WO2019220454A1 - Process for purification of olefin feed comprising 1234yf - Google Patents

Process for purification of olefin feed comprising 1234yf Download PDF

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Publication number
WO2019220454A1
WO2019220454A1 PCT/IN2019/050380 IN2019050380W WO2019220454A1 WO 2019220454 A1 WO2019220454 A1 WO 2019220454A1 IN 2019050380 W IN2019050380 W IN 2019050380W WO 2019220454 A1 WO2019220454 A1 WO 2019220454A1
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WO
WIPO (PCT)
Prior art keywords
l234yf
composition
feed
ofcb
l225zc
Prior art date
Application number
PCT/IN2019/050380
Other languages
French (fr)
Inventor
Jose GEORGE
Sunil RAJ
Ambuj Kumar MISHRA
Anurag KATIYAR
Anurag Jain
Sudip Maity
Original Assignee
Srf Limited
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Publication date
Application filed by Srf Limited filed Critical Srf Limited
Priority to JP2020558421A priority Critical patent/JP2021523884A/en
Priority to US17/054,863 priority patent/US11225447B2/en
Priority to EP19803085.0A priority patent/EP3793968A4/en
Publication of WO2019220454A1 publication Critical patent/WO2019220454A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons

Definitions

  • the present invention relates to a process for purifying olefin feed comprising R- l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB.
  • Refrigerant is the substance which is used as working fluid in a thermodynamic cycle, undergoes a phase change from liquid to vapour and produces cooling. These are used in refrigeration, air conditioning, and heat pumping systems. They absorb heat from one area, such as an air conditioned space, and reject it into another, such as outdoors, usually through evaporation and condensation, respectively. These phase changes occur both in absorption and mechanical vapour compression refrigeration systems, but they do not occur in systems operating on a gas cycle using a fluid such as air. Fluorocarbon based fluids have found widespread use in industry in a number of applications, including as refrigerants, aerosol propellants, blowing agents, heat transfer media, and gaseous dielectrics.
  • Tetrafluoropropenes having zero ozone depletion and low global warming potential, have been identified as favorable refrigerant over other refrigerants.
  • One tetrafluoropropene having valuable properties is 2,3,3,3-tetrafluoropropene (R-l234yf).
  • organofluorine compounds often results in the formation of other organofluorine compounds, organochlorines, and chlorofluorocarbons (collectively referred to herein as ‘coproducts of organofluorine production’ or simply ‘coproducts’), as both intermediate products and coproducts that appear in the final reaction mixture.
  • coproducts of organofluorine production or simply ‘coproducts’
  • U.S. Pat. No. 2,931,840 describes a reaction involving the pyrolysis of chloromethane with tetrafluoroethylene, or alternatively chloromethane with chlorodifluorome thane. It is very difficult to remove unreacted chloromethane and other side products from the reaction product stream. It does not mention the process for removing unreacted chloromethane and the side products from the reaction mixture.
  • U.S. Pat. No. 9,302,964 discloses a method for producing 2,3,3,3-tetrafluoropropene, the method comprising contacting an azeotropic composition or azeotrope-like composition of 2,3,3,3-tetrafluoropropene and chloromethane with an extraction solvent to obtain 2,3,3,3-tetrafluoropropene containing substantially no chloromethane.
  • PCT publication no. 2017/108519 discloses a process forpurifying 2,3,3,3-tetrafluoro- l-propene (R-l234yf) from a first composition comprising 2,3,3,3-tetrafluoro-l- propene, 3,3,3-trifluoropropene (R-l243zf), trans-l, 3,3,3-tetrafluoro-l-propene (R- l234ze-E) and optionally or not at least one compound selected from the group consisting of chloromethane (R-40), l,l-difluoroethane (R-l52a), chloropentafluoroethane (R-115), 1 , 1 , 1 ,2-tetrafluoroethane (R-l34a), trans-l, 2, 3,3,3- pentafluoropropene (R-l225ye-E); wherein the said process involves solvent extraction and extractive distillation methods.
  • PCT publication no. 2017/108522 discloses a process for purifying 2, 3,3,3-tetrafluoro- l-propene (R-l234yf) from a first composition comprising 2, 3,3,3-tetrafluoro-l- propene and chloromethane (R-40); wherein the said process involves solvent extraction and extractive distillation methods.
  • R-l234yf 2, 3,3,3-tetrafluoro- l-propene
  • R-40 chloromethane
  • 2017/108524 discloses a process for purifying 2,3,3, 3-tetrafluoro- l-propene (R-l234yf) from a first composition comprising 2,3,3,3-tetrafluoro-l- propene, l,l,l,2,2-pentafluoropropane (R-245cb) and trans-l,3,3,3-tetrafluoro-l- propene (R-l234ze-E); wherein the said process involves solvent extraction and extractive distillation methods.
  • Compounds having close boiling point to 2,3,3,3-tetrafluoropropene are 1, 1, 1,2- tetrafluoroethane (R-l34a), l, l,3,3,3-pentafluoropropene (l225zc), 1, 1,2,2- tetrafluoroethane (R-134), chlorotrifluoroethene (CTFE) and chloromethane (R-40). Separation of these compounds by normal distillation is very difficult.
  • a first aspect of the present invention provides a process for purification of R- l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprises a step of separating a ternary azeotrope composition“A” comprising R-l234yf, R-40 and R-l34a.
  • An important embodiment of the first aspect of the present invention provides a process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, the process comprising the steps of:
  • step b) optionally passing the ternary azeotrope composition“A” comprising R- l234yf, R-40 and R-l34a through any one or more selected from an absorption tower, an adsorption tower and a semipermeable membrane; c) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“B” comprising R-l234yf and R-l34a and bottom composition comprising substantially pure R-l234yf.
  • Another embodiment of present invention provides a process for purification of R- l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprises a step of separating a binary azeotrope composition“B” comprising of 10 mole % to 35 mole % of R-l34a and 60 mole % to 90 mole % of l234yf.
  • a second aspect of the present invention provides a process for purification of R- l234yf feed comprising R-22, R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprising the steps of separating a top composition comprising R-22, OFCB, R- l234yf, R-40 and R-l34a.
  • An embodiment of second aspect of the present invention provides a process for purification of R-l234yf feed comprising R-22, R-l234yf, R-40, R-l34a, R-134, R- l225zc, and OFCB, the process comprising the steps of:
  • step c) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“B” comprising R-l234yf and R-l34a and bottom composition comprising pure R-l234yf.
  • a third aspect of the present invention provides a process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, the process comprising the steps of:
  • An embodiment of third aspect of the present invention provides a process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, the process comprising the steps of:
  • step b) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“D” comprising R-l234yf and R-134 and a bottom composition comprising substantially pure R-l234yf;
  • An embodiment of third aspect of the present invention provides a process for purification of R-l234yf feed comprising R-l234yf, R-134, the process comprising the steps of:
  • step b) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“D” comprising R-l234yf and R-134 and a bottom composition comprising substantially pure R-l234yf;
  • a fourth aspect of the present invention provides a process for separating chlorocarbon from a feed comprising at least one fluoroolefinic and chlorocarbon by contacting the feed with a semipermeable membrane to obtain the feed substantially free of the chlorocarbon.
  • a fifth aspect of the present invention provides a process for preparing l234yf, the process comprising the steps of:
  • FIG. 1 illustrates the process for preparation of feed.
  • Figure 2 illustrates first aspect of the present invention.
  • FIG. 3 illustrates second aspect of the present invention.
  • Figure 4 illustrates third aspect of the present invention.
  • FIG. 5 illustrates fourth aspect of the present invention. DETAILED DESCRIPTION
  • azeotrope or azeotrope like is intended in its broad sense to include both compositions that are strictly azeotropic and compositions that behave like azeotropic mixtures.
  • An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the stated pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant boiling and cannot be separated during a phase change.
  • the term‘heavies’ refers to a mixture comprising mainly of high boiling components having boiling points greater than R40 such as octafluorocyclobutane (OFCB), tetrafluorochloroethane, tetrafluoroethane, R-l224zc (3-chloro-l,l,3,3-tetrafluoropropene), R-l 112 (2,2-dichloro-l,l-difluororoethene), R-236ca (l, l,2,2,3,3-Hexafluoropropane), R-236ea (l,l,l,2,3,3-Hexafluoropropane), R-l 122 (2-chloro-l,l-difluoroethene), R-227ca (l,l,l,2,2,3,3-Heptafluoropropane), R-227ea (l,l,l,2,3,3,3-H
  • feed used in the present invention refers to crude composition obtained by the reaction of tetrafluoroethylene/ chlorodifluoromethane with chloromethane/methane, optionally in presence of initiator or catalyst known in the art.
  • feed contains components selected from VdF (Vinylidenefluoride), tetrafluoroethene (TFE), R-32 (Difluoromethane), R-40 (chlorome thane), R-l234yf (2,3,3,3-tetrafluoropropene), HFP (Hexafluoropropene), OFCB
  • the feed can also be obtained by following the process disclosed in PCT publication PCT/IN2017/050006 and/or PCT publication PCT/IN2017/050555 filed by the same applicant.
  • fluoroolefinic compounds used in the present invention refers to unsaturated organofluorine compound.
  • unsaturated organofluorine compounds includes R-l234yf, R-l234ze, R-l243zf, R-l233zd, R-l233xf, R-l225zc and mixtures thereof.
  • chlorocarbon used in the present invention refers to chlorinated hydrocarbons and chlorofluorocarbons (CFCs).
  • CFCs includes CFC-l l (CClsF), CFC-12 (CCI2F2), HCFC-21 (CHCI2F), HCFC-22 (R22; CHCIF2), HCFC-23 (CHF3).
  • chlorinated hydrocarbons includes chloromethane, methylene chloride, and carbon tetrachloride.
  • the selective permeability of a membrane is characterized by a separation factor a, which is a measure of the preferential permeability of one compound or type of compound over another compound or type of compound.
  • the separation factor is the ratio of the relative amount of a compound that permeates through the membrane to the relative amount of another compound that permeates the membrane.
  • the permeability is function of temperature, pressure and time.
  • the operable temperature ranges from 0°C to 50°C.
  • the operable pressure ranges from 1 bar to 10 bars
  • permeate refers to the component of the feed that permeates through semipermeable membrane.
  • the term“retantate” refers to the component of the feed that does not permeates through semipermeable membrane.
  • substantially free used in the present invention refers to a composition that is 80% free of chlorocarbon compared to the feed.
  • anhydrous used in the present invention refers to water content of less than 50 ppm
  • the feed is a non- azeotrope mixture obtained by passing the products obtained by the reaction of tetrafluoroethylene/ chlorodifluoromethane and chloromethane/methane, through successive distillation columns.
  • the feed is a non-azeotrope mixture obtained by passing the product obtained by the reaction of tetrafluoroethylene/ chlorodifluoromethane and chloromethane/methane, through three successive distillation columns, heat quencher, alkali scrubber, and/or sulfuric acid to remove moisture and/or alumina to remove moisture/acid to obtain a stream of gases free from moisture and acid.
  • the feed is obtained from the process illustrated in Figure 1.
  • ‘10’ of Figure 1 represent chlorodifluoromethane being charged to the reactor‘20’ maintained at a temperature of about 700°C to about 800°C using an electric heater or steam.
  • the stream of gases ‘30’ mainly comprising tetrafluoroethene, along with‘40’ comprising of R-40 and an initiator such as carbon tetrachloride/hexachloroethane/trichloroacetylchloride/chloroform is fed to another reactor‘50’ maintained at a temperature of about 500°C to about 800°C using electrical heater or fired furnace.
  • the stream‘60’ recovered from‘50’ is passed through quencher (heat quencher), alkali scrubber, sulfuric acid and alumina to obtain a stream of gases free of acid and moisture is fed to the distillation column‘70’.‘80’, the lower boiling fractions recovered from‘70’ are fed back to the reactor‘50’, and the higher boiling fractions‘90’ comprising R-40, R-l234yf, HFP, OFCB, R-l225zc, R-l34a, R-134, R-22, CTFE, and heavies are fed to the next distillation column‘100’.
  • ‘110’, low boiling fraction comprising R-22 is fed to the reactor‘20’.‘120’, the high boiling fraction comprising R-40, R-l234yf, OFCB, R-l225zc, R-l34a, R-134, and heavies is fed to the next distillation column‘130’.‘140’, the lower boiling fraction comprising R-l234yf, R-l225zc, R-l34a, R-134, R-40, and OFCB is passed through absorption tower ‘160’ to obtain feed ‘170’. ‘150’, the higher boiling fractions comprising heavies is recycled back to the reactor‘50’.
  • the feed“170” may additionally contain R-22.
  • the feed is a non-azeotrope mixture obtained from the distillation column maintained at a temperature range of -29°C to - 23°C at an atmospheric pressure.
  • reaction of tetrafluoroethylene/chlorodifluoromethane with chloromethane/methane can be done in a batch reactor or semi-batch reactor or continuous reactor.
  • process of purification is performed in a continuous reactor.
  • the feed comprises non-azeotrope mixture comprises of R-l234yf, R-40, R-l34a, R-l225zc, R-134, and OFCB.
  • the feed may contain heavies.
  • the feed comprises non-azeotrope mixture comprises of about 20 mole% to about 35 mole % of R-l234yf, about 5 mole % to about 15 mole % of R-40, of about 0.5 mole % to about 20 mole % of R-l34a, about 1 mole % to about 4 mole % of R-l225zc, about 1 mole % to about
  • R- 134 4 mole % of R- 134, about 20 mole % to about 45 mole % of OFCB and about 5 mole % to about 10 mole % of heavies and lights.
  • the feed comprises non-azeotrope mixture comprises of R-22, R-l234yf, R-40, R-l34a, R-l225zc, R-134, OFCB and heavies.
  • R-22 may be added to the feed additionally before feeding it to the distillation column.
  • the feed may contain heavies.
  • the feed comprises non-azeotrope mixture comprises of about 5 mole % to about 25 mole % of R-22, of about 15 mole% to about 35 mole % of R-l234yf, about 20 mole % to about 45 mole % of R-40, of about 0.5 mole % to about 10 mole % of R-l34a, about 0.1 mole % to about 10 mole % of R-l225zc, about 0.1 mole % to about 10 mole % of R- 134, about 5 mole % to about 45 mole % of OFCB and about 3 mole % to about
  • absorption tower refers to the tower containing adsorption solvent selected from an alcohol, nitrile, chlorinated hydrocarbon, amides, ethers or esters.
  • the absorption tower contains a solvent selected from a group consisting of dichlorome thane, chloromethane, carbon tetrachloride, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, dimethylformamide, or the like.
  • the absorption tower contains chloroform or methanol.
  • the adsorption tower contains molecular sieves having mean pore diameter of the size ranging from 3 A to 12 ⁇ .
  • the adsorption tower contains molecular sieves having mean pore diameter of the size ranging from 3 A to 5 A.
  • semipermeable membrane refers to polymeric membrane that allows selective permeability of one compound over the other in the feed.
  • polymeric membrane include polyethene, polypropylene, polyester, polyamide, nylon, nitrile rubber, neoprene, polydimethylsiloxane (silicone rubber), chlorosulfonated polyethylene, polysilicone-carbonate copolymers, fluoroelastomer, polyvinylchloride, plasticized polyvinylchloride, polyurethane, cis-polybutadiene, cis-polyisoprene, poly(butene-l), polystyrene-butadiene copolymers, styrene/butadiene/styrene block copolymers, styrene/ethylene/butylene block copolymers, thermoplastic polyolefin elastomers, and block copolymers of polyethers and polyesters.
  • the semipermeable membrane includes polyethene or polypropylene.
  • the ternary azeotrope composition“A” essentially contains R-l234yf, R-l34a and R-40.
  • the ternary azeotrope composition“A” may contain less than about 5 mole % of other components selected from the group consisting of R- 134, R-22, R- l225zc and OFCB.
  • the ternary azeotrope composition“A” comprises about 52 mole % to about 62 mole % of R-l234yf, about 25 mole % to about 34 mole % of R-40 and about 2 mole % to about 25 mole % of R- l34a.
  • the ternary azeotrope composition“A” comprises about 51.5 mole % of R-l234yf, about 30 mole % of R- 40 and about 16 mole % of R-l34a.
  • the ternary azeotrope composition“A” comprises about 51 mole % of R-l234yf, about 30 mole % of R-40 and about 15 mole % of R-l34a.
  • the ternary azeotrope composition“A” comprises about 52.5 mole % of R-l234yf, about 27.2 mole % of R- 40 and about 17.5 mole % of R-l34a.
  • R-l34a may be added to the distillation column to obtain the ternary azeotrope composition.
  • R-l34a may be recovered through pressure swing distillation.
  • the mixture collected at the bottom of the distillation column after the separation of ternary composition is recycled back to one of the initial distillation columns.
  • the binary azeotrope composition“B” essentially contains R-l234yf and R-l34a.
  • the binary azeotrope composition“B” may contain less than about 5 mole % of other components selected from a group consisting of R-134, OFCB, R-l225zc and R-22.
  • the binary azeotrope composition“B” contains about 10 mole % to about 35 mole % of R-l34a and about 60 mole % to about 90 mole % of l234yf.
  • the binary azeotrope composition“B” is recycled back to the initial distillation columns.
  • the process is as depicted in Figure 2.
  • the feed‘170’ is fed to the distillation column‘180’ to recover R-22, which is fed back to the reactor, a low boiling fraction comprising a ternary azeotrope‘190’ and a high boiling fraction‘200’.
  • the ternary composition is fed to series of absorption tower, adsorption tower and semipermeable membranes‘210’.
  • the stream obtained through‘210’ is fed to another distillation column‘220’ to recover binary azeotrope composition‘230’, which is fed back to the distillation column‘180’ and‘240’ comprising substantially of l234yf is recovered or optionally distilled.
  • the top composition comprises about 0.2 mole % to about 10 mole % of OFCB, about 1 mole % to about 10 mole % of R-l34a, about 35 mole % to about 55 mole % of R-l234yf, about 12 mole % to about 40 mole % of R-22 and about 10 mole % to about 40 mole % of R- 40.
  • the R-22 may be added to the feed before passing to the distillation column.
  • the top composition has less than 500 ppm of R-l225zc and R-134.
  • R-l225zc and R-134 are completely not detectable in the top composition.
  • R-22 improves separation of R- l234yf from R-l225zc and R-134 by increasing the relative volatility of R-l234yf.
  • R-22 improves separation of R- l234yf from R-l225zc and R-134 by increasing the relative volatility of R-l234yf.
  • ternary azeotrope of R-l234yf, R40 and R-l34a comes along with binary azeotrope of OFCB and R40 which leads to the suppression of close boiling components like R-l225zc and R-134.
  • the process is as depicted in Figure 3.
  • the feed“170” is fed to the distillation column“180” to recover a low boiling fraction“190”, comprising R-22, R-l234yf, R- 40, R-l34a and OFCB and a high boiling fraction“200”.
  • the low boiling composition is fed to series of absorption tower, adsorption tower and semipermeable membranes “210”.
  • the stream obtained through“210” is fed to another distillation column“220” to recover R-22, the binary azeotrope composition“230” and“240” a high boiling fraction at the bottom of the column.
  • the recovered R-22 is either sent back to the reactor“20” or to the distillation column“180”.“240” is fed to the distillation column “250” to get a binary azeotrope composition“260” that is fed back to the distillation column“180” and“270” comprising substantially of l234yf is recovered or optionally distilled.
  • the mixture collected at the bottom of the distillation column after the separation of top composition is recycled back to one of the initial distillation columns.
  • the ternary azeotrope composition“C” of the third aspect of the present invention essentially contains R-l234yf, R-l34a and R-134.
  • the ternary azeotrope composition of the third aspect of the present invention may contain less than about 5 mole % of other components selected from a group consisting of OFCB and l225zc.
  • R-134 is added to the distillation column to obtain the ternary azeotrope composition“C”.
  • the ternary azeotrope composition“C” comprises of about 70 mole % to about 85 mole % of R- l234yf, about 5 mole % to about 15 mole % of R- 134 and about 2 mole % to about 20 mole % of R- 134a.
  • the ternary azeotrope composition“C” is recycled back to one of the initial distillation columns and the composition at the bottom of the distillation tower contains substantially pure R-l234yf.
  • the composition collected at the bottom of the distillation after the separation of ternary azeotrope composition“C” is sent for final distillation to get R-l234yf of purity more than 99%.
  • the feed after sequential treatment through adsorption tower, absorption tower and semipermeable membrane gets distilled out as a binary azeotrope composition“D” essentially containing R-l234yf and R-134.
  • the binary azeotrope composition“D” essentially contains R-l234yf and R-134.
  • the binary azeotrope composition“D” may contain less than about 5 mole % of other components.
  • the binary azeotrope composition“D” comprises about 5 mole % to about 15 mole % of R- 134 and about 85 mole % to about 95 mole % of l234yf.
  • the binary azeotrope composition“D” comprises about 5 mole % to about 20 mole % of R- 134 and about 80 mole % to about 95 mole % of l234yf.
  • the binary azeotrope is recycled back to the initial distillation columns.
  • the process is as depicted in Figure 4.
  • the feed‘170’ is fed to a series of absorption tower, adsorption towers or semipermeable membranes‘180’ to recover ‘190’, comprising ofR-l34, R-l225zc, R-l234yf, R-l34a and OFCB and high boiling fractions.
  • the stream of ‘190’ is fed to a distillation column to recover the ternary azeotrope composition‘220’ comprising R-l234yf, R-l34a and R-134 or R-l234yf and R-134, and‘230’ comprising substantially of l234yf.‘220’ is fed to the distillation column‘180’ and‘230’ comprising substantially of l234yf is recovered or optionally distilled.
  • the present invention provides a process for separating chlorinated hydrocarbon from a composition comprising at least one fluoroolefinic compound by contacting the feed with a semipermeable membrane.
  • the present invention provides a process for separating chlorinated hydrocarbon from a composition comprising at least one R- l234yf and/or R-l234ze/R-l225zc/R-l233zd/R-l243zf by contacting the feed with a semipermeable membrane.
  • the present invention provides a process for separating chloromethane from a composition comprising at least one R-l234yf and/or R-l234ze by contacting the feed with a semipermeable membrane.
  • the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane.
  • the present invention provides a process for separating chloromethane through semipermeable membrane, further recovering chloromethane and reusing recovered chloromethane for preparation of R- l234yf.
  • the present invention provides a continuous process for separating, recovering and reusing chloromethane comprising the step of contacting a feed containing at least one R-l234yf and/or R-l234ze with a semipermeable membrane.
  • the present invention provides a process for separating chloromethane (R-40) from a feed comprising R-l234yf, vinyledenefluoride, R-l24a, HFP, OFCB, R-22, R-1122, R-236ca, R-226cb, R-32, TFE, trans R-l225ye, cis R-l225ye, R-l243zf, R-l234ze and R-40 by contacting the feed with a semipermeable membrane.
  • fourth aspect of the present invention provides a process for separating chlorocarbon from a feed comprising at least one fluoroolefinic and chlorocarbon by contacting the feed with a semipermeable membrane to obtain a retantate substantially free of the chlorocarbon.
  • the present invention provides a process for separating chlorinated hydrocarbon from a feed comprising at least one fluoroolefinic compound by contacting the feed with a semipermeable membrane to obtain a retantate substantially free of the chlorocarbon.
  • the present invention provides a process for separating chlorinated hydrocarbon from a feed comprising at least one R-l234yf and/or R-l234ze/R-l225zc/R-l233zd/R-l243zf by contacting the said composition with a semipermeable membrane to obtain a retantate substantially free of the chlorocarbon.
  • the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane to obtain a retantate substantially free of the chlorocarbon.
  • the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane to obtain a retantate having not more than 10% of chlorocarbon compared to the feed.
  • the present invention provides a process for separating chloromethane from a composition comprising R- 1234yf by contacting the feed with a semipermeable membrane to obtain a retantate having not more than 5% of chloromethane compared to the feed.
  • the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane to obtain a retantate having not more than 2% of chlorocarbon compared to the feed.
  • the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane to obtain a retantate having not more than 0.5%, of chloromethane compared to the feed.
  • the present invention provides a process for separating chloromethane (R-40) from a feed comprising R-l234yf, VdF, R-l24a, HFP, OFCB, R-22, R-1122, R-236ca, R-226cb, R-32, TFE, trans R-l225ye, cis R- l225ye, R-l243zf, R-l234ze and R-40 by contacting the feed with a semipermeable membrane to obtain a retantate substantially free of R-40.
  • the present invention provides a process of using the retantate for preparing single fluoroolefinic compound.
  • the present invention provides a process of using the retantate for preparing Rl234yf.
  • the“mixture 1” comprises l234yf, unreacted tetrafluoroethylene, chloromethane, chlorodifluoromethane and carbon monoxide.
  • the“mixture 2” comprises l234yf, unreacted tetrafluoroethylene, chloromethane, and chlorodifluoromethane.
  • the“mixture 3” comprises unreacted tetrafluoroethylene, chloromethane, and chlorodifluoromethane.
  • the“mixture 4” comprises l234yf.
  • the mixture 2 is substantially free from carbon monoxide.
  • the mixture 3 comprising unreacted tetrafluoroethylene, chloromethane, and chlorodifluoromethane is recycled back to the pyrolysis reactor.
  • the mixture 4 is passed through three successive distillation columns to obtain pure l234yf.
  • the distillation od performed as illustrated in figure 5.
  • Chlorodifluoromethane is charged to the reactor maintained at a temperature of about 700°C to about 800°C.
  • the stream of gases mainly comprising tetrafluoroethylene, along with R-40 and an initiator is fed to another reactor“1” maintained at a temperature of about 500°C to about 750°C.
  • quencher heat quencher
  • alkali scrubber sulfuric acid and alumina
  • feed“2” comprising carbon monoxide, tetrafluoroethylene, HFP, OFCB, R-l225zc, R-l34a, R- 134, R-22, CTFE, R-236ca, R-236ca, R-1122, heavies and is fed to the distillation column‘3’.
  • ‘4’ comprising carbon monoxide is vented out from the distillation column and heavier boiling fraction“5” comprising mixture 2 is fed to another column “6” to distill and recycle“7” comprising tetrafluoroethylene, the heavies “8” comprising l234yf are passed through successive distillation columns to obtain l234yf of high purity.
  • EXAMPLE 1 Process for purifying l234yf through formation of ternary azeotrope composition“A” and binary azeotrope composition“B”
  • Tetrafluoroethene and chloromethane was reacted in the presence of initiator at a temperature range of 500-750°C.
  • Low boiling fractions were removed from the resulting reactor outlet stream.
  • the reactor outlet feed after removal of low boiling fraction and heavies have the following composition was transferred into distillation column.
  • Table 1 shows the composition of the feed sent to the distillation column.
  • Table 2 shows the composition of the different fractions in the distillation column 1.
  • a ternary azeotropic or azeotrope-like composition comprising R-1234yf: 52.5 mol%; R-134a: 17.5 mol% and R-40: 27.2 mol% is sent to the absorption, adsorption tower, semipermeable membrane and the next distillation tower.
  • Table 3 shows the composition of the different fractions in the distillation column 2.
  • top composition is sent back to the distillation column 1 and bottom composition contains R-l234yf of more than 99% purity.
  • EXAMPLE 2 Process for purifying l234yf through formation of top composition using R-22
  • Tetrafluoroethene and chloromethane was reacted in the presence of initiator at a temperature range of 500-750°C. Low boiling fractions were removed from the resulting reactor outlet stream.
  • the reactor outlet feed have the following composition was transferred into distillation column.
  • the reactor outlet stream comprising 10 to 15 % R-22 is transferred into a distillation column. Presence of R-22 improves separation of R-l234yf from R-l225zc and R-134 by increasing the relative volatility as R-l234yf , R40 and R-l34a comes along with R-22 without close boiling compounds like R-l225zc, R-134 etc.
  • EXAMPLE 3 Process for purifying l234yf through formation of ternary azeotrope composition“C” and binary composition“D”
  • Tetrafluoroethene and chloromethane was reacted in the presence of intiator at a temperature range of 500-750°C.
  • Low boiling fractions were removed from the resulting reactor outlet stream.
  • the reactor outlet stream after removal of low boiling fraction and heavies have the following composition was transferred into distillation column.
  • Distillation step 1 Example 3a: The reactor outlet composition after removal of low boiling components is passed through a series of absorption column followed by adsorption column. The product stream is then passed through a distillation column from where R-l34a, R- l234yf and R-134 is recovered from the top and bottom containing majority of R- l234yf is transferred to another distillation column from where pure R-l234yf is recovered.
  • composition at the top of the second column from where R-l34a, R-l234yf and R-134 is removed was R-l34a : 4.0; R-l234yf : 83 % and R-134 : 13 %
  • Example 3b The product stream is then passed through a distillation column from where R-l234yf and R-134 is recovered from the top and bottom containing majority of R-l234yf is transferred to another distillation column from where pure R-l234yf is recovered.
  • a binary azeotrope of R-134 and R-l234yf is formed having a composition of 80-98 % 2,3,3,3-tetrafluoropropene and 2-20 % 1 , 1 ,2,2-tetrafluoroethane
  • the top composition is sent back to the distillation column 1 and bottom composition is distilled at a pressure of atmospheric to 15 bar to get R-l234yf of more than 99% purity.
  • Comparative example 5a Tetrafluoroethene and chloromethane was reacted in the presence of carbon monoxide at a reaction temperature of 650°C - 700°C.
  • Table 8 shows the composition of the furnace (reactor) inlet and outlet data when the pyrolysis is carried out in presence of carbon monoxide.
  • Comparative example 5b Tetrafluoroethene and chloromethane was reacted in the presence of carbon monoxide at a reaction temperature of 650°C - 700°C.
  • Table 2 also shows the composition of the furnace (reactor) inlet and outlet data when the pyrolysis is carried out in presence of carbon monoxide.
  • the comparative examples clearly indicate that when pyrolysis is carried out in presence of carbon monoxide, the formation of 2, 3, 3, 3 tetrafluoropropene is less than 5 %, conversion of TFE is less than 85 % and selectivity towards 2, 3,3,3- tetrafluoropropene is below 35 %.
  • Example 5c Tetrafluoroethene and chloromethane was reacted in the absence of carbon monoxide at a reaction temperature of 650°C - 700°C.
  • Table 10 shows the composition of the furnace (reactor) inlet and outlet data when the pyrolysis is carried out in absence of carbon monoxide.
  • Example 5d Tetrafluoroethene and chloromethane was reacted in the absence of carbon monoxide at a reaction temperature of 650°C - 700°C.
  • Table 11 shows the composition of the furnace (reactor) inlet and outlet data when the pyrolysis is carried out in absence of carbon monoxide.

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Abstract

The present invention relates to a process for purifying olefin feed comprising R-5 1234yf, R-40, R-134a, R-134, R-1225zc, and OFCB, comprising the step of separating different ternary and binary azeotrope compositions comprising 1234yf. The olefin feed is obtained from the pyrolysis of tetrafluoroethylene/ chlorodifluoromethane with chloromethane/methane, optionally in presence of initiator.

Description

PROCESS FOR PURIFICATION OF OLEFIN FEED COMPRISING 1234YF
FIELD OF THE INVENTION
The present invention relates to a process for purifying olefin feed comprising R- l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB.
BACKGROUND OF THE INVENTION
Refrigerant is the substance which is used as working fluid in a thermodynamic cycle, undergoes a phase change from liquid to vapour and produces cooling. These are used in refrigeration, air conditioning, and heat pumping systems. They absorb heat from one area, such as an air conditioned space, and reject it into another, such as outdoors, usually through evaporation and condensation, respectively. These phase changes occur both in absorption and mechanical vapour compression refrigeration systems, but they do not occur in systems operating on a gas cycle using a fluid such as air. Fluorocarbon based fluids have found widespread use in industry in a number of applications, including as refrigerants, aerosol propellants, blowing agents, heat transfer media, and gaseous dielectrics. Tetrafluoropropenes, having zero ozone depletion and low global warming potential, have been identified as favorable refrigerant over other refrigerants. One tetrafluoropropene having valuable properties is 2,3,3,3-tetrafluoropropene (R-l234yf).
However, the production of these and other organofluorine compounds often require substantial separation steps to isolate the compounds from other components present in the reaction product, including unreacted feedstock, undesirable byproducts, and coproducts.
Production of organofluorine compounds often results in the formation of other organofluorine compounds, organochlorines, and chlorofluorocarbons (collectively referred to herein as ‘coproducts of organofluorine production’ or simply ‘coproducts’), as both intermediate products and coproducts that appear in the final reaction mixture.
In prior art several methods have been disclosed for preparing R-l234yf, wherein by products have been removed by using several techniques such as distillation, azeotropic distillation, adsorption, absorption, membrane separation and a like or combination thereof to achieve high yield.
U.S. Pat. No. 2,931,840 describes a reaction involving the pyrolysis of chloromethane with tetrafluoroethylene, or alternatively chloromethane with chlorodifluorome thane. It is very difficult to remove unreacted chloromethane and other side products from the reaction product stream. It does not mention the process for removing unreacted chloromethane and the side products from the reaction mixture.
U.S. Pat. No. 9,302,964 discloses a method for producing 2,3,3,3-tetrafluoropropene, the method comprising contacting an azeotropic composition or azeotrope-like composition of 2,3,3,3-tetrafluoropropene and chloromethane with an extraction solvent to obtain 2,3,3,3-tetrafluoropropene containing substantially no chloromethane.
PCT publication no. 2017/108519 discloses a process forpurifying 2,3,3,3-tetrafluoro- l-propene (R-l234yf) from a first composition comprising 2,3,3,3-tetrafluoro-l- propene, 3,3,3-trifluoropropene (R-l243zf), trans-l, 3,3,3-tetrafluoro-l-propene (R- l234ze-E) and optionally or not at least one compound selected from the group consisting of chloromethane (R-40), l,l-difluoroethane (R-l52a), chloropentafluoroethane (R-115), 1 , 1 , 1 ,2-tetrafluoroethane (R-l34a), trans-l, 2, 3,3,3- pentafluoropropene (R-l225ye-E); wherein the said process involves solvent extraction and extractive distillation methods.
PCT publication no. 2017/108522 discloses a process for purifying 2, 3,3,3-tetrafluoro- l-propene (R-l234yf) from a first composition comprising 2, 3,3,3-tetrafluoro-l- propene and chloromethane (R-40); wherein the said process involves solvent extraction and extractive distillation methods. PCT publication no. 2017/108524 discloses a process for purifying 2,3,3, 3-tetrafluoro- l-propene (R-l234yf) from a first composition comprising 2,3,3,3-tetrafluoro-l- propene, l,l,l,2,2-pentafluoropropane (R-245cb) and trans-l,3,3,3-tetrafluoro-l- propene (R-l234ze-E); wherein the said process involves solvent extraction and extractive distillation methods.
Compounds having close boiling point to 2,3,3,3-tetrafluoropropene are 1, 1, 1,2- tetrafluoroethane (R-l34a), l, l,3,3,3-pentafluoropropene (l225zc), 1, 1,2,2- tetrafluoroethane (R-134), chlorotrifluoroethene (CTFE) and chloromethane (R-40). Separation of these compounds by normal distillation is very difficult.
There is therefore a need to develop a process for purifying olefin feed by removing compounds having close boiling point to 2,3,3,3-tetrafluoropropene by mean of binary or ternary azeotrope or azeotrope like formation.
SUMMARY OF THE INVENTION
A first aspect of the present invention provides a process for purification of R- l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprises a step of separating a ternary azeotrope composition“A” comprising R-l234yf, R-40 and R-l34a.
An important embodiment of the first aspect of the present invention provides a process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, the process comprising the steps of:
a) passing the feed to a distillation column to separate top composition of ternary azeotrope containing R-l234yf, R-40 and R-l34a;
b) optionally passing the ternary azeotrope composition“A” comprising R- l234yf, R-40 and R-l34a through any one or more selected from an absorption tower, an adsorption tower and a semipermeable membrane; c) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“B” comprising R-l234yf and R-l34a and bottom composition comprising substantially pure R-l234yf.
Another embodiment of present invention provides a process for purification of R- l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprises a step of separating a binary azeotrope composition“B” comprising of 10 mole % to 35 mole % of R-l34a and 60 mole % to 90 mole % of l234yf.
A second aspect of the present invention provides a process for purification of R- l234yf feed comprising R-22, R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprising the steps of separating a top composition comprising R-22, OFCB, R- l234yf, R-40 and R-l34a.
An embodiment of second aspect of the present invention provides a process for purification of R-l234yf feed comprising R-22, R-l234yf, R-40, R-l34a, R-134, R- l225zc, and OFCB, the process comprising the steps of:
a) passing the feed to a distillation column to separate top composition comprising R-22, OFCB, R-l234yf, R-40 and R-l34a;
b) passing the top composition comprising R-22, OFCB, R-l234yf, R-40 and R-l34a through any one of more selected from an absorption tower, adsorption tower and semipermeable membrane;
c) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“B” comprising R-l234yf and R-l34a and bottom composition comprising pure R-l234yf.
A third aspect of the present invention provides a process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, the process comprising the steps of:
a) passing the feed through any one or more selected from an absorption tower, adsorption tower and semipermeable membrane; b) passing the composition obtained from step b) to another distillation column to separate top composition of ternary azeotrope composition“C” comprising R-l234yf, R-134, and R-l34a and a bottom composition comprising substantially pure R-l234yf;
c) recycling the top composition of ternary azeotrope composition“C”.
An embodiment of third aspect of the present invention, provides a process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, the process comprising the steps of:
a) passing the feed through any one or more selected from an absorption tower, adsorption tower and semipermeable membrane;
b) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“D” comprising R-l234yf and R-134 and a bottom composition comprising substantially pure R-l234yf;
c) recycling the top composition of binary azeotrope composition“D”.
An embodiment of third aspect of the present invention, provides a process for purification of R-l234yf feed comprising R-l234yf, R-134, the process comprising the steps of:
a) passing the feed through any one or more selected from an absorption tower, adsorption tower and semipermeable membrane;
b) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“D” comprising R-l234yf and R-134 and a bottom composition comprising substantially pure R-l234yf;
c) recycling the top composition of binary azeotrope composition“D”.
A fourth aspect of the present invention provides a process for separating chlorocarbon from a feed comprising at least one fluoroolefinic and chlorocarbon by contacting the feed with a semipermeable membrane to obtain the feed substantially free of the chlorocarbon.
A fifth aspect of the present invention provides a process for preparing l234yf, the process comprising the steps of:
a) combining chlorodifluoromethane/tetrafluoroethylene and chloromethane/methane at a temperature to establish pyrolysis reaction to obtain a mixture 1 ;
b) distilling the mixture 1 to vent out carbon monoxide to obtain mixture 2; c) distilling mixture 2 to vent out mixture 3 and obtain mixture 4;
d) recycling the mixture 3;
e) distilling mixture 4 to obtain l234yf.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1 illustrates the process for preparation of feed.
Figure 2 illustrates first aspect of the present invention.
Figure 3 illustrates second aspect of the present invention.
Figure 4 illustrates third aspect of the present invention.
Figure 5 illustrates fourth aspect of the present invention. DETAILED DESCRIPTION
As used herein, the term‘azeotrope or azeotrope like’ is intended in its broad sense to include both compositions that are strictly azeotropic and compositions that behave like azeotropic mixtures. An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the stated pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant boiling and cannot be separated during a phase change. As used herein, the term‘heavies’ refers to a mixture comprising mainly of high boiling components having boiling points greater than R40 such as octafluorocyclobutane (OFCB), tetrafluorochloroethane, tetrafluoroethane, R-l224zc (3-chloro-l,l,3,3-tetrafluoropropene), R-l 112 (2,2-dichloro-l,l-difluororoethene), R-236ca (l, l,2,2,3,3-Hexafluoropropane), R-236ea (l,l,l,2,3,3-Hexafluoropropane), R-l 122 (2-chloro-l,l-difluoroethene), R-227ca (l,l,l,2,2,3,3-Heptafluoropropane), R-227ea (l,l,l,2,3,3,3-Heptafluoropropane), R-124 (2-chloro- 1 , 1 , 1 ,2- tetrafluoroethane) which are recycled back to the reactor may be sent to incinerator. As used herein, the term‘lights’ refers to component having boiling points lower than Rl234yf such as R22 which are recycled back to the reactor.
As used herein, the term ‘feed’ used in the present invention refers to crude composition obtained by the reaction of tetrafluoroethylene/ chlorodifluoromethane with chloromethane/methane, optionally in presence of initiator or catalyst known in the art.
As used herein, feed contains components selected from VdF (Vinylidenefluoride), tetrafluoroethene (TFE), R-32 (Difluoromethane), R-40 (chlorome thane), R-l234yf (2,3,3,3-tetrafluoropropene), HFP (Hexafluoropropene), OFCB
(octafluorocyclobutane), R-l225zc (l,l,3,3,3-pentafluoropropene), R-l34a (1, 1,1,2- tetrafluoroethane), R-l 34 (l,l,2,2-tetrafluoroethane), R-22 (Chlorodifluoromethane), CTFE (chlorotrifluoroethene), and heavies.
The feed can also be obtained by following the process disclosed in PCT publication PCT/IN2017/050006 and/or PCT publication PCT/IN2017/050555 filed by the same applicant.
The term “fluoroolefinic compounds” used in the present invention refers to unsaturated organofluorine compound. Examples of unsaturated organofluorine compounds includes R-l234yf, R-l234ze, R-l243zf, R-l233zd, R-l233xf, R-l225zc and mixtures thereof.
The term “chlorocarbon” used in the present invention refers to chlorinated hydrocarbons and chlorofluorocarbons (CFCs). Examples of CFCs includes CFC-l l (CClsF), CFC-12 (CCI2F2), HCFC-21 (CHCI2F), HCFC-22 (R22; CHCIF2), HCFC-23 (CHF3). Examples of chlorinated hydrocarbons includes chloromethane, methylene chloride, and carbon tetrachloride.
The selective permeability of a membrane is characterized by a separation factor a, which is a measure of the preferential permeability of one compound or type of compound over another compound or type of compound. The separation factor is the ratio of the relative amount of a compound that permeates through the membrane to the relative amount of another compound that permeates the membrane.
The separation factor
a = [ A ] permeate / [ B ] permeate [ A ] retantate / [ B ] retentate
The permeability is function of temperature, pressure and time.
The operable temperature ranges from 0°C to 50°C. The operable pressure ranges from 1 bar to 10 bars
The term“permeate” refers to the component of the feed that permeates through semipermeable membrane.
The term“retantate” refers to the component of the feed that does not permeates through semipermeable membrane.
The term“substantially free” used in the present invention refers to a composition that is 80% free of chlorocarbon compared to the feed.
The term“anhydrous” used in the present invention refers to water content of less than 50 ppm
In an embodiment of the present invention, the feed is a non- azeotrope mixture obtained by passing the products obtained by the reaction of tetrafluoroethylene/ chlorodifluoromethane and chloromethane/methane, through successive distillation columns.
In an embodiment of the present invention, the feed is a non-azeotrope mixture obtained by passing the product obtained by the reaction of tetrafluoroethylene/ chlorodifluoromethane and chloromethane/methane, through three successive distillation columns, heat quencher, alkali scrubber, and/or sulfuric acid to remove moisture and/or alumina to remove moisture/acid to obtain a stream of gases free from moisture and acid.
In another embodiment of the present invention, the feed is obtained from the process illustrated in Figure 1.‘10’ of Figure 1 represent chlorodifluoromethane being charged to the reactor‘20’ maintained at a temperature of about 700°C to about 800°C using an electric heater or steam. The stream of gases ‘30’ mainly comprising tetrafluoroethene, along with‘40’ comprising of R-40 and an initiator such as carbon tetrachloride/hexachloroethane/trichloroacetylchloride/chloroform is fed to another reactor‘50’ maintained at a temperature of about 500°C to about 800°C using electrical heater or fired furnace. The stream‘60’ recovered from‘50’ is passed through quencher (heat quencher), alkali scrubber, sulfuric acid and alumina to obtain a stream of gases free of acid and moisture is fed to the distillation column‘70’.‘80’, the lower boiling fractions recovered from‘70’ are fed back to the reactor‘50’, and the higher boiling fractions‘90’ comprising R-40, R-l234yf, HFP, OFCB, R-l225zc, R-l34a, R-134, R-22, CTFE, and heavies are fed to the next distillation column‘100’.
‘110’, low boiling fraction comprising R-22 is fed to the reactor‘20’.‘120’, the high boiling fraction comprising R-40, R-l234yf, OFCB, R-l225zc, R-l34a, R-134, and heavies is fed to the next distillation column‘130’.‘140’, the lower boiling fraction comprising R-l234yf, R-l225zc, R-l34a, R-134, R-40, and OFCB is passed through absorption tower ‘160’ to obtain feed ‘170’. ‘150’, the higher boiling fractions comprising heavies is recycled back to the reactor‘50’.
In another embodiment, the feed“170” may additionally contain R-22.
In another embodiment of the present invention, the feed is a non-azeotrope mixture obtained from the distillation column maintained at a temperature range of -29°C to - 23°C at an atmospheric pressure.
In another embodiment of the present invention, the reaction of tetrafluoroethylene/chlorodifluoromethane with chloromethane/methane can be done in a batch reactor or semi-batch reactor or continuous reactor. In a preferred embodiment of the present invention, the process of purification is performed in a continuous reactor.
In an embodiment of first and third aspects of the present invention, the feed comprises non-azeotrope mixture comprises of R-l234yf, R-40, R-l34a, R-l225zc, R-134, and OFCB.
In an embodiment of first and third aspects of the present invention, the feed may contain heavies.
In an embodiment of first and third aspects of the present invention, the feed comprises non-azeotrope mixture comprises of about 20 mole% to about 35 mole % of R-l234yf, about 5 mole % to about 15 mole % of R-40, of about 0.5 mole % to about 20 mole % of R-l34a, about 1 mole % to about 4 mole % of R-l225zc, about 1 mole % to about
4 mole % of R- 134, about 20 mole % to about 45 mole % of OFCB and about 5 mole % to about 10 mole % of heavies and lights.
In an embodiment of the second aspect of the present invention, the feed comprises non-azeotrope mixture comprises of R-22, R-l234yf, R-40, R-l34a, R-l225zc, R-134, OFCB and heavies.
In another embodiment of the second aspect of the present invention, R-22 may be added to the feed additionally before feeding it to the distillation column.
In another embodiment of the second aspect of the present invention, the feed may contain heavies.
In another embodiment of the second aspect of the present invention, the feed comprises non-azeotrope mixture comprises of about 5 mole % to about 25 mole % of R-22, of about 15 mole% to about 35 mole % of R-l234yf, about 20 mole % to about 45 mole % of R-40, of about 0.5 mole % to about 10 mole % of R-l34a, about 0.1 mole % to about 10 mole % of R-l225zc, about 0.1 mole % to about 10 mole % of R- 134, about 5 mole % to about 45 mole % of OFCB and about 3 mole % to about
5 mole % of heavies. As used herein, the term absorption tower refers to the tower containing adsorption solvent selected from an alcohol, nitrile, chlorinated hydrocarbon, amides, ethers or esters.
In an embodiment of the present invention the absorption tower contains a solvent selected from a group consisting of dichlorome thane, chloromethane, carbon tetrachloride, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, dimethylformamide, or the like.
In a preferred embodiment of the present invention the absorption tower contains chloroform or methanol.
In another embodiment of the present invention the adsorption tower contains molecular sieves having mean pore diameter of the size ranging from 3 A to 12Ά.
In another embodiment of the present invention the adsorption tower contains molecular sieves having mean pore diameter of the size ranging from 3 A to 5 A.
As used herein, the term semipermeable membrane refers to polymeric membrane that allows selective permeability of one compound over the other in the feed. Examples of polymeric membrane include polyethene, polypropylene, polyester, polyamide, nylon, nitrile rubber, neoprene, polydimethylsiloxane (silicone rubber), chlorosulfonated polyethylene, polysilicone-carbonate copolymers, fluoroelastomer, polyvinylchloride, plasticized polyvinylchloride, polyurethane, cis-polybutadiene, cis-polyisoprene, poly(butene-l), polystyrene-butadiene copolymers, styrene/butadiene/styrene block copolymers, styrene/ethylene/butylene block copolymers, thermoplastic polyolefin elastomers, and block copolymers of polyethers and polyesters.
In another embodiment of the present invention, the semipermeable membrane includes polyethene or polypropylene.
As used herein, the ternary azeotrope composition“A” essentially contains R-l234yf, R-l34a and R-40. The ternary azeotrope composition“A” may contain less than about 5 mole % of other components selected from the group consisting of R- 134, R-22, R- l225zc and OFCB.
In an embodiment of the first aspect of the present invention, the ternary azeotrope composition“A” comprises about 52 mole % to about 62 mole % of R-l234yf, about 25 mole % to about 34 mole % of R-40 and about 2 mole % to about 25 mole % of R- l34a.
In an embodiment of the first aspect of the present invention, the ternary azeotrope composition“A” comprises about 51.5 mole % of R-l234yf, about 30 mole % of R- 40 and about 16 mole % of R-l34a.
In an embodiment of the first aspect of the present invention, the ternary azeotrope composition“A” comprises about 51 mole % of R-l234yf, about 30 mole % of R-40 and about 15 mole % of R-l34a.
In an embodiment of the first aspect of the present invention, the ternary azeotrope composition“A” comprises about 52.5 mole % of R-l234yf, about 27.2 mole % of R- 40 and about 17.5 mole % of R-l34a.
In another embodiment of the first aspect of the present invention, R-l34a may be added to the distillation column to obtain the ternary azeotrope composition.
In another embodiment of the first aspect of the present invention, R-l34a may be recovered through pressure swing distillation.
In an embodiment of the first aspect of the present invention, the mixture collected at the bottom of the distillation column after the separation of ternary composition, is recycled back to one of the initial distillation columns.
As used herein, the binary azeotrope composition“B” essentially contains R-l234yf and R-l34a. The binary azeotrope composition“B” may contain less than about 5 mole % of other components selected from a group consisting of R-134, OFCB, R-l225zc and R-22. In an embodiment of the present invention, the binary azeotrope composition“B” contains about 10 mole % to about 35 mole % of R-l34a and about 60 mole % to about 90 mole % of l234yf.
In another embodiment of the present invention, the binary azeotrope composition“B” is recycled back to the initial distillation columns.
In another embodiment of the first aspect of the present invention, the process is as depicted in Figure 2. As referred in Figure 2, the feed‘170’ is fed to the distillation column‘180’ to recover R-22, which is fed back to the reactor, a low boiling fraction comprising a ternary azeotrope‘190’ and a high boiling fraction‘200’. The ternary composition is fed to series of absorption tower, adsorption tower and semipermeable membranes‘210’. The stream obtained through‘210’ is fed to another distillation column‘220’ to recover binary azeotrope composition‘230’, which is fed back to the distillation column‘180’ and‘240’ comprising substantially of l234yf is recovered or optionally distilled.
In one embodiment of the second aspect of the present invention, the top composition comprises about 0.2 mole % to about 10 mole % of OFCB, about 1 mole % to about 10 mole % of R-l34a, about 35 mole % to about 55 mole % of R-l234yf, about 12 mole % to about 40 mole % of R-22 and about 10 mole % to about 40 mole % of R- 40.
In an embodiment of the second aspect of the present invention, the R-22 may be added to the feed before passing to the distillation column.
In another embodiment of the second aspect of the present invention, the top composition has less than 500 ppm of R-l225zc and R-134.
In another embodiment of the second aspect of the present invention, R-l225zc and R-134 are completely not detectable in the top composition.
It has been observed by the present inventors that R-22 improves separation of R- l234yf from R-l225zc and R-134 by increasing the relative volatility of R-l234yf. Thus enabling l234yf, R-40 and R-l34a to boil along with R-22 without the close boiling components such as R-l225zc and R-134.
In the presence of R-22, ternary azeotrope of R-l234yf, R40 and R-l34a comes along with binary azeotrope of OFCB and R40 which leads to the suppression of close boiling components like R-l225zc and R-134.
In another embodiment of the second aspect of the present invention, the process is as depicted in Figure 3. As referred in Figure 3, the feed“170” is fed to the distillation column“180” to recover a low boiling fraction“190”, comprising R-22, R-l234yf, R- 40, R-l34a and OFCB and a high boiling fraction“200”. The low boiling composition is fed to series of absorption tower, adsorption tower and semipermeable membranes “210”. The stream obtained through“210” is fed to another distillation column“220” to recover R-22, the binary azeotrope composition“230” and“240” a high boiling fraction at the bottom of the column. The recovered R-22 is either sent back to the reactor“20” or to the distillation column“180”.“240” is fed to the distillation column “250” to get a binary azeotrope composition“260” that is fed back to the distillation column“180” and“270” comprising substantially of l234yf is recovered or optionally distilled.
In another embodiment of second aspect of the present invention, the mixture collected at the bottom of the distillation column after the separation of top composition, is recycled back to one of the initial distillation columns.
As used herein, the ternary azeotrope composition“C” of the third aspect of the present invention essentially contains R-l234yf, R-l34a and R-134. The ternary azeotrope composition of the third aspect of the present invention may contain less than about 5 mole % of other components selected from a group consisting of OFCB and l225zc. In another embodiment of the third aspect of the present invention, R-134 is added to the distillation column to obtain the ternary azeotrope composition“C”.
In another embodiment of the third aspect of the present invention, the ternary azeotrope composition“C” comprises of about 70 mole % to about 85 mole % of R- l234yf, about 5 mole % to about 15 mole % of R- 134 and about 2 mole % to about 20 mole % of R- 134a.
In another embodiment of the third aspect of the present invention, the ternary azeotrope composition“C”, is recycled back to one of the initial distillation columns and the composition at the bottom of the distillation tower contains substantially pure R-l234yf.
In another embodiment of the third aspect of the present invention, the composition collected at the bottom of the distillation after the separation of ternary azeotrope composition“C” is sent for final distillation to get R-l234yf of purity more than 99%. In another embodiment of the third aspect of the present invention, the feed after sequential treatment through adsorption tower, absorption tower and semipermeable membrane, gets distilled out as a binary azeotrope composition“D” essentially containing R-l234yf and R-134.
As used herein, the binary azeotrope composition“D” essentially contains R-l234yf and R-134. The binary azeotrope composition“D” may contain less than about 5 mole % of other components.
In an embodiment of the present invention, the binary azeotrope composition“D” comprises about 5 mole % to about 15 mole % of R- 134 and about 85 mole % to about 95 mole % of l234yf.
In an embodiment of the present invention, the binary azeotrope composition“D” comprises about 5 mole % to about 20 mole % of R- 134 and about 80 mole % to about 95 mole % of l234yf.
In another embodiment of the present invention, the binary azeotrope is recycled back to the initial distillation columns.
In another embodiment of the third aspect of the present invention, the process is as depicted in Figure 4. As referred in Figure 4, the feed‘170’ is fed to a series of absorption tower, adsorption towers or semipermeable membranes‘180’ to recover ‘190’, comprising ofR-l34, R-l225zc, R-l234yf, R-l34a and OFCB and high boiling fractions. The stream of ‘190’ is fed to a distillation column to recover the ternary azeotrope composition‘220’ comprising R-l234yf, R-l34a and R-134 or R-l234yf and R-134, and‘230’ comprising substantially of l234yf.‘220’ is fed to the distillation column‘180’ and‘230’ comprising substantially of l234yf is recovered or optionally distilled.
In an embodiment of fourth aspect, the present invention provides a process for separating chlorinated hydrocarbon from a composition comprising at least one fluoroolefinic compound by contacting the feed with a semipermeable membrane.
In another embodiment of fourth aspect, the present invention provides a process for separating chlorinated hydrocarbon from a composition comprising at least one R- l234yf and/or R-l234ze/R-l225zc/R-l233zd/R-l243zf by contacting the feed with a semipermeable membrane.
In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane from a composition comprising at least one R-l234yf and/or R-l234ze by contacting the feed with a semipermeable membrane.
In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane.
In an embodiment of fourth aspect, the present invention provides a process for separating chloromethane through semipermeable membrane, further recovering chloromethane and reusing recovered chloromethane for preparation of R- l234yf.
In an embodiment of fourth aspect, the present invention provides a continuous process for separating, recovering and reusing chloromethane comprising the step of contacting a feed containing at least one R-l234yf and/or R-l234ze with a semipermeable membrane.
In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane (R-40) from a feed comprising R-l234yf, vinyledenefluoride, R-l24a, HFP, OFCB, R-22, R-1122, R-236ca, R-226cb, R-32, TFE, trans R-l225ye, cis R-l225ye, R-l243zf, R-l234ze and R-40 by contacting the feed with a semipermeable membrane.
In another embodiment of fourth aspect of the present invention provides a process for separating chlorocarbon from a feed comprising at least one fluoroolefinic and chlorocarbon by contacting the feed with a semipermeable membrane to obtain a retantate substantially free of the chlorocarbon.
In another embodiment of fourth aspect, the present invention provides a process for separating chlorinated hydrocarbon from a feed comprising at least one fluoroolefinic compound by contacting the feed with a semipermeable membrane to obtain a retantate substantially free of the chlorocarbon.
In another embodiment of fourth aspect, the present invention provides a process for separating chlorinated hydrocarbon from a feed comprising at least one R-l234yf and/or R-l234ze/R-l225zc/R-l233zd/R-l243zf by contacting the said composition with a semipermeable membrane to obtain a retantate substantially free of the chlorocarbon.
In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane to obtain a retantate substantially free of the chlorocarbon.
In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane to obtain a retantate having not more than 10% of chlorocarbon compared to the feed.
In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane from a composition comprising R- 1234yf by contacting the feed with a semipermeable membrane to obtain a retantate having not more than 5% of chloromethane compared to the feed. In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane to obtain a retantate having not more than 2% of chlorocarbon compared to the feed.
In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane from a composition comprising R-l234yf by contacting the feed with a semipermeable membrane to obtain a retantate having not more than 0.5%, of chloromethane compared to the feed.
In another embodiment of fourth aspect, the present invention provides a process for separating chloromethane (R-40) from a feed comprising R-l234yf, VdF, R-l24a, HFP, OFCB, R-22, R-1122, R-236ca, R-226cb, R-32, TFE, trans R-l225ye, cis R- l225ye, R-l243zf, R-l234ze and R-40 by contacting the feed with a semipermeable membrane to obtain a retantate substantially free of R-40.
In another embodiment of fourth aspect, the present invention provides a process of using the retantate for preparing single fluoroolefinic compound.
In another embodiment of fourth aspect, the present invention provides a process of using the retantate for preparing Rl234yf.
In an embodiment of fifth aspect of the present invention, the“mixture 1” comprises l234yf, unreacted tetrafluoroethylene, chloromethane, chlorodifluoromethane and carbon monoxide.
In another embodiment of fifth aspect of the present invention, the“mixture 2” comprises l234yf, unreacted tetrafluoroethylene, chloromethane, and chlorodifluoromethane.
In another embodiment of fifth aspect of the present invention, the“mixture 3” comprises unreacted tetrafluoroethylene, chloromethane, and chlorodifluoromethane. In another embodiment of fifth aspect of the present invention,, the“mixture 4” comprises l234yf. In another embodiment of fifth aspect of the present invention, the mixture 2 is substantially free from carbon monoxide.
In another embodiment of fifth aspect of the present invention, the mixture 3 comprising unreacted tetrafluoroethylene, chloromethane, and chlorodifluoromethane is recycled back to the pyrolysis reactor.
In another embodiment of fifth aspect of the present invention, the mixture 4 is passed through three successive distillation columns to obtain pure l234yf.
In another embodiment of fifth aspect of the present invention, the distillation od performed as illustrated in figure 5. Chlorodifluoromethane is charged to the reactor maintained at a temperature of about 700°C to about 800°C. The stream of gases mainly comprising tetrafluoroethylene, along with R-40 and an initiator is fed to another reactor“1” maintained at a temperature of about 500°C to about 750°C. The stream passed through quencher (heat quencher), alkali scrubber, sulfuric acid and alumina to obtain a stream of gases free of acid and moisture to obtain feed“2” comprising carbon monoxide, tetrafluoroethylene, HFP, OFCB, R-l225zc, R-l34a, R- 134, R-22, CTFE, R-236ca, R-236ca, R-1122, heavies and is fed to the distillation column‘3’. ‘4’, comprising carbon monoxide is vented out from the distillation column and heavier boiling fraction“5” comprising mixture 2 is fed to another column “6” to distill and recycle“7” comprising tetrafluoroethylene, the heavies “8” comprising l234yf are passed through successive distillation columns to obtain l234yf of high purity.
The present invention has been described in terms of its specific embodiments, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the present invention.
The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention. EXAMPLES
EXAMPLE 1: Process for purifying l234yf through formation of ternary azeotrope composition“A” and binary azeotrope composition“B”
Tetrafluoroethene and chloromethane was reacted in the presence of initiator at a temperature range of 500-750°C. Low boiling fractions were removed from the resulting reactor outlet stream. The reactor outlet feed after removal of low boiling fraction and heavies have the following composition was transferred into distillation column.
Distillation step 1 :
Table 1 shows the composition of the feed sent to the distillation column.
Table 1
Figure imgf000021_0001
* l34a was added to the above feed
Table 2 shows the composition of the different fractions in the distillation column 1.
Table 2
Figure imgf000021_0002
Figure imgf000022_0001
It is clear from the Table 2 that the separation of ternary azeotrope suppresses contamination like l225zc and 134.
A ternary azeotropic or azeotrope-like composition comprising R-1234yf: 52.5 mol%; R-134a: 17.5 mol% and R-40: 27.2 mol% is sent to the absorption, adsorption tower, semipermeable membrane and the next distillation tower.
Distillation step 2:
Table 3 shows the composition of the different fractions in the distillation column 2.
Table 3
Figure imgf000022_0002
The top composition is sent back to the distillation column 1 and bottom composition contains R-l234yf of more than 99% purity. EXAMPLE 2: Process for purifying l234yf through formation of top composition using R-22
Tetrafluoroethene and chloromethane was reacted in the presence of initiator at a temperature range of 500-750°C. Low boiling fractions were removed from the resulting reactor outlet stream. The reactor outlet feed have the following composition was transferred into distillation column.
The reactor outlet stream comprising 10 to 15 % R-22 is transferred into a distillation column. Presence of R-22 improves separation of R-l234yf from R-l225zc and R-134 by increasing the relative volatility as R-l234yf , R40 and R-l34a comes along with R-22 without close boiling compounds like R-l225zc, R-134 etc.
Example 2a
Distillation step 1 :
Table 4
Figure imgf000023_0001
Example 2b
Table 5
Figure imgf000024_0001
The results depicted in Tables 4 and 5 clearly indicates that impurities like R-l225zc and R-134 can be completely eliminated from the top composition. The product from the distillation column is then sent to a series of absorption, semipermeable membrane and adsorption tower. The product stream is then passed to a series of distillation column to remove R22, and the binary azeotrope containing R-l34a and R-l234yf. The top composition is sent back to the distillation column 1 and bottom composition is distilled to get R-l234yf of more than 99% purity.
EXAMPLE 3: Process for purifying l234yf through formation of ternary azeotrope composition“C” and binary composition“D”
Tetrafluoroethene and chloromethane was reacted in the presence of intiator at a temperature range of 500-750°C. Low boiling fractions were removed from the resulting reactor outlet stream. The reactor outlet stream after removal of low boiling fraction and heavies have the following composition was transferred into distillation column.
Distillation step 1 : Example 3a: The reactor outlet composition after removal of low boiling components is passed through a series of absorption column followed by adsorption column. The product stream is then passed through a distillation column from where R-l34a, R- l234yf and R-134 is recovered from the top and bottom containing majority of R- l234yf is transferred to another distillation column from where pure R-l234yf is recovered.
The composition at the top of the second column from where R-l34a, R-l234yf and R-134 is removed was R-l34a : 4.0; R-l234yf : 83 % and R-134 : 13 %
Example 3b: The product stream is then passed through a distillation column from where R-l234yf and R-134 is recovered from the top and bottom containing majority of R-l234yf is transferred to another distillation column from where pure R-l234yf is recovered. A binary azeotrope of R-134 and R-l234yf is formed having a composition of 80-98 % 2,3,3,3-tetrafluoropropene and 2-20 % 1 , 1 ,2,2-tetrafluoroethane
The top composition is sent back to the distillation column 1 and bottom composition is distilled at a pressure of atmospheric to 15 bar to get R-l234yf of more than 99% purity.
EXAMPLE 4
The experiments were performed to show that the permeation of chloromethane from the feed is a function of temperature, pressure and time. Table 1 and Table 2 shows the results of permeation of chloromethane at 25°C and a pressure of 1.1 bars. In this experiment, feed was allowed to pass through polyethene and analyzed over a period of time.
Table 6
Figure imgf000026_0001
Table 7
Figure imgf000026_0002
EXAMPLE 5
Comparative example 5a: Tetrafluoroethene and chloromethane was reacted in the presence of carbon monoxide at a reaction temperature of 650°C - 700°C.
Table 8 shows the composition of the furnace (reactor) inlet and outlet data when the pyrolysis is carried out in presence of carbon monoxide.
Table 8
Figure imgf000026_0003
Figure imgf000027_0001
Figure imgf000027_0002
Comparative example 5b: Tetrafluoroethene and chloromethane was reacted in the presence of carbon monoxide at a reaction temperature of 650°C - 700°C.
Table 2 also shows the composition of the furnace (reactor) inlet and outlet data when the pyrolysis is carried out in presence of carbon monoxide.
Table 9
Figure imgf000027_0003
Figure imgf000028_0001
Figure imgf000028_0002
The comparative examples clearly indicate that when pyrolysis is carried out in presence of carbon monoxide, the formation of 2, 3, 3, 3 tetrafluoropropene is less than 5 %, conversion of TFE is less than 85 % and selectivity towards 2, 3,3,3- tetrafluoropropene is below 35 %.
Example 5c: Tetrafluoroethene and chloromethane was reacted in the absence of carbon monoxide at a reaction temperature of 650°C - 700°C.
Table 10 shows the composition of the furnace (reactor) inlet and outlet data when the pyrolysis is carried out in absence of carbon monoxide.
Figure imgf000029_0001
Figure imgf000029_0002
Example 5d: Tetrafluoroethene and chloromethane was reacted in the absence of carbon monoxide at a reaction temperature of 650°C - 700°C.
Table 11 shows the composition of the furnace (reactor) inlet and outlet data when the pyrolysis is carried out in absence of carbon monoxide.
Figure imgf000030_0002
Figure imgf000030_0003
The experimental data obtained in examples 5c and 5d clearly indicate the advantage of CO removal on the conversion of TFE and on selectivity of 2, 3,3,3- tetrafluoropropene.
Figure imgf000030_0001

Claims

1. A process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprises a step of separating a ternary azeotrope composition“A” comprising R-l234yf, R-40 and R-l34a.
2. A process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprises a step of separating a binary azeotrope composition“B” comprising R-l234yf and R-l34a.
3. A process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB,
the process comprising the steps of:
a) passing the feed to a distillation column to separate top composition of ternary azeotrope composition“A” comprising R-l234yf, R-40 and R- l34a;
b) optionally passing the ternary azeotrope composition“A” comprising R- l234yf, R-40 and R-l34a through any one or more selected from an absorption tower, an adsorption tower and semipermeable membrane; c) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“B” comprising R-l234yf and R-l34a and bottom composition comprising substantially pure R-l234yf.
4. A process for purification of R-l234yf feed comprising R-22, R-l234yf, R-40, R- l34a, R-134, R-l225zc, and OFCB,
the process comprising the steps of:
d) passing the feed to a distillation column to separate top composition comprising R-22, OFCB, R-l234yf, R-40 and R-l34a; e) passing the top composition comprising R-22, OFCB, R-l234yf, R-40 and R-l34a through any one of more selected from an absorption tower, adsorption tower and semipermeable membrane;
f) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“B” comprising R-l234yf and R-l34a and bottom composition comprising pure R-l234yf.
5. A process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprises a step of separating a ternary azeotrope composition“C” comprising R-l234yf, R-l34a and R-134.
6. A process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB, comprises a step of separating a binary azeotrope composition“D” comprising R-l234yf and R-134.
7. A process for purification of R-l234yf feed comprising R-l234yf, R-40, R-l34a, R-134, R-l225zc, and OFCB,
the process comprising the steps of:
a) passing the feed through any one or more selected from an absorption tower, adsorption tower and semipermeable membrane;
b) passing the composition obtained from step b) to another distillation column to separate top composition of ternary azeotrope composition“C” comprising R-l234yf, R-134, and R-l34a and bottom composition comprising substantially pure R-l234yf;
c) recycling the top composition of ternary azeotrope.
8. A process for purification of R-l234yf feed comprising R-l234yf, R-40, R-134, R- l225zc, and OFCB,
the process comprising the steps of:
a) passing the feed through any one or more selected from an absorption tower, adsorption tower and semipermeable membrane;
b) passing the composition obtained from step b) to another distillation column to separate top composition of binary azeotrope composition“D” comprising R-l234yf and R-134 and bottom composition comprising substantially pure R-l234yf;
c) recycling the top composition of binary azeotrope composition.
9. The process as claimed in previous claims, wherein absorption tower contains a solvent selected from a group consisting of dichloromethane, chlorome thane, carbon tetrachloride, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, dimethylformamide, or the like
10. The process as claimed in previous claims, wherein the absorption tower contains chloroform or methanol.
11. The process as claimed in previous claims, wherein the adsorption tower contains molecular sieves having mean pore diameter of the size ranging from 3 A to 5Ά
12. A process for separating chlorinated hydrocarbon from a feed comprising l234yf and chlorinated hydrocarbon by contacting the feed with a semipermeable membrane to obtain a feed substantially free of the chlorinated hydrocarbon.
13. The process as claimed in previous claims, wherein semipermeable membrane includes polyethene or polypropylene
14. The process as claimed in claim 12, wherein the chlorinated hydrocarbons includes chloromethane, methylene chloride, and carbon tetrachloride.
15. A process for preparing l234yf, the process comprising the steps of:
a) combining tetrafluoroethylene/chlorodifluoromethane and chlorome thane/methane to obtain a mixture 1, comprising l234yf, unreacted tetrafluoroethylene, chloromethane, chlorodifluoromethane and carbon monoxide;
b) distilling the mixture 1 to vent out carbon monoxide to obtain mixture 2, comprising l234yf, unreacted tetrafluoroethylene, chloromethane, and chlorodifluoromethane ;
c) distilling mixture 2 to vent out mixture 3 comprising unreacted tetrafluoroethylene, chloromethane, and chlorodifluoromethane and obtain mixture 4 comprising l234yf;
d) recycling the mixture 3;
e) distilling mixture 4 to obtain l234yf.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111253211A (en) * 2020-03-16 2020-06-09 天津绿菱气体有限公司 Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf

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FR3137846A1 (en) * 2022-07-12 2024-01-19 Arkema France Chlorotrifluoroethylene purification process
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015053339A1 (en) * 2013-10-09 2015-04-16 旭硝子株式会社 Method for purifying 2,3,3,3-tetrafluoropropene
WO2017122222A1 (en) * 2016-01-14 2017-07-20 Srf Limited Process for the preparation of olefin containing fluorine

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2931840A (en) 1958-11-25 1960-04-05 Du Pont Process for preparing 2, 3, 3, 3-tetrafluoropropene
JP2016027005A (en) * 2012-11-22 2016-02-18 旭硝子株式会社 Production method of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethylene
WO2014103582A1 (en) 2012-12-27 2014-07-03 旭硝子株式会社 Method for purifying tetrafluoropropene
EP3590913A1 (en) * 2013-07-12 2020-01-08 Arkema Inc. Method of separating organofluorine compounds using membrane
FR3046163B1 (en) 2015-12-23 2019-12-13 Arkema France PROCESS FOR THE PRODUCTION AND PURIFICATION OF 2,3,3,3-TETRAFLUORO-1-PROPENE.
FR3046161B1 (en) 2015-12-23 2019-12-13 Arkema France PROCESS FOR THE PRODUCTION AND PURIFICATION OF 2,3,3,3-TETRAFLUORO-1-PROPENE.
FR3046165B1 (en) 2015-12-23 2019-12-13 Arkema France PROCESS FOR THE PRODUCTION AND PURIFICATION OF 2,3,3,3-TETRAFLUORO-1-PROPENE
JP6680355B2 (en) 2016-05-20 2020-04-15 アイシン・エィ・ダブリュ株式会社 Map display system and map display program
JP6995872B2 (en) * 2016-11-29 2022-01-17 エスアールエフ リミテッド Improved method for preparing 2,3,3,3-tetrafluoropropene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015053339A1 (en) * 2013-10-09 2015-04-16 旭硝子株式会社 Method for purifying 2,3,3,3-tetrafluoropropene
WO2017122222A1 (en) * 2016-01-14 2017-07-20 Srf Limited Process for the preparation of olefin containing fluorine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3793968A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111253211A (en) * 2020-03-16 2020-06-09 天津绿菱气体有限公司 Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf
CN111253211B (en) * 2020-03-16 2022-08-05 天津绿菱气体有限公司 Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf

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