WO2015050953A1 - Procédé de déshydrofluoration pour fabriquer des hydrofluorooléfines - Google Patents

Procédé de déshydrofluoration pour fabriquer des hydrofluorooléfines Download PDF

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Publication number
WO2015050953A1
WO2015050953A1 PCT/US2014/058571 US2014058571W WO2015050953A1 WO 2015050953 A1 WO2015050953 A1 WO 2015050953A1 US 2014058571 W US2014058571 W US 2014058571W WO 2015050953 A1 WO2015050953 A1 WO 2015050953A1
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solvent
aqueous solution
mixtures
basic aqueous
group
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PCT/US2014/058571
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English (en)
Inventor
Xuehui Sun
Mario Joseph Nappa
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E. I. Du Pont De Nemours And Company
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Publication of WO2015050953A1 publication Critical patent/WO2015050953A1/fr

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    • 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

Definitions

  • This disclosure relates in general to processes for the production of fluorinated olefins.
  • chlorofluorocarbons CFCs
  • HCFCs hydrochlorofluorocarbons
  • HFC hydrofluorocarbon
  • compositions that have not only low ozone depletion potentials, but also low global warming potentials. Certain hydrofluoroolefins meet both goals. Thus there is a need for manufacturing processes that provide
  • halogenated hydrocarbons and fluoroolefins that contain no chlorine and also have lower global warming potential than current commercial refrigeration products.
  • Disclosed is a process for the manufacture of hydrofluoroolefins of the structure CF 3 CH CHY, wherein Y can be Br, CI or F, through reacting at least one fluoropropane reactant of the structure CF 3 CH 2 CXYH, where X can be CI, Br or F and Y can be CI. Br or F, with a basic aqueous solution in the presence of a nonaqueous, nonalcoholic solvent.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • a process for the manufacture of hydrofluoroolefins of the structure CF 3 CH CHY, wherein Y can be Br, CI or F, comprising at least one fluoropropane reactant of the structure CF 3 CH 2 CXYH, where X can be CI, Br or F and Y can be CI.
  • Br or F with a basic aqueous solution in the presence of a nonaqueous, nonalcoholic solvent, and in the absence of a phase transfer catalyst. While they can be effective, phase transfer catalysts are expensive, contribute to waste streams, and can be difficult to separate from solvents which may need to be recycled.
  • phase transfer catalysts if other methods are available.
  • the hydrofluoroolefin produced by the disclosed embodiments are 1 ,3,3,3-tetrafluoro-1 -propene (HFC-1234ze)(E and Z isomers) and 1 -chloro-3,3,3-trifluoro-1 -propene (HCFO- 1233zd)(both E and Z isomers), each having zero or low ozone depletion potential and low global warming potential and having been identified as potential refrigerants, foam expansion agents, and or solvents.
  • the basic aqueous solution is a liquid (whether a solution, dispersion, emulsion, or suspension and the like) that is primarily an aqueous liquid having a pH of over 7. In some embodiments the basic aqueous solution has a pH of over 8. In some embodiments, the basic aqueous solution has a pH of over 10. In some embodiments, the basic aqueous solution has a pH of 10-13. In some embodiments, the basic aqueous solution contains small amounts of organic liquids which may be miscible or immiscible with water. In some embodiments, the liquid medium in the basic aqueous solution is at least 90% water. In one embodiment the water is tap water; in other embodiments the water is deionized or distilled.
  • the base in the aqueous basic solution is selected from the group consisting of hydroxide, oxide, carbonate, or phosphate salts of alkali, alkaline earth metals and mixtures thereof.
  • bases which may be used include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, or mixtures thereof.
  • the non-aqueous non-alcoholic solvent is selected from the group consisting of alkyl and aryl nitriles, alkyl and aryl ethers, amides, ketones, sulfoxides, phosphate esters and mixtures thereof.
  • Said alkyl groups may be cyclic or acyclic and straight-chain or branched alkyl groups.
  • the solvent is selected from the group consisting of acetonitrile, propionitrile, butyronitrile, methyl glutaronitrile, adiponitrile, benzonitrile, ethylene carbonate, propylene carbonate, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, anisole, 2-methyltetrahydrofuran, tetrahydrofuran, dioxane, diglyme, triglyme, tetraglyme, ⁇ , ⁇ -dimethyl formamide, ⁇ , ⁇ -dimethyl acetamide, N- methyl pyrrolidinone, sulfolane, dimethyl sulfoxide, peril uoro-N-methyl morpholine, perfluorotetrahydrofuran, trialkylamines, dialkylamines, benzene, toluene, xylene, naphthalene, methylnapt
  • the process is for the manufacture of 1 ,3,3,3- tetrafluoro-1 -propene (HFO-1234ze) by dehydrofluorination of 1 ,1 ,1 ,3,3- pentafluoropropane (HFC-245fa).
  • HFO-1234ze may exist as two configurational isomers, E, or Z.
  • HFO-1234ze as used herein refers to the isomers, E-HFO-1234ze (CAS RN 291 18-24-9) or Z-HFO-1234ze (CAS RN 291 18-25-0), as well as any combinations or mixtures of such isomers.
  • the process is for the manufacture of 1 ,3,3,3- tetrafluoro-1 -propene (HCF-1234ze) by dehydrochlorination of 1 -chloro- 1 ,3,3,3-tetrafluoropropane (HCFC-244fb).
  • the process is for the manufacture of 1 -chloro-3,3,3-trifluoro-1 -propene
  • HCFO-1233zd by dehydrofluorination of 1 -chloro-1 ,3,3,3- tetrafluoropropane (HCFC-244fb).
  • the process is for the manufacture of 1 -chloro-3,3,3-trifluoro-1 -propene (HCFO-1233zd) by dehydrochlorination of 1 ,1 -dichloro-3,3,3-trifluoropropane (HCFC- 243fa).
  • HCFO-1233zd may exist as two configurational isomers, E, or Z.
  • HCFO-1233zd refers to the isomers, E-HCFO-1233zd (CAS RN 102687-65-0) or Z-HCFO-1233zd (CAS RN 2730-43-0), as well as any combinations or mixtures of such isomers.
  • the fluoropropane is 1 ,1 ,1 ,3,3- pentafluoropropane (HFC-245fa) which can be produced by many known methods in the art.
  • HFC-245fa can be prepared by reaction of 1 ,1 ,1 ,3,3-pentachloropropane with HF in the presence of an antimony catalyst.
  • the fluoropropane is 1 -chloro-1 ,3,3,3- tetrafluoropropane (HCFC-244fa) which can be produced by many known methods in the art.
  • HCFC-244fa can be prepared by reaction of 1 ,1 ,1 ,3,3-pentachloropropane with HF in the presence of an antimony catalyst under conditions where complete fluorination to the pentafluoropropane does not occur and one chlorine remains.
  • the fluoropropane is 1 ,1 -dichloro-3,3,3- trifluoropropane (HCFC-243fa) which can be produced by many know methods in the art.
  • HCFC-243fa can be prepared by reaction of 1 ,1 ,1 ,3,3-pentachloropropane with HF in the presence of an antimony catalyst under conditions where complete fluorination to the pentafluoropropane does not occur and two chlorine substituents remain.
  • the dehydrofluorination of fluoropropane is accomplished using a basic aqueous solution in the presence of a nonaqueous, non-alcoholic solvent in which the fluoropropane is at least partially miscible.
  • the base in the basic aqueous solution includes alkali metal or alkaline earth metal hydroxides and oxides, or mixtures thereof, which can include without limitation lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium
  • the amount of base (in the basic aqueous solution) required to convert a fluoropropane to a hydrofluoroolefin is approximately the stoichiometric quantity or about 1 mole of base to one mole of
  • fluoropropane it may desirable (e.g., to increase reaction rate) to employ a ratio of base to fluoropropane of greater than one. In some embodiments, large excesses of base (in the basic aqueous solution) are to be avoided as further reaction of the desired
  • hydrofluoroolefin may occur.
  • the molar ratio of base (in the basic aqueous solution) to fluoropropane is from about 0.75:1 to about 10:1 .
  • the molar ratio of base (in the basic aqueous solution) to fluoropropane is from about 0.9:1 to about 5:1 .
  • the molar ratio of base to fluoropropane is from about 1 :1 to about 4:1 .
  • the dehydrofluorination may occur by reverse addition whereby the reactor is filled with fluoroalkane and solvent and a solution of base is added so that the stoichiometry remains less than one and the lower boiling fluoroolefin leaves the reactor so it does not further react.
  • the dehydrofluorination can occur in this manner from 10°C to about 150°C or from about 5 degrees above the freezing point of the solvent whichever is higher.
  • the dehydrofluorination is conducted within a temperature range at which the fluoropropane will dehydrofluorinate. In one embodiment, such temperatures can be from about 10 °C to about 150 °C. In another embodiment, the reaction is conducted in the range of from about 30 °C to about 1 10 °C. In yet another embodiment, the reaction is carried out in the range of from about 40 °C to about 90 °C.
  • the reaction pressure is not critical. The reaction can be conducted at atmospheric pressure, super-atmospheric pressure, or under reduced pressure. In one embodiment, the reaction is carried out at atmospheric pressure.
  • the reaction is carried out with agitation.
  • reactants are in the same phase, as in solution, thermal motion brings them into contact.
  • the reaction is limited to the interface between the reactants. Reaction can occur only at their area of contact; in the case of a liquid and a gas, at the surface of the liquid. In the case of a liquid and a solid, reaction can occur at the surface of the solid. In the case of a liquid and a liquid, at the interface of the two liquids. Vigorous shaking, agitation, and/or stirring may be needed to bring the reaction to
  • agitation depends on the desired reaction rate which is dependent on the reactor geometry, residence time, agitator and baffling design, and solubility or miscibility of the reactants.
  • a solid base e.g., KOH, NaOH, LiOH or mixtures thereof
  • a concentrated solution of a base e.g., 50% by weight aqueous potassium hydroxide
  • a solvent for the reaction can be a nitrile, ether, amide, ketone, sulfoxide, phosphate ester, or mixtures thereof.
  • the solvent is selected from the group consisting of acetonitrile, adiponitrile, 2-methyltetrahydrofuran, tetrahydrofuran, dioxane, diglyme, tetraglyme, perfluorotetrahydrofuran, and mixtures thereof.
  • the dehydrofluorination process is carried out in batch techniques and in other embodiments the
  • dehydrofluorination process can be carried out in a continuous mode of operation.
  • the above described components are combined in a suitable vessel for a time sufficient to convert at least a portion of the fluoropropane to hydrofluoroolefin and then the hydrofluoroolefin is recovered from the reaction mixture.
  • the above described components are combined in a suitable vessel for a time sufficient to convert at least a portion of the hydrochlorofluoropropane to hydrochlorofluoroolefin and then the hydrochlorofluoroolefin is recovered from the reaction mixture.
  • reaction vessel in a continuous mode of operation, is charged with the basic aqueous solution and
  • reaction vessel is fitted with a condenser cooled to a temperature sufficient to reflux the fluoropropane, but the hydrofluoro olefin is permitted to exit the reaction vessel and collect in an appropriate vessel such as cold trap.
  • the above described components are combined in a suitable vessel for a time sufficient to convert at least a portion of the fluoropropane to hydrofluoroolefin and then the hydrofluoroolefin is recovered from the reaction mixture.
  • Example 1 Dehydrofluorination of 245fa by aqueous KOH and triethylamine.
  • Example 3 Dehydrofluorination of 245fa by aqueous KOH and toluene without presence of a phase transfer catalyst
  • Example 5 Dehydrofluorination of 245fa by aqueous KOH without presence of a solvent or a phase transfer catalyst
  • Examples 1 -5 show that the desired product may be manufactured without the use of a phase transfer catalyst. Comparing Examples 1 and 6 below demonstrates that some solvents actually perform better than phase transfer catalysts.
  • ND not determined.
  • Example 7 Dehydrochlorination of 243fa by aqueous NaOH and triethylamine without presence of a phase transfer catalyst. 10 g triethylamine, 30 g 243fa and 7.2g 30% NaOH solution are added into a 250 ml three-neck round bottomed flask which is equipped with an overhead magnetic stirrer. The mixture is stirred for 2 hours and a little less than 0.1 ml of organic samples are taken and analyzed by GC-MS during the run. The expected results of analysis are listed in Table 7, which shows triethylamine greatly promotes 243fa dehydrochlorination reaction without the need of a phase transfer catalyst. Also the product does not contain any trifluoropropyne.
  • Comparative Example 8 Dehydrochlorination of 243fa by aqueous NaOH without presence of a solvent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé pour la fabrication d'hydrofluorooléfines CF3CH=CHY, où Y peut être Cl ou F, comprenant la réaction d'au moins un réactif fluoropropane représenté par la structure CF3CH2CYXH, dans laquelle X et Y peuvent chacun indépendamment représenter l'un ou l'autre de F, Cl ou Br, avec une solution aqueuse basique en présence d'un solvant non aqueux non alcoolique et en l'absence d'un catalyseur de transfert de phase.
PCT/US2014/058571 2013-10-02 2014-10-01 Procédé de déshydrofluoration pour fabriquer des hydrofluorooléfines WO2015050953A1 (fr)

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US61/885,532 2013-10-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106946647A (zh) * 2017-02-08 2017-07-14 陕西延长石油矿业有限责任公司 一种混合料常温异构化制备反式‑1,3,3,3‑四氟丙烯的方法
CN107922294A (zh) * 2015-09-11 2018-04-17 科慕埃弗西有限公司 氢氯氟烃的脱卤化氢

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050090698A1 (en) * 2003-10-27 2005-04-28 Honeywell International, Inc. Process for producing fluoropropenes
WO2008030439A2 (fr) * 2006-09-05 2008-03-13 E. I. Du Pont De Nemours And Company Procédé de déshydrofluoration pour fabriquer des hydrofluorooléfines
US20100174123A1 (en) * 2009-01-05 2010-07-08 E. I. Du Pont De Nemours And Company Preparation of hydrofluoroolefins by dehydrofluorination

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050090698A1 (en) * 2003-10-27 2005-04-28 Honeywell International, Inc. Process for producing fluoropropenes
WO2008030439A2 (fr) * 2006-09-05 2008-03-13 E. I. Du Pont De Nemours And Company Procédé de déshydrofluoration pour fabriquer des hydrofluorooléfines
US20100174123A1 (en) * 2009-01-05 2010-07-08 E. I. Du Pont De Nemours And Company Preparation of hydrofluoroolefins by dehydrofluorination

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"CRC Handbook of Chemistry and Physics", 2000

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107922294A (zh) * 2015-09-11 2018-04-17 科慕埃弗西有限公司 氢氯氟烃的脱卤化氢
JP2018526389A (ja) * 2015-09-11 2018-09-13 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー ヒドロクロロフルオロカーボンの脱ハロゲン化水素
EP3347334A4 (fr) * 2015-09-11 2019-05-01 The Chemours Company FC, LLC Déshydrohalogénation d'hydrochlorofluorocarbones
JP2021102657A (ja) * 2015-09-11 2021-07-15 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー ヒドロクロロフルオロカーボンの脱ハロゲン化水素
CN113968769A (zh) * 2015-09-11 2022-01-25 科慕埃弗西有限公司 氢氯氟烃的脱卤化氢
US11440860B2 (en) 2015-09-11 2022-09-13 The Chemours Company Fc, Llc Dehydrohalogenation of hydrochlorofluorocarbons
JP7274520B2 (ja) 2015-09-11 2023-05-16 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー ヒドロクロロフルオロカーボンの脱ハロゲン化水素
US11840492B2 (en) 2015-09-11 2023-12-12 The Chemours Company, Fc, Llc Dehydrohalogenation of hydrochlorofluorocarbons
CN106946647A (zh) * 2017-02-08 2017-07-14 陕西延长石油矿业有限责任公司 一种混合料常温异构化制备反式‑1,3,3,3‑四氟丙烯的方法
CN106946647B (zh) * 2017-02-08 2019-10-11 陕西延长石油矿业有限责任公司 一种混合料常温异构化制备反式-1,3,3,3-四氟丙烯的方法

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