WO2018231764A1 - Procédé de production de hfo-1234yf à partir de tcp par suppression du point de bulle/rosée - Google Patents

Procédé de production de hfo-1234yf à partir de tcp par suppression du point de bulle/rosée Download PDF

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Publication number
WO2018231764A1
WO2018231764A1 PCT/US2018/037010 US2018037010W WO2018231764A1 WO 2018231764 A1 WO2018231764 A1 WO 2018231764A1 US 2018037010 W US2018037010 W US 2018037010W WO 2018231764 A1 WO2018231764 A1 WO 2018231764A1
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hcfc
hfc
heat exchanger
tcp
shell
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PCT/US2018/037010
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English (en)
Inventor
Haluk Kopkalli
Yuon Chiu
Richard HORWATH
Robert A. Smith
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Honeywell International Inc.
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Publication of WO2018231764A1 publication Critical patent/WO2018231764A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention provides a process for producing 2 ⁇ chloro ⁇ 3,3,3-trifluoropropene (HCFC- 1233xf) from a starting organic composition comprising, for example, 1,1,2,3-tetrachloropropene (HCO-1230xa; also known as TCP) and hydrogen fluoride (HF) wherein a third component, 2- chloro-l,l,l 5 2-tetrafluoroethane (HCFC-124), which is more volatile than either TCP or HF, is added to the reaction mixture.
  • the invention also provides a process for producing HCFC- 1233xf wherein at least a portion of starting organic composition, e.g.
  • TCP is vaporized in a shell-and-tube heat exchanger; in another practice of the invention, the starting organic composition, e.g., TCP, is contacted with a vaporized superheated co-feed of HCFC-124, the contacting occurring in a shell-and-tube heat exchanger.
  • HCFC-1233xf is useful as an intermediate in the production of 2,3,3,3,-tetraf!uoropropene (HFO-1234yf).
  • Hydrofluoroolefins such as tetrafiuoropropenes, including 2,3,3,3- tetrafluoropropene (HFO-1234yf) are known to be effective refrigerants, heat transfer media, propel!ants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers,
  • HFO-1234yf has also been shown to be a low global warming compound with low toxicity and, hence, can meet increasingly stringent requirements for refrigerants in mobile air conditioning. Accordingly, compositions containing HFO-1234yf are among the materials being developed for use in many of the aforementioned applications.
  • TCP trifluoropropene
  • TCP used in Step (1) has a high normal boiling point (circa 166° C) and is suspected of having thermal stability issues, a large excess of HF to TCP is considered to be required, even in the presence of under-fluorinated recycle and the desired HCFC-1233xf product. Notwithstanding this, the complete vaporization temperature (dew point) of a mixture of TCP and HF is still fairly high under usual reaction pressure conditions which run around 100 psig. Indeed, it is believed that TCP may be breaking down and causing fouling in vaporization equipment, as well as fouling the solid catalyst itself, oftentimes related to unwanted
  • an effective amount of an organic co-feed having a boiling point lower than various starting materials, including TCP is employed.
  • co-feeds in this regard are: trichlorofluoropropene (1231); 2,3-dichloro ⁇ 3,3 ⁇ diiluoropropene (1232xf); l,2 ⁇ dichloro-3,3,3- trifluoropropene (1223xd); 2 ⁇ chloro-3,3,3-trifluoropropene (1233xf); 2-chloro-l ,l,l,2- tetrachloropropane (244bb); 1,1,1,2,2-pentafluoropropane (HFC ⁇ 245cb); difluoromethane (HFC- 32); 1,1,1,2,2-pentafluoroethane (HFC-125); 1,1,1,2-tetrafluoroethane (HFC- 134a
  • HFC- 143 trifluoroethane (HFC- 143) (including all isomers thereof); and 1,1,1,3,3-pentafluoropropane (HFC-245fa).
  • HFC-245fa 1,1,1,3,3-pentafluoropropane
  • the present invention is to a process for producing 2-chloro-3,3,3- trifluoropropene (HCFC-1233xf) comprising contacting (i) a starting organic composition comprising a compound of formulas (I), (II), and/or (III):
  • a co-feed comprising 2-chloro-l,l,l,2-tetrafluoroethane (HCFC-124), and (iii) optionally hydrogen fluoride (HF), wherein X is independently selected from F, CI, Br, and I, provided that at least one X is not fluorine, under conditions effective to produce a product comprising HCFC-1233xf.
  • the starting organic composition comprises 1,1 ,2,3- tetrachloropropene (TCP).
  • TCP 1,1 ,2,3- tetrachloropropene
  • the process co-produces 1 ,1,1,2,2- pentafluoroethane (HFC- 125).
  • the invention is to a process for producing HCFC-1233xf comprising at least partially vaporizing, in a shell -and- tube heat exchanger, a liquid starting organic
  • the process further comprises superheating the liquid starting orgamc composition in the shell-and-tube heat exchanger.
  • the shell-and- tube heat exchanger has a tube side inlet plenum, and the liquid starting organic composition is introduced into the tube side inlet plenum under conditions effective to at least partially vaporize the liquid starting organic composition inside the tubes of the shell-and-tube heat exchanger.
  • the present invention is to a process for producing HCFC-1233xf comprising: (a) contacting (i) a liquid starting organic composition, e.g., comprising TCP, with (ii) a vaporized superheated co-feed comprising HCFC-124; and (b) contacting the result of (a) with HF in the presence of a catalyst under conditions effective to produce a product, comprising HCFC-1233xf, wherein the contacting of (i) and (ii) is in a shell-and-tube heat exchanger.
  • a liquid starting organic composition e.g., comprising TCP
  • a vaporized superheated co-feed comprising HCFC-124
  • the HCFC-1233xf produced can be employed as an intermediate in the productio of 2,3,3,3-tetrafluoropropene (HFO-1234yf).
  • HFO-1234yf 2,3,3,3-tetrafluoropropene
  • the invention is directed to a process for producing 2-chloro-3,3,3- trifluoropropene (HCFC-1233xf) comprising contacting (i) a starting organic composition comprising a compound of formulas (I), (IT), and/or (III):
  • a co-feed comprising 2-chloro-l ,l,l,2-tetrafluoroethane (HCFC-124), and (iii) optionally hydrogen fluoride (HF), wherein X is independently selected from F, CI, Br, and I, provided that at least one X is not fluorine, under conditions effective to produce a product comprising HCFC-1233xf.
  • the process co-produces 1,1,1,2,2- pentafluoroethane (HFC-125) along with HCFO-1233xf. That, is, the product of the process of the invention further comprises HFC-125. This is in addition to HCFC-1233xf present in the product.
  • the HFC-125 and HCFC ⁇ 1233xf can be separated by methods known in the art.
  • the HFC-125 can then be recovered, purified, and reused or sold.
  • HFC-125 may be passed to Step (2) and Step (3) of the process described above to recover HFC-125 and HFO-1234yf.
  • the co-feed (ii) further comprises, in addition to HCFC- 124, one or more of the following; HF, HCFC-1233xf, HCFO-1231, HCFO-1232xf, HCFO- 1223xd, HCFO-1233xf, HCFC-244bb, HFC-245cb, HFC-32, HFC- 125, HFC- 134a, HFC-255fa, and HFC- 143 including all isomers thereof.
  • the co-feed comprising HCFC-124 can be either liquid or vapor.
  • the starting organic composition (i) is a liquid; and the co-feed (ii) is a vaporized superheated co- feed comprising HCFC-124.
  • the starting organic composition (i) is a liquid; and the co-feed (ii) is a liquid comprising HCFC-124.
  • An example of a starting organic composition of formula (I) is 1,1,2,3-tetrachloropropene (HCO-1230xa; also known as TCP); an example of a starting organic composition of formula (II) is 2,3,3,3-tetrachoropropene (HCO- 1230xf); an example of a starting organic composition of formula (III) is 1,1,1,2,3- pentachloropropane (HFC-240db).
  • Other processes and practices applicable to the present invention include, without limitation, integrated multistep processes as described in U.S. Pat. No. 8,084,653 and U.S. Published Patent Application 2009/0240090, the contents of each of which are incorporated herein by reference.
  • the amount of HCFC-124 employed in co-feed (ii) can vary.
  • HCFC-124 is present in an amoun t of between about 0.1 to about 99.9 wt % based on the starting organic composition.
  • the HCFC-124 is present in an amount of between about 1 to about 50 wt %, preferably between about 5 to about 15 wt%, based on the starting organic composition.
  • 10 wt% HCFC-124 based on the starting organic composition would ensue when there are 10 lbs of HCFC-124 and 90 lbs of TCP.
  • HCFC-124 based on starting organic composition would ensue with 10 lbs of HCFC-124, 10 lbs of HCFO-1233xf, and 80 lbs of TCP.
  • HCFC-124 will react with HF to form HFC- 125. Any unreacted HCFC-124 and/or co-produced HFC- 125 can be recovered and recycled. Unreacted HCFC-124 can be recovered or recycled back to the process, for example, back to the vaporizatio system.
  • organic composition as used herein includes compounds containing carbon, and excludes HF and the like. [0015] In one embodiment, the step of contacting occurs in the presence of hydrogen fluoride (HF), or another fluorinating agent.
  • the step of contacting the organic starting composition with HF and HCFC-124 occurs in the presence of a catalyst; in one practice of this embodiment, the contacting step occurs in a vapor phase in the presence of a vapor phase catalyst.
  • Serviceable vapor phase catalysts include, but are not limited to, a chromium oxide, a chromium hydroxide, a chromium halide, a chromium oxyhalide, an aluminum oxide, an aluminum hydroxide, an aluminum halide, an aluminum oxyhalide, a cobalt oxide, a cobalt hydroxide, a cobalt halide, a cobalt oxyhalide, a manganese oxide, a manganese hydroxide, a manganese halide, a manganese oxyhalide, a nickel oxide, a nickel hydroxide, a nickel halide, a nickel oxyhalide, an iron oxide, an iron hydroxide, an iron halide, an iron oxyhalide
  • liquid TCP, HF, and HCFC-124 are fed continuously to a steam vaporizer.
  • the steam pressure can be varied in a wide range from 30 to 250 psig, preferably from 100-200 psig, and even more preferably from 140-160 psig.
  • the mol ratio of HF to TCP is 1 : 1 to 100:1 , and preferably from about 10: 1 to about 50:1. In another practice, the mol ratio of HF to TCP is from about 20:1 to about 50: 1.
  • the vaporizer can be operated at a pressure of 200 psig or lower, preferably 100 psig or lower, and even more preferably 80 psig or lower.
  • the process temperature at the outlet of the vaporizer is inherently determined by the dew point of the mixture, its dimension and efficiency, as well as steam and process conditions.
  • TCP as an example of the liquid starting organic composition
  • a compound of formulas (I), (II), and/or (III) can be employed.
  • the process uses 2 ⁇ chloro ⁇ l,l ,l,2-tetrafluorethane (HFC- 124) to aid the vaporization of 1,1,2,3- tetrachloropropene (1230xa) in producing 2-chloro-3,3,3, riffuoropropene.
  • HFC- 124 2 ⁇ chloro ⁇ l,l ,l,2-tetrafluorethane
  • liquid TCP is contacted with a vaporized superheated co-feed stream of HFC- 124 to promote a cleaner vaporization prior to the vapor-phase reaction.
  • the vaporized co-feed stream contains a combination of HFC- 124, PIF, I-ICFC-1233x.fl and/or other co-feed materials such as HCFO-1231 , HCFO-1232xf, HCFO-1223xd, HCFO-1233xf, HCFC- 244bb, HFC-245cb, HFC-32, HFC-125, HFC-134a, HFC- 143 (including all isomers thereof), and HFC-245fa.
  • the co-feed stream is a super-heated vapor prior to contacting with TCP.
  • liquid TCP is contacted with the superheated vapor co-feed stream by spraying or injecting liquid TCP inside the lower head of a vertical shell-and- tube heat exchanger which is simultaneously fed with the superheated co-feed, allowing the TCP to partially or completely vaporize inside the lubes of the vertical shell and tube heat exchanger.
  • the liquid TCP is contacted with a co-feed stream of liquid HFC- 124 prior to vaporization.
  • Other practices include preheating the liquid TCP to a temperature below, but near the bubble point prior to contact with the vapor co-feed stream.
  • the liquid TCP is contacted with a co-feed liquid stream that contains a combination of HFC- 124, HF, HCFC-1233xf, and other co-feeds, such as trichlorofluoropropene (1231); 2,3-dichloro-3,3- difluoropropene (1232xf); l,2-dichloro-3,3,3-trifluoropropene (1223xd); 2-chloro-3,3,3- trifluoropropene (1233x1); 2-chloro-l,l ,l,2-tetrachloropropane (244bb); 1,1,1,2,2- pentafluoropropane (HFC-245cb); dif!uoromethane (HFC-32); 1,1,1 ,2,2-pentafluoroethane (HFC-125); 1,1,1,2-tetrafluoroethane (HFC- 134a); trifluoroethane (HFC- 14
  • the invention is directed to a process for producing 2-chloro- 3,3,3-trifluoropropene (HCFC-1233xf) comprising: (a) at least partially vaporizing, in a shell- and-tube heat exchanger, a liquid starting organic composition comprising a compound of formulas ( ⁇ ), (II), and/or (III), as these formulas are defined herein, and (b) contacting the result of (a) with hydrogen fluoride (HF) in the presence of a catalyst under conditions effective to produce a product comprising HCFC-1233xf.
  • the process further comprises superheating the liquid starting organic composition in the shell-and-tube heat exchanger.
  • the shell -and- tube heat exchanger can be of any suitable design, but preferably has a tube side inlet plenum, and the liquid starting organic composition is introduced into the tube side inlet plenum under conditions effective to at least partially vaporize the liquid starting organic composition inside the tubes of the shell-and-tube heat exchanger.
  • the shell-and-tube heat exchanger is a vertical shell-and-tube heat exchanger having a lower head section wherein the tube side inlet plenum is at the lower head section, and wherein the vertical shell-and-tube heat exchanger optionally includes one or more of the following: a vapor distributor, an internal liquid feed pipe, a liquid distributor, and a liquid restriction plate.
  • the liquid starting organic composition is introduced into the tube side inlet plenum by spray or injection or both.
  • the liquid starting organic composition is partially vaporized inside the tubes of the shell-and-tube heat exchanger, and wherein the process further comprises removing the unvaporized liquid starting organic composition prior to step (b).
  • the liquid starting organic composition is pre-heated prior to step (a).
  • step (a) comprises: contacting the liquid starting organic composition with a vaporized superheated co- feed comprising 2-chloro-l,l,l ,2-tetrafluoroethane (HCFC-124), wherein the contacting is in the shell-and-tube heat exchanger, and wherein the liquid starting organic composition comprises 1 ,1,2,3-tetrachloropropene (TCP).
  • the liquid starting organic composition e.g. which can comprise TCP
  • the vaporized superheated co-feed comprising HCFC-124 are introduced into the tube side inlet plenum substantially simultaneously.
  • the vaporized superheated co-feed comprising HC FC-124 can, but need not, further comprise one of more of the following: HF, HCFC-1233xf, HCFO-1231, HCFO-1232xf, HCFO-1223xd, HCFO-1233xf, HCFC-244bb, HFC-245cb, HFC-32, HFC-125, HFC-134a, HFC-245fa, and HFC-143 including all isomers thereof.
  • the product further comprises 1,1,1, 2,2 -pentafluoroethane (HFC-125), and, optionally, the process further comprises separating the HFC-125 from the HCFC-1233xf.
  • step (a) requires no co-feed, including without limitation HCFC-124.
  • the invention is to a process for producing HCFC-1233xf comprising: (a) contacting (i) a liquid starting organic composition comprising TCP with (ii) a vaporized superheated co-feed comprising HCFC-124; and (b) contacting the result of (a) with hydrogen fluoride (HF) in the presence of a catalyst under conditions effective to produce a product comprising HCFC-1233xf, wherein the contacting of (i) and (ii) is in a sheil-and-tube heat exchanger, wherein the sheil-and-tube heat exchanger has a tube side inlet plenum, and the liquid starting organic comprising TCP, and the vaporized superheated co-feed comprising HCFC-124, are introduced into the tube side inlet plenum substantially simultaneously under conditions effective to at least partially vaporize the TCP inside the tubes of the she l-and-tube heat exchanger, wherein any unvaporized TCP is removed prior to step (b).
  • HF hydrogen fluoride
  • the invention is to a process for producing 2,3,3,3- tetrafluoropropene (HFO-1234yf) comprising: a) preparing a first intermediate composition comprising 2-chloro-HCFC-1233xf prepared in accordance with the foregoing; b) contacting said first intermediate composition comprising HCFC-1233xf with HF in the presence of a fluorination catalyst under conditions effective to produce a second intermediate composition comprising HCFC-244bb; and c) dehydrochlorinating at least a portion of said second intermediate composition comprising HCFC-244bb to produce a reaction product comprising HFO-1234yf, and optionally 1,1,1,2,2-pentafluoroethane (HFC-125).
  • HFO-1234yf 2,3,3,3- tetrafluoropropene
  • the invention is directed to a process for producing 2-chloro- 3,3,3-trifluoropropene (HCFC-1233xf) comprising; (a) contacting (i) a liquid starting organic composition comprising a compound of formulas (I), (II), and/or (III):
  • X is independently selected from F, CI, Br, and I, provided that at least one X is not fluorine, with (ii) a vaporized superheated co-feed comprising 2-chloro-l,l,l 5 2-tetrafluoroethane (HCFC-124); and (b) contacting the result of (a) with hydrogen fluoride (HF) in the presence of a catalyst under conditions effective to produce a product comprising HCFC-1233xf, wherein the product optionally further comprises 1,1,1,2,2-pentafluoroethane (HFC-125), wherein the process can optionally further comprise separating the HFC-125 from the HCFC-1233xf, and wherein the contacting of (i) and (ii) is in a heat exchanger, e.g.
  • the liquid starting organic composition of (i) comprises 1 ,1,2,3- tetrachloropropene (TCP).
  • TCP ,1,2,3- tetrachloropropene
  • the course of the following discussion will use TCP as an example of the liquid starting organic composition comprising a compound of formulas (I), (II), and/or (III).
  • the shell-and-tube heat exchanger for purposes of the invention as described herein can be of conventional design.
  • the shell-and-tube heat exchanger has a tube side inlet plenum.
  • the shell-and-tube heat exchanger is a vertical shell- and-tube heat exchanger that has a lower head section, and the tube side inlet plenum is at the lower head section of this vertical shell-and-tube heat exchanger.
  • the shell-and-tube heat exchanger may include other known desig details, e.g. a vapor distributor, an internal liquid feed pipe, a liquid distributor, and liquid restriction plate to promote better mixing and efficient vaporization with minimal fouling.
  • the shell side of the heat exchanger may be fed with steam or any other suitable heat transfer medium as know in the art.
  • the shell-and-tube heat exchanger has a tube side inlet plenum, and the liquid starting organic composition of (i) comprises TCP, and the vaporized superheated co-feed comprising HCFC-124 of (ii), are introduced into the tube side inlet plenum under conditions effective to at least partially vaporize the TCP inside the tubes of the shell-and- tube heat exchanger.
  • partially vaporized it is meant that less than 100% of the TCP liquid feed is vaporized. Whe partial vaporization is employed, the effluent from partial vaporizatio can be phase separated to remove the unvaporized liquid for recycle while allowing the vapor to proceed forward .
  • Benefi ts of partial vaporization include reduced fouling of the heat exchanger tubes, reduced oligomer formation, higher yields, and longer run time of the vaporization apparatus and process.
  • the TCP is completely (100%) vaporized.
  • the liquid comprising TCP of (i) is introduced into the tube side inlet plenum by spray or injection or both.
  • the liquid comprising TCP of (i), and the vaporized superheated co-feed comprising HCFC-124 of (ii) are introduced into the tube side inlet plenum substantially simultaneously.
  • the TCP is partially vaporized inside the tubes of the shell-and-tube heat exchanger, and wherein the process further comprises removing the unvaporized TCP prior to step (b).
  • the TCP is pre-heated prior to step (a).
  • the vaporized superheated co-feed comprising HCFC-124 of (ii) further comprises one of more of the following: HF, HCFC-1233xf, HCFO-1231, HCFO-1232xf, HCFO-1223xd, MCFO- i 233xf, HCFC-244bb, HFC-245cb, HFC-32, HFC-125, HFC- 134a, HFC-245fa, and HFC- 143 including all isomers thereof.
  • contacting step (b) of the above process comprises a vapor phase process and suitable catalysts are as hereinabove described, e.g. chromium oxide and the like.
  • the invention is directed to a process for producing 2,3,3,3- tetrafluoropropene (HFO-1234yf) comprising: a) preparing a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene (HCFC-1233xf) prepared using the process as hereinabove described, e.g.
  • a practice that includes a shell-and-tube heat exchanger wherein liquid comprising TCP of (i), and vaporized superheated co-feed comprising HCFC-124 of (ii) are introduced into a tube side inlet plenum under conditions effective to at least partially vaporize the TCP inside the tubes of the shell-and-tube heat exchanger; and b) contacting said first intermediate composition comprising HCFC-1233xf with HF in the presence of a
  • the vaporized mixture is then fed into a fluorination reactor charged with a fluorinated chromia catalyst to convert the starting material(s) into 1233xf.
  • the fluorination reaction may be carried out at a temperature from about 150° C. to about 400° C. (preferably from about 180° C. to about. 300° C.) and at a pressure from about 0 psig to about 200 psig, preferably from about 0 psig to about 100 psig, and even more preferably from about 0 psig to about 70 psig.
  • Contact time of organic feeds with the catalyst may range from about 1 second to about 60 seconds, however, longer or shorter times can be used.
  • the fluorination reaction is preferably carried out to attain a conversion of about 50% or, preferably, about 90% or higher. Conversion is calculated by the number of moles of reactant consumed divided by number of moles of reactant fed to the reactor multiplied by 100.
  • the selectivity for 1233xf attained is preferably about 60% or higher and more preferably about 80% or higher. Selectivity is calculated by number of moles of product (HCFC-1233xf) formed divided by number of moles of reactant consumed.
  • This reaction may be conducted in any reactor suitable for a vapor phase fluorination reaction.
  • the reactor is constructed frorn materials which are resistant to the corrosive effects of hydrogen fluoride and catalyst such as Hastelloy 1M , Nickel, Incoloy iM , Inconel 1M , Monel IM and fluoropolymer linings.
  • the vessel is a fixed catalyst bed or fluidized bed. If desired, inert gases such as nitrogen or argon may be employed in the reactor during operation.
  • the effluent from the fluorination reaction step may be processed to achieve desired degrees of separation and/or other processing.
  • the effluent will generally also include HC1 and one or more of HF, 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), l,2-dichloro-3,3,3-trifSuoropropene
  • HCFO-1223xd trichlorofluoropropene
  • HCFO-1231 trichlorofluoropropene isomers
  • 2-chloro-l,l,l,2- tetrachloropropane HCFC-244bb
  • HCF-245cb 1 ,1,1,2,2-pentafluoropropane
  • HFC-125 pentafluoroethane
  • HCO-1230xa unreacted HCO-1230xf
  • HCFC-124 unreacted HCO-1230xf
  • HCC-240db unreacted HCO-1230xa
  • HCO-1230xf unreacted HCO-1230xf
  • HCC-240db unreacted HCO-1230xa
  • HCO-1230xf unreacted HCO-1230xa
  • HCFC-124 HCFC-124 and/or HCC-240db
  • HCO-1230xf unreacted HCO-1230xf
  • HCFC-124 unreacted HCO-1230xf
  • HCFC-124 unreacted HCO-1230xf
  • HCC-240db unreacted HCO-1230x
  • hydrogen chloride is then recovered from the result of the fluorination reaction.
  • Recovering of hydrogen chloride is conducted by conventional distillation where it is removed from the distillate.
  • HC1 can be recovered or removed by using water or caustic scrubbers. When a water extractor is used, HC1 is removed as an aqueous solution. When caustic scrubbers are used, HQ is just removed from system as a chloride salt in aqueous solution.
  • a stream containing HF, HCFC-124, and HCFO-1233xf is vaporized in a conventional kettle type vaporizer using steam as the heating medium.
  • the vaporized stream is further superheated in a conventional shell and tube heat exchanger with tube side heating utilizing steam or other suitable heat exchange medium.
  • This superheated stream is fed to the lower head of a heat exchanger and is contacted with a liquid TCP stream which is injected into the lower head into the path of the superheated HF, HCFC-124 and HCFG-1233xf.
  • Vaporized TCP, HF, HCFC-124, and HCFO-1233xf are further superheated to reactio temperature and fed to a reactor containing a chrome oxyfluoride catalyst.
  • the exit gases from the reactor comprise HCFO ⁇ 1233xf, HFC-125, and HC1 as the principal products, as well as unreacted TCP, HCFC- 124 and HF.
  • the mixture is subjected to conventional unit operations including cooling and distillation to recover HCFO-1233xf and HFC-125 while unreacted starting materials are recycled for further reaction .
  • HCFO-1233xf may be used to produce HCFC-244bb in Step 2 of a process for making HFO-1234yf. This HCFC-244bb may then be dehydrochlorinated to form HFO ⁇ 1234yf.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de certains composés halogénés, tels que le 2-chloro-3,3,3-trifluoropropène (HCFC-1233xf), utiles en tant qu'intermédiaires dans la production de fluorooléfines, telles que le 2,3,3,3-tétrafluoropropène (HFO-1234 yf)).Dans un mode de réalisation, le procédé de la présente invention comprend la mise en contact d'un matériau de départ, tel que le 1,1,2,3-tétrachloropropène (TCP) avec du 2-chloro-1,1,1,2-tétrafluoroéthane (HCFC-124) et du fluorure d'hydrogène.Le procédé réduit l'oligomérisation et la polymérisation et améliore la stabilité catalytique. Le procédé permet également la coproduction de HFC-125, en plus du HFO-1234yf. Dans un autre mode de réalisation, l'invention vaporise un matériau de départ, tel que TCP, au moins en partie dans un échangeur de chaleur à faisceaux et calandre ; dans un autre mode de réalisation, l'invention met en contact un matériau de départ tel que TCP avec une co-alimentation de vapeur surchauffée comprenant du HCFC-124 dans un échangeur de chaleur à faisceaux et calandre.
PCT/US2018/037010 2017-06-12 2018-06-12 Procédé de production de hfo-1234yf à partir de tcp par suppression du point de bulle/rosée WO2018231764A1 (fr)

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CN109856187B (zh) * 2019-02-01 2021-06-22 中国石油天然气集团有限公司 一种输气管道烃露点在线实时检测方法

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