFC141b add-on (g/h)
2 3 4 5 6 7 8 9 Bi 2O 2-MnCl a/AlF a B i 3+3％Mn 2+2％ FeCl 3/C Fe 3+7％ CrClX/C Cr 3+14％ Bi 2O 3-CrCl 3/AlF 3 Bi 3+1％ Cr 2+2％ Bi 2O 3-CoCl 3/AlF 2Bi 3+1％ Co 3+2％ Cr 2O 3/AlF 3 Cr 2O 310％ Cr 2O 3Bi 2O a-MnCl 2/Al 2O 3 Bi 3+3％ Mn 2+2％ 220 290 380 230 230 230 210 230 165 110 125 165 165 185 165 165 450 300 350 450 450 450 450 450
Table three
Sequence number Reaction product is formed M% HFC143a output gram/gram. hour CH 3CClF
HFC143a HFC142b HFC141b Transformation efficiency % Selectivity %
2 3 4 5 6 7 8 9 99.5 99.3 99.3 99.5 99.5 99.5 99.6 99.5 0.3 0.4 0.4 0.3 0.3 0.3 0.3 0.3 0.1 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.80 0.53 0.62 0.80 0.80 0.80 0.80 0.80 99.9 99.8 99.8 99.9 99.8 99.9 99.9 99.9 99.6 89.4 99.4 99.6 99.6 99.8 99.6 99.6

Claims (3)

1, a kind of preparation 1,1, the method for 1-Halothane is characterized in that by 1,1 1-chloro fluoroethane and anhydrous hydrogen fluoride be gas phase fluorination in the presence of solid catalyst, catalyzer adopts with gac, AlF 3Or activated alumina is carrier, carries the metal Fe of attached 0.5-10 weight % 3+, Be 2+, B 3+, Cr 3+, Ni 2+, Co 3+, Mn 2+, Bi 3+, Cu 2+Or Ag +Oxide compound or halogenide or carrier-free Cr 2O 3Or AlF 3-Cr 2O 3, HF and 1,1, the mole proportioning 2.0-2.5 of 1-chloro fluoroethane, temperature of reaction is controlled at 160-350 ℃, reaction pressure 0.10-1.5MPa.
2,, it is characterized in that adopting containing 0.5-10 weight %Bi by the said method of claim 1 3+, Mn 2+Or Co 3+Oxide compound or halides be attached to AlF 3Or Al 2O 3Supported catalyst or contain 2-25%Cr 2O 3AlF 3-Cr 2O 3Composite catalyst, HF and 1,1, the mole proportioning 2.1-2.3 of 1-chloro fluoroethane, temperature of reaction 200-280 ℃, reaction pressure 0.5-1.0MPa.
3, by claim 1,2 said methods, it is characterized in that the metal halides in the catalyst system therefor is fluorochemical or muriate or fluorochemical and muriatic mixture.
CN94101618A 1994-02-08 1994-02-08 1,1,1-trifluoroethane preparation by gas-phase fluorization of 1,1,1-dichlorofluoroethane Expired - Lifetime CN1044803C (en)

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CN106964402A (en) * 2017-04-14 2017-07-21 张玲 A kind of preparation method for being fluorinated hydrogen activation catalyst

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0036123A1 (en) * 1980-03-14 1981-09-23 Hoechst Aktiengesellschaft Process for the preparation of very pure, partially fluorinated ethanes
EP0234478A2 (en) * 1986-02-25 1987-09-02 Toyota Jidosha Kabushiki Kaisha Internal combustion engine siamese port type intake system construction with internal ridge structure partially separating helical port and bypass passage
US4849555A (en) * 1987-07-03 1989-07-18 Societe Atochem Synthesis of 1-chloro-1, 1-difluoroethane
DE4005945A1 (en) * 1990-02-26 1991-08-29 Kali Chemie Ag METHOD FOR PRODUCING AETHANE DERIVATIVES

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0036123A1 (en) * 1980-03-14 1981-09-23 Hoechst Aktiengesellschaft Process for the preparation of very pure, partially fluorinated ethanes
EP0234478A2 (en) * 1986-02-25 1987-09-02 Toyota Jidosha Kabushiki Kaisha Internal combustion engine siamese port type intake system construction with internal ridge structure partially separating helical port and bypass passage
US4849555A (en) * 1987-07-03 1989-07-18 Societe Atochem Synthesis of 1-chloro-1, 1-difluoroethane
DE4005945A1 (en) * 1990-02-26 1991-08-29 Kali Chemie Ag METHOD FOR PRODUCING AETHANE DERIVATIVES

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