CN101687737A - 通过卤代烃的催化脱卤化氢制备氟化烯烃 - Google Patents
通过卤代烃的催化脱卤化氢制备氟化烯烃 Download PDFInfo
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 22
- 238000006704 dehydrohalogenation reaction Methods 0.000 title description 8
- 230000003197 catalytic effect Effects 0.000 title description 3
- 150000008282 halocarbons Chemical class 0.000 title 1
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 28
- 150000005309 metal halides Chemical class 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 40
- 238000007033 dehydrochlorination reaction Methods 0.000 claims description 14
- 238000005660 chlorination reaction Methods 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 12
- QBTUCBKAWGUMMK-UHFFFAOYSA-N C=CC.[F] Chemical group C=CC.[F] QBTUCBKAWGUMMK-UHFFFAOYSA-N 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- PFDZQZAOZNELDX-UHFFFAOYSA-N 1-chloro-3-fluoropropane Chemical class FCCCCl PFDZQZAOZNELDX-UHFFFAOYSA-N 0.000 claims description 4
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- JODPGPKOJGDHSV-UHFFFAOYSA-N 1-chloro-1,1,2,3,3,3-hexafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)Cl JODPGPKOJGDHSV-UHFFFAOYSA-N 0.000 claims description 2
- JSECXTYNFBONSF-UHFFFAOYSA-N 3-chloro-1,1,1,2-tetrafluoropropane Chemical compound ClCC(F)C(F)(F)F JSECXTYNFBONSF-UHFFFAOYSA-N 0.000 claims description 2
- ZGOMEYREADWKLC-UHFFFAOYSA-N 3-chloro-1,1,1,3-tetrafluoropropane Chemical compound FC(Cl)CC(F)(F)F ZGOMEYREADWKLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 24
- 150000002739 metals Chemical class 0.000 abstract description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 239000007789 gas Substances 0.000 description 5
- 238000005658 halogenation reaction Methods 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 230000026030 halogenation Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005796 dehydrofluorination reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NXRVIYWUCXPXLM-UHFFFAOYSA-N 3-chloro-1-fluoroprop-1-ene Chemical class FC=CCCl NXRVIYWUCXPXLM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 229920002313 fluoropolymer Polymers 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- -1 sterilant Substances 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical group ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZYRCHSMEYOVADI-UHFFFAOYSA-N FC(C(F)(F)F)(C)F.[Cl] Chemical compound FC(C(F)(F)F)(C)F.[Cl] ZYRCHSMEYOVADI-UHFFFAOYSA-N 0.000 description 1
- FKHKBOBPZPAKKU-UHFFFAOYSA-N FC(C(F)(F)F)C.[Cl] Chemical compound FC(C(F)(F)F)C.[Cl] FKHKBOBPZPAKKU-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229910000934 Monel 400 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- OANFWJQPUHQWDL-UHFFFAOYSA-N copper iron manganese nickel Chemical compound [Mn].[Fe].[Ni].[Cu] OANFWJQPUHQWDL-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 229910001119 inconels 625 Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07B35/06—Decomposition, e.g. elimination of halogens, water or hydrogen halides
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
本发明涉及一种制备氟化烯烃的方法,所述方法具有使具有至少一个氢原子和至少一个在相邻碳原子上的氯原子的氢氯氟烃脱氯化氢的步骤,所述步骤优选在催化剂存在下进行,所述催化剂选自(i)一种或多种金属卤化物、(ii)一种或多种卤化金属氧化物、(iii)一种或多种零价金属/金属合金和(iv)两种或更多种上述催化剂的组合。
Description
相关申请的交叉引用
本申请要求2007年7月6日提交的美国临时申请第60/958,468号的优先权,该申请通过引用结合到本文中来。
发明背景
1.发明领域
本发明涉及含卤素化合物的脱卤化氢。本发明还涉及氢氯氟烃(hydrochlorofluorocarbon)转化为氟化烯烃的脱氯化氢。
2.相关技术的描述
含氯化合物如氯氟烃(CFC)已被用作冷冻剂、发泡剂、清洁剂、溶剂、传热介质、杀菌剂、气溶胶推进剂、电介质、灭火剂和动力循环工作流体。然而,已证明CFC对地球臭氧层有害。CFC的常规替代物包括氢氟烃(HFC);然而,已发现这些化合物促进全球变暖。为此,全世界努力开发环境友好的新化合物。
部分或完全氟化的烯烃(包括氢氟烯烃)(下文中统称为氟化烯烃)为HFC和CFC的潜在代替者。它们可在一些上述应用中使用且还可用作合成含氟聚合物和其它大分子化合物的原料单体。
已知用于制备某些氟化烯烃的多种方法,包括涉及氢氯氟烃的脱氯化氢的方法。例如,美国专利申请第11/619,592号公开了一种借助于催化剂通过1,1,1,2-四氟-2-氯丙烷(244bb)的脱氯化氢制备2,3,3,3-四氟丙烯(1234yf)的方法。244bb反应物可通过1,1,1-三氟-2-氯丙烯(1233xf)与HF的液相或气相催化氟化制备,1233xf又可通过CCl2=CClCH2Cl(1,1,2,3-四氯丙烯)与HF的气相氟化制得。该‘592申请还指出基于碳和/或金属的催化剂在244bb到1234yf的转化中的用途。取决于反应条件,244bb的转化率可高达98%,但对1234yf的选择性仅为69%-86%。因此,仍需要开发一种不仅具有活性而且对1234yf具有更高选择性的商业上可行的催化剂。
然而,通过常规方法将氢氯氟烃转化为氟化烯烃存在问题,因为副产物经常形成且进行竞争性脱氟化氢反应。因此,将有利的是开发可抑制不合需要的脱氟化氢反应的催化剂体系,以便可增加所要氟化烯烃的单程生产量和产率。
发明概述
本发明了提供一种通过具有至少一个氢原子和至少一个在相邻碳原子上的氯原子的氢氯氟烃的脱氯化氢制备氟化烯烃的方法。所述脱氯化氢在催化剂存在下进行,所述催化剂选自:(i)一种或多种金属卤化物、(ii)一种或多种卤化金属氧化物、(iii)一种或多种零价金属/金属合金和(iv)两种或更多种上述催化剂的组合。优选的氟化烯烃产物如下:2,3,3,3-四氟丙烯(1234yf)、1,3,3,3-四氟丙烯(反/顺-1234ze)、1,2,3,3,3-五氟丙烯(Z/E-1255ye)、1,1,3,3,3-五氟丙烯(1225zc)和1,1,2,3,3,3-六氟丙烯(1216)。
发明详述
在本发明中,使具有至少一个氢和至少一个在相邻碳上的氯的氢氯氟烃在催化剂存在下脱氯化氢以形成其中具有氟化烯烃的产物。表1列出氟化烯烃和由其可获得所述氟化烯烃的前体氢氯氟烃的实例(即,氢氯氟烃在左列中,相应氟化烯烃在右列中)。
表1
氢氯氟烃 | 氟化烯烃 |
氯四氟丙烷 | 四氟丙烯 |
氯五氟丙烷 | 五氟丙烯 |
氯六氟丙烷 | 六氟丙烯 |
1,1,1,2-四氟-2-氯丙烷CF3CFClCH3(244bb) | 2,3,3,3-四氟丙烯CF3CF=CH2(1234yf) |
1,1,1,2-四氟-3-氯丙烷CF3CHFCH2Cl(244eb) | 2,3,3,3-四氟丙烯CF3CF=CH2(1234yf) |
1,1,1,3-四氟-3-氯丙烷CF3CH2CHFCl(244fa) | 1,3,3,3-四氟丙烯CF3CH=CHF(反/顺-1234ze) |
1,1,1,3-四氟-2-氯丙烷CF3CHClCH2F(244db) | 1,3,3,3-四氟丙烯CF3CH=CHF(反/顺-1234ze) |
1,1,1,2,3-五氟-2-氯丙烷CF3CFClCH2F(235bb) | 1,2,3,3,3-五氟丙烯CF3CF=CHF(Z/E-1225ye) |
1,1,1,2,3-五氟-3-氯丙烷CF3CHFCHFCl(235ea) | 1,2,3,3,3-五氟丙烯CF3CF=CHF(Z/E-1225ye) |
1,1,1,3,3-五氟-3-氯丙烷CF3CH2CF2Cl(235fa) | 1,1,3,3,3-五氟丙烯CF3CH=CF2(1225zc) |
1,1,1,3,3-五氟-2-氯丙烷CF3CHClCHF2(235da) | 1,1,3,3,3-五氟丙烯CF3CH=CF2(1225zc) |
1,1,1,2,3,3-六氟-2-氯丙烷CF3CFClCHF2(226ba) | 1,1,2,3,3,3-六氟丙烯CF3CF=CF2(1216) |
1,1,1,2,3,3-六氟-3-氯丙烷CF3CHFCF2Cl(226ea) | 1,1,2,3,3,3-六氟丙烯CF3CF=CF2(1216) |
在本发明的方法中,使用所选择的催化剂来增加氢氯氟烃到氟化烯烃的选择性和/或转化率。所述催化剂对于产生氟化烯烃的脱氯化氢反应比对于产生不合需要的副产物含氯烯烃的竞争性脱氟化氢副反应更具选择性。
可在本发明中使用的有三类优选的催化剂:(i)金属卤化物、(ii)卤化金属氧化物和(iii)零价金属/金属合金。
第一类催化剂为金属卤化物,优选为一价、二价和三价金属卤化物和其混合物/组合,更优选为一价和二价金属卤化物和其混合物/组合。金属组分包括但不限于Cr3+、Fe3+、Mg2+、Ca2+、Ni2+、Zn2+、Pd2+、Li+、Na+、K+和Cs+。卤素组分包括但不限于F-、Cl-、Br-和I-。有用一价或二价金属卤化物的实例包括但不限于LiF、NaF、KF、CsF、MgF2、CaF2、LiCl、NaCl、KCl和CsCl。所述催化剂可为负载型或非负载型。一种优选的催化剂为CsCl/MgF2组合。一种特别优选的催化剂为CsCl/MgF2组合,其中CsCl的存在量基于催化剂的总重量计算为约5.0%重量-约50%重量。
第二类催化剂为卤化金属氧化物,优选为卤代一价、二价和三价金属氧化物和其混合物/组合,更优选为卤代一价和二价金属氧化物和其混合物/组合。组分金属包括但不限于Cr3+、Fe3+、Mg2+、Ca2+、Ni2+、Zn2+、Pd2+、Li+、Na+、K+和Cs+。卤化处理可包括现有技术中已知的卤化处理中的任一种,特别是使用HF、F2、HCl、Cl2、HBr、Br2、HI和I2作为卤化源的卤化处理。有用的卤代一价和二价金属氧化物的实例包括但不限于氟化或氯化MgO、氟化或氯化CaO、氟化或氯化Li2O、氟化或氯化Na2O、氟化或氯化K2O和氟化或氯化Cs2O。所述催化剂可为负载型或非负载型。
第三类催化剂为中性(即零价)金属、金属合金和其混合物。有用的金属包括但不限于Pd、Pt、Rh、Fe、Co、Ni、Cu、Mo、Cr、Mn和上述金属以合金或混合物形式的组合。所述催化剂可为负载型或非负载型。金属合金的有用的实例包括但不限于SS 316、Monel 400、Inconel 825、Inconel 600和Inconel 625。
除所述氟化烯烃(即氢氟烃或氟烃)之外,产物混合物还可具有未转化的氢氯氟烃和氯化氢。
对于目标产物增加或改善的选择性是本发明的一个重要特征。脱氯化氢反应优选以至少约50%,更优选至少约70%,最优选至少约80%的选择性进行。转化率优选为约25%或更高,最优选为约40%或更高。
脱氯化氢可在约200℃至约800℃,优选约300℃至约600℃,更优选约400℃至约500℃的温度范围内在催化剂存在下进行。预期可使用多种反应压力,如高于大气压、大气压和低于大气压。优选大气压。
脱氯化氢可任选在存在或不存在氧化剂的情况下进行。氧化剂的有用实例包括但不限于氧气和二氧化碳。氧化剂的使用可延长催化剂的寿命。所述氧化剂可为纯净的或在引入反应器之前用惰性气体如氮气稀释。基于有机原料的体积计算,氧化剂的含量通常为约1体积%至约10体积%,优选为约2体积%至5体积%。
还可有利地在延长使用之后在反应器中就地使催化剂周期性再生。催化剂的再生可通过本领域已知的任何方式实现。一种方法是在约200℃至约600℃(优选约350℃至约450℃)的温度下使氧气或用氮气稀释的氧气通过催化剂,历时约0.5小时至约3天,接着在约25℃至约400℃(优选约200℃至约350℃)的温度下卤化处理卤化金属氧化物催化剂和金属卤化物催化剂或在约100℃至约600℃(优选约200℃至约350℃)的温度下还原处理金属催化剂。
脱氯化氢优选在耐蚀反应容器中进行。耐蚀材料的实例有Hastelloy、Inconel、Monel和含氟聚合物内衬。所述容器可具有固定催化剂床或流化催化剂床。如果需要,则在操作期间在反应器中可使用惰性气体如氮气或氩气。
实施例
以下为本发明的实施例并且不应将其理解为起限制作用。
实施例1:用金属氟化物和氟化金属氧化物催化剂的244bb脱卤
化氢
将一系列一价、二价和三价金属氟化物和氟化二价和三价金属氧化物用作脱卤化氢催化剂。在一个典型试验中使用约20ml催化剂丸。在200℃-600℃范围的温度下使含有97.2重量%244bb和2.0重量%1233xf的混合物以6g/h的速率穿过催化剂床。测量催化剂床底部和催化剂床顶部的温度。
如表2中所示,NaF、MgF2、CaF2和氟化MgO能够提供高于80%的对1234yf的选择性,而FeF3和氟化Cr2O3显示出高于80%的对1233xf的选择性。选择性基于摩尔百分比计算。这些结果表明一价和二价金属卤化物以及卤代一价和二价金属氧化物比其三价对应物更合适作为244bb脱氯化氢的催化剂。在NaF、MgF2、CaF2和氟化MgO中,MgF2显示出最佳性能,在8h(小时)运行之后其提供高于50%的244bb转化率和高于85%的对1234yf的选择性。
实施例2:用碱金属氯化物掺杂的MgF
2
催化剂的244bb脱卤化
氢
出于改善对1234yf的选择性的目的将一系列碱金属氯化物作为MgF2的添加剂来研究。出于比较目的,还报道了用MgF2催化剂得到的结果。在一个典型试验中使用约20ml催化剂丸。在470℃-520℃范围的温度下使含有97.2重量%244bb和2.0重量%1233xf的混合物以6g/h(克/小时)的速率通过催化剂床。测量催化剂床底部和催化剂床顶部的温度。
如表3中所示,MgF2提供53-55%的244bb转化率、80-87%的1234yf选择性和8-15%的1233xf选择性;10%LiCl/MgF2提供低于45%的244bb转化率、约90%的1234yf选择性和约5%的1233xf选择性;10%KCl/MgF2提供低于50%的244bb转化率、约96%的1234yf选择性和约1%的1233xf选择性;且10%CsCl/MgF2提供50-52%的244bb转化率、约97%的1234yf选择性且基本未形成1233xf。CsCl显示出最好结果,而10%CsCl/MgF2催化剂提供与MgF2相当的活性和最高的1234yf选择性同时不产生1233xf。
实施例3:用CsCl/MgF
2
催化剂的244bb脱卤化氢
出于优化CsCl加载量的目的研究一系列具有不同CsCl加载量的CsCl/MgF2催化剂。在一个典型试验中使用20ml催化剂丸。在470℃-520℃范围的温度下使含有97.2重量%244bb和2.0重量%1233xf的混合物以6g/h的速率通过催化剂床。测量催化剂床顶部和底部的温度。如表4中所示,基于催化剂的总重量计算,对1233xf的选择性随CsCl加载量从0.0增加到5.0重量%而降低,用加载≥7.5重量%的CsCl量的催化剂没有形成1233xf。
实施例4:用非贵金属掺杂的MgF
2
催化剂的244bb脱卤化氢
出于改善对1234yf的选择性的目的研究一系列非贵金属作为MgF2的添加剂。出于比较目的,还报道了用MgF2催化剂得到的结果。在一个典型试验中使用约20ml催化剂丸。在440℃-540℃范围的温度下使含有97.2重量%244bb和2.0重量%1233xf的混合物以6g/h的速率通过催化剂床。测量催化剂床顶部和底部的温度。
如表5中所示,加入钴且尤其是镍引起对1233xf的选择性降低,而加入铁引起对1233xf的选择性增加。12重量%Ni/MgF2催化剂提供约95%的1234yf选择性和约2%的1233xf选择性。
实施例5:用金属和金属合金催化剂的244bb脱卤化氢
将一系列负载型和非负载型金属以及金属合金用作脱卤化氢催化剂。在一个典型试验中使用20ml催化剂丸或4英寸长金属网辊。在420℃-480℃范围的温度下使含有97.2重量%244bb和2.0重量%1233xf的混合物以6g/h的速率通过催化剂床。测量催化剂床顶部和底部的温度。如表6中所示,所有所述金属和金属合金催化剂均具有活性且对244bb脱氯化氢极具选择性(1234yf选择性>95%),同时未产生1233xf。与金属卤化物和/或卤化金属氧化物催化剂相比较,所述金属催化剂不需要如此高的操作温度。
应当理解的是上述说明书仅仅是本发明的说明。本领域的技术人员可在不脱离本发明的情况下设计多种供选物和改进。因此,本发明旨在包含落入附加权利要求书范围之内的所有此类供选物、改进和变化。
Claims (24)
1.一种制备氟化烯烃的方法,所述方法包括:
使具有至少一个氢和至少一个在相邻碳上的氯的氢氯氟烃在催化剂存在下脱氯化氢,所述催化剂选自(i)一种或多种金属卤化物、(ii)一种或多种卤化金属氧化物、(iii)一种或多种零价金属/金属合金和(iv)两种或更多种这些催化剂的组合。
2.权利要求1的方法,其中所述氢氯氟烃和生成的氟化烯烃选自1,1,1,2-四氟-2-氯丙烷和2,3,3,3-四氟丙烯、1,1,1,2-四氟-3-氯丙烷和2,3,3,3-四氟丙烯、1,1,1,3-四氟-3-氯丙烷和1,3,3,3-四氟丙烯、1,1,1,3-四氟-2-氯丙烷和1,3,3,3-四氟丙烯、1,1,1,2,3-五氟-2-氯丙烷和1,2,3,3,3-五氟丙烯、1,1,1,2,3-五氟-3-氯丙烷和1,2,3,3,3-五氟丙烯、1,1,1,3,3-五氟-3-氯丙烷和1,1,3,3,3-五氟丙烯、1,1,1,3,3-五氟-2-氯丙烷和1,1,3,3,3-五氟丙烯、1,1,1,2,3,3-六氟-2-氯丙烷和1,1,2,3,3,3-六氟丙烯、和1,1,1,2,3,3-六氟-3-氯丙烷和1,1,2,3,3,3-六氟丙烯。
3.权利要求1的方法,其中所述氢氯氟烃为1,1,1,2-四氟-2-氯丙烷,所述氟化烯烃为2,3,3,3-四氟丙烯。
4.权利要求1的方法,其中所述催化剂为一种或多种金属卤化物,其中一种或多种金属卤化物为一价金属卤化物、二价金属卤化物、三价金属卤化物或两种或更多种这些金属卤化物的组合。
5.权利要求4的方法,其中所述一种或多种金属卤化物具有选自Mg2+、Ca2+、Ni2+、Zn2+、Pd2+、Li+、Na+、K+和Cs+的金属和选自F-、Cl-、Br-和I-的卤素原子。
6.权利要求5的方法,其中所述一种或多种金属卤化物选自LiF、NaF、KF、CsF、MgF2、CaF2、LiCl、NaCl、KCl、CsCl或两种或更多种这些金属卤化物的组合。
7.权利要求1的方法,其中所述催化剂为一种或多种卤化金属氧化物,其中所述一种或多种卤化金属氧化物选自一价卤化金属氧化物、二价卤化金属氧化物、三价卤化金属氧化物或两种或更多种这些卤化金属氧化物的组合。
8.权利要求7的方法,其中所述一种或多种卤化金属氧化物选自一价卤化金属氧化物、二价卤化金属氧化物和两种或更多种这些卤化金属氧化物的组合。
9.权利要求7的方法,其中所述一种或多种卤化金属氧化物选自氟化或氯化MgO、氟化或氯化CaO、氟化或氯化Li2O、氟化或氯化Na2O、氟化或氯化K2O、氟化或氯化Cs2O和两种或更多种这些卤化金属氧化物的组合。
10.权利要求1的方法,其中所述催化剂为一种或多种零价金属/金属合金。
11.权利要求10的方法,其中所述一种或多种零价金属/金属合金选自Pd、Pt、Rh、Fe、Co、Ni、Cu、Mo、Cr、Mn及其组合。
12.权利要求11的方法,其中所述一种或多种零价金属/金属合金选自Pd、Fe、Co、Ni及其组合。
13.权利要求2的方法,其中所述催化剂为一种或多种金属卤化物,其中所述一种或多种金属卤化物选自一价金属卤化物、二价金属卤化物和两种或更多种这些金属卤化物的组合。
14.权利要求2的方法,其中所述催化剂为一种或多种卤化金属氧化物,其中所述卤化金属氧化物选自一价卤化金属氧化物、二价卤化金属氧化物和两种或更多种这些卤化金属氧化物的组合。
15.权利要求2的方法,其中所述催化剂为一种或多种零价金属/金属合金。
16.权利要求3的方法,其中所述催化剂为一种或多种金属卤化物,其中所述一种或多种金属卤化物选自一价金属卤化物、二价金属卤化物和两种或更多种这些金属卤化物的组合。
17.权利要求3的方法,其中所述催化剂为一种或多种卤化金属氧化物,其中所述卤化金属氧化物选自一价卤化金属氧化物、二价卤化金属氧化物和两种或更多种这些卤化金属氧化物的组合。
18.权利要求3的方法,其中所述催化剂为零价金属/金属合金。
19.权利要求1的方法,其中所述催化剂为CsCl/MgF2组合。
20.权利要求19的方法,其中基于所述催化剂的总重量计算所述CsCl为所述组合的约5.0重量%至约50.0重量%。
21.权利要求2的方法,其中所述催化剂为CsCl/MgF2组合。
22.权利要求21的方法,其中基于所述催化剂的总重量计算所述CsCl为所述组合的约5.0重量%至约50.0重量%。
23.权利要求3的方法,其中所述催化剂为CsCl/MgF2组合。
24.权利要求23的方法,其中基于所述催化剂的总重量计算所述CsCl为所述组合的约5.0重量%至约50.0重量%。
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KR20100040897A (ko) | 2010-04-21 |
EP2164824A4 (en) | 2011-11-16 |
EP2164824B1 (en) | 2019-01-16 |
KR20150129062A (ko) | 2015-11-18 |
EP2164824A1 (en) | 2010-03-24 |
US10807925B2 (en) | 2020-10-20 |
MX2009013376A (es) | 2010-01-25 |
US9040759B2 (en) | 2015-05-26 |
KR20170024136A (ko) | 2017-03-06 |
KR101875204B1 (ko) | 2018-07-06 |
US20150368169A1 (en) | 2015-12-24 |
JP5436417B2 (ja) | 2014-03-05 |
JP2010532762A (ja) | 2010-10-14 |
CN101687737B (zh) | 2013-10-30 |
KR101711140B1 (ko) | 2017-02-28 |
WO2009009421A1 (en) | 2009-01-15 |
US20090043136A1 (en) | 2009-02-12 |
ES2719478T3 (es) | 2019-07-10 |
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