CN102065999A - 制备氟化化合物的方法 - Google Patents
制备氟化化合物的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000005796 dehydrofluorination reaction Methods 0.000 claims description 15
- 239000011651 chromium Substances 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- SUAMPXQALWYDBK-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluoropropane Chemical compound FCC(F)(F)C(F)(F)F SUAMPXQALWYDBK-UHFFFAOYSA-N 0.000 abstract 1
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
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- 230000004913 activation Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
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- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
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- 238000003682 fluorination reaction Methods 0.000 description 3
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- 150000002815 nickel Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- WHEOOESXUFDZMQ-UHFFFAOYSA-N [O-2].[Cr+3].[F].[O-2].[O-2].[Cr+3] Chemical compound [O-2].[Cr+3].[F].[O-2].[O-2].[Cr+3] WHEOOESXUFDZMQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001398 aluminium Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- -1 fluorine compounds 1 Chemical class 0.000 description 2
- FDRDRAQDNZWSDQ-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium nickel Chemical compound [Ni].[Cr](=O)(=O)(O)O[Cr](=O)(=O)O FDRDRAQDNZWSDQ-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 1
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 238000013019 agitation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- XTPPTOYOHVLSHK-UHFFFAOYSA-L dihydroxy(dioxo)chromium nickel Chemical compound [Ni].O[Cr](O)(=O)=O XTPPTOYOHVLSHK-UHFFFAOYSA-L 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 239000004811 fluoropolymer Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
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- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
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- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及在氢气的存在下使1,1,1,2,2,3-六氟丙烷脱氟化氢以产生1,2,3,3,3-五氟-1-丙烯的方法。
Description
技术领域
本发明涉及用于制备氟化合物,特别是氟化合物1,2,3,3,3-五氟-1-丙烯(1225ye)的方法。
背景技术
氢氟烃(HFC)且特别是氢氟烯烃(HFO)是因其作为下列用途的性质而众所周知的化合物:制冷剂和热交换剂、灭火剂、推进剂、发泡剂、膨胀剂、电介质气体、聚合或单体介质、载流体(support fluid)、研磨剂、干燥剂以及能量产生装置用流体。不同于对臭氧层具有潜在威胁的CFC和HCFC,HFO不含氯并且因而不给臭氧层带来问题。
文献WO2008/040969描述了经由使含有3~6个碳原子的氢(卤代)氟代烷在包含铬和/或锌化合物的催化剂的存在下脱卤化氢而制备含有3~6个碳原子的(氢)氟烯烃。该文献教导所述脱氟化氢可在不存在HF(氢氟酸)的情况下进行,但是优选使用HF以避免或阻止有机进料(charge)的分解和/或催化剂的结焦(通过焦炭的沉积而结垢)。
文献WO2008/008350描述了由选自1,1,1,2,3,3-六氟丙烷(HFC 236ea)和1,1,1,2,2,3-六氟丙烷(HFC 236cb)的六氟丙烷在氟氧化铬催化剂的存在下制备1,2,3,3,3-五氟-1-丙烯(1225ye)的E异构体和Z异构体的混合物。该文献的实施例1说明1,1,1,2,2,3-六氟丙烷(HFC 236cb)到1,2,3,3,3-五氟-1-丙烯(1225ye)的脱氟化氢反应,并且显示在26小时的官能化之后,236cb的转化率大大降低,对1225ye的选择性也大大降低。为了再次建立催化活性,该文献教导经由使用空气和HF的处理使催化剂再生。
需要容许随时间推移的稳定性的用于由236cb制备1225ye的方法。
发明内容
因而,本发明提供在氢气的存在下使1,1,1,2,2,3-六氟丙烷脱氟化氢以产生1,2,3,3,3-五氟-1-丙烯的方法。
根据一些实施方式:
-所述反应在具有0.3~30的H2/1,1,1,2,2,3-六氟丙烷摩尔比的气相中进行。
-所述反应在具有0.5~20且有利地为1~10的H2/1,1,1,2,2,3-六氟丙烷摩尔比的气相中进行。
-所述方法在脱氟化氢催化剂的存在下进行。
-所述脱氟化氢催化剂为基于铬的催化剂。
-所述方法在150℃~500℃且优选为300℃~400℃的温度下进行。
-所述方法以0.1~100秒、优选1~50秒且有利地5~40秒的接触时间进行。
具体实施方式
本发明是基于如下发现:当236cb的脱氟化氢反应在氢气的存在下进行时,其提供关于转化率和对1225ye的选择性两者的随时间推移的稳定性。
总的来说,将氢气随着起始进料(charge)注入,例如连续地或者以交替方式注入。H2/起始进料摩尔比可在宽的范围内变化,特别为0.3~30,尤其为0.5~20且有利地为1~10。
在氢气存在下的脱氟化氢反应的使用提供高的随时间推移的稳定性。氢气的存在也使得可减少反应期间重质产物的产生。
使用脱氟化氢催化剂进行脱氟化氢反应。该催化剂为,例如,基于金属特别是过渡金属或者这样的金属的氧化物、卤化物或卤氧化物衍生物的催化剂。催化剂为例如FeCl3、氟氧化铬、Ni(包括Ni晶格)、NiCl2、CrF3、及其混合物。其它可能的催化剂为负载在炭(charcoal)上的催化剂、基于锑的催化剂、基于铝的催化剂(例如AlF3、Al2O3、氟氧化铝和氟化的氧化铝)、钯、铂、铑和钌。可参考文献US-P-5396000第1栏第50行到第2栏第2行中给出的名单或者WO2007/056194第16页第13-23行中给出的名单。
根据一个变型,使用含有铬和镍两者的混合催化剂。关于金属元素,Cr∶Ni摩尔比通常为0.5~5,例如0.7~2,特别为1左右。所述催化剂可含有以重量计的0.5~20%的铬和0.5~20%的镍,优选2%~10%的铬和2%~10%的镍。
所述金属可以金属形式或以衍生物(特别是氧化物、卤化物或卤氧化物)的形式存在,这些衍生物(特别是卤化物和卤氧化物)是经由催化金属的活化得到的。虽然所述金属的活化不是必需的,但其是优选的。
载体是基于铝。可提及几种可能的载体,例如氧化铝、经活化的氧化铝或铝衍生物。这些铝衍生物特别是卤化铝或卤氧化铝,其描述于例如US-P-4902838中或者经由下面描述的活化方法得到。
所述催化剂可包含在载体上的经活化的形式或未经活化的形式的铬和镍,所述载体也已经经历了所述金属的活化,或者没有经历所述金属的活化。
所述催化剂可由氧化铝(通常为“经活化的”氧化铝;该经活化的氧化铝为高孔隙率的氧化铝,并且不同于已经历金属活化处理的氧化铝)制备。在第一步骤中,通过使用空气和氢氟酸进行氟化将氧化铝转化为氟化铝或者转化为氟化铝和氧化铝的混合物,氧化铝转化为氟化铝的转化率主要取决于进行氧化铝的氟化的温度(通常为200℃~450℃并优选为250℃~400℃)。然后使用铬盐和镍盐的水溶液或者使用铬酸、镍盐和甲醇(用作铬还原剂)的水溶液浸渍载体。可使用的铬盐和镍盐包括氯化物,或其它盐例如草酸盐、甲酸盐、乙酸盐、硝酸盐和硫酸盐,或重铬酸镍,条件是这些盐可溶于可被载体吸收的量的水中。所述催化剂也可经由借助于以上提及的铬化合物和镍化合物的溶液对氧化铝(其通常是经活化的)进行直接浸渍而制备。在这种情况下,在所述催化剂的金属的活化步骤期间进行至少部分(例如70%或更多)的氧化铝到氟化铝或氟氧化铝的转化。
可用于制备所述催化剂的经活化的氧化铝是公知的市售产品。它们通常通过氧化铝水合物(氢氧化铝)在300℃~800℃的温度下的煅烧制备。
优选地,但不是必须的,经由预备“活化”操作对催化剂进行调理(condition)或活化,即将其转化为活性和稳定(在反应条件下)的成分。该处理可“原位”(在脱氟化氢反应器中)或在合适的设计成耐受活化条件的装置中进行。
该活化步骤通常包括下列步骤:
-干燥步骤。该干燥步骤在氮气或空气流下通常在高温(250℃~450℃,且优选300℃~350℃)下进行。在第一阶段中,在该干燥步骤之前,可任选地具有在空气或氮气的存在下在低温(100℃~150℃,且优选110℃~120℃)下进行干燥的第一步骤。该干燥步骤的持续时间可为1~50小时。
-氟化步骤。该氟化步骤使用氢氟酸和氮气的混合物在低温(180℃~350℃)下在控制HF含量使得温度不超过350℃的同时进行。该氟化步骤的持续时间可为1~50小时。
-任选的精制(finishing)步骤,其在纯氢氟酸流或用氮气稀释的氢氟酸流下在可最高达450℃的温度下进行。该精制步骤的持续时间可为1~15小时。
在该操作期间,催化前体(例如镍和铬的卤化物、铬酸镍或重铬酸镍、氧化铬)转化为相应的氟化物和/或氟氧化物,这导致释放出水和/或氢氯酸。在该活化之后的元素(铬、镍、氟、铝、氧)的化学分析可确认催化剂的无机组成。
这样的催化剂描述于EP-A-486333中,特别是第3页第11~48行,实施例1A、2A和4A中,参考这些段落。
所述脱氟化氢反应通常在气相中进行。
所述催化剂可以任何合适的形式,例如以固定床或流化床的形式存在,优选作为固定床存在。流动的方向可为向下的或向上的。
温度可为150℃~600℃,优选为300℃~500℃且有利地为300℃~450℃。
压力可为大气压,或者低于或高于该大气压。
接触时间(催化剂的体积与总的进料流量之比)通常为0.1~100秒,优选为1~50秒且有利地为5~40秒。
可在所述反应中使用稀释气体(氮气、氦气或氩气)。
所述反应在专用于涉及卤素的反应的反应器中进行。这样的反应器是本领域技术人员已知的,并且可包括基于例如或含氟聚合物的衬里。如果必要,所述反应器也可包括热交换装置。
以常规方式分离所述反应的最终产物,并且有利地将未反应的反应物再循环到所述方法中。回顾(recall):
-转化率是已反应的原料的百分比(反应的原料的摩尔数/引入的原料的摩尔数);
-对所需产物的选择性是所形成的所需产物的摩尔数/已反应的原料的摩尔数之比;
-所需产物的产率是所形成的所需产物的摩尔数/引入的原料的摩尔数之比,所需产物的产率也可定义为转化率和选择性的乘积;
-接触时间是气时空速(GHSV)的倒数;
-空间速度是在标准温度和压力条件下气态物流的总的体积通过量与催化剂床的体积之比;
-生产能力表示为每单位时间每单位(质量或体积)的催化剂得到的所需产物的质量;该生产能力与接触时间有关。
实施例
下列实施例说明本发明但不限制本发明。
实施例1催化剂的制备
使用的催化剂为Ni-Cr/AlF3催化剂,其如下制备。
将343g在前面的步骤中通过在约280℃下使用空气和氢氟酸(该酸在空气中的体积浓度为5%~10%)对Grace HSA氧化铝进行氟化得到的载体置于旋转蒸发器中作为固定床。Grace HSA起始氧化铝具有下列物理化学特性:
-形状:直径为0.5~2mm的珠
-BET表面积:220m2/g
-孔体积:1.3cm3/g
分别制备两种单独的水溶液:
(a)增补有氯化镍的铬溶液,其含有:
(b)甲醇溶液,其含有:
在40℃的温度下在大气压下在搅拌下以约2小时将这两种溶液同时引入到载体上。在氮气下的熟化步骤之后,将催化剂在氮气下干燥,然后在真空下在65℃下干燥,然后在真空下在约90℃下干燥6小时。
将500g经浸渍的固体置于Inconel管式反应器中。首先将催化剂在氮气流下在低温下干燥,然后在高达320℃的温度下在大气压下干燥。然后,将该催化剂在氢氟酸/氮气混合物(该酸在氮气中的体积浓度为5%~10%)的存在下在320℃下并且然后在高达390℃的温度下进行氟化。然后停止HF进料。在390℃下用氮气持续冲洗15分钟,然后将该催化剂在氮气流下冷却至60℃。
活化之后的催化剂的特性如下:
-BET表面积:40m2/g
-孔体积:0.4cm3/g
-以重量计的化学组成,:
■Al:25%
■F:58%
■Cr:5.3%
■Ni:6.4%
实施例2236cb脱氟化氢生成1225ye
使用容积为50cm3且直径为2.1cm的反应器,其含有高度为6.6cm的固定床形式的20g催化剂。压力为1巴。温度为375℃。
向所述反应器中引入100mmol/h的236cb和450mmol/h的氢气,即氢气/236cb摩尔比=4.5。
接触时间为6.7秒。
在100小时的运行之后,236cb的转化率和对1225ye的选择性保持不变。
Claims (7)
1.使1,2,2,3-六氟丙烷脱氟化氢以产生1,2,3,3,3-五氟-1-丙烯的方法,其在氢气的存在下进行。
2.权利要求1的方法,其中所述反应在具有0.3~30的H2/1,1,1,2,3,3-六氟丙烷摩尔比的气相中进行。
3.权利要求1或2的方法,其中所述反应在具有0.5~20和有利地1~10的H2/1,1,1,2,3,3-六氟丙烷摩尔比的气相中进行。
4.权利要求1~3中任一项的方法,其在脱氟化氢催化剂的存在下进行。
5.权利要求4的方法,其中所述脱氟化氢催化剂为在基于铝的载体上的基于铬和镍的混合催化剂。
6.权利要求1~5中任一项的方法,其在150℃~500℃和优选在300℃~400℃的温度下进行。
7.权利要求1~6中任一项的方法,其以0.1~100秒、优选1~50秒和有利地5~40秒的接触时间进行。
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