CN108911947B - 一种1,1,1,2,4,4,4-七氟-2-丁烯的制备方法 - Google Patents
一种1,1,1,2,4,4,4-七氟-2-丁烯的制备方法 Download PDFInfo
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- YIFLMZOLKQBEBO-UPHRSURJSA-N (z)-1,1,1,2,4,4,4-heptafluorobut-2-ene Chemical compound FC(F)(F)C(/F)=C/C(F)(F)F YIFLMZOLKQBEBO-UPHRSURJSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011651 chromium Substances 0.000 claims abstract description 41
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical group [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 4
- 239000011636 chromium(III) chloride Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium nitrate Inorganic materials [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- 238000003682 fluorination reaction Methods 0.000 abstract description 10
- 125000004122 cyclic group Chemical group 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KAHIKRWJVIBASP-UHFFFAOYSA-N 1,2-dichloro-3,3,4,4-tetrafluorocyclobutene Chemical compound FC1(F)C(Cl)=C(Cl)C1(F)F KAHIKRWJVIBASP-UHFFFAOYSA-N 0.000 description 3
- XDIDQEGAKCWQQP-UHFFFAOYSA-N 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C(Cl)=C(Cl)C(F)(F)F XDIDQEGAKCWQQP-UHFFFAOYSA-N 0.000 description 3
- JRENXZBKMHPULY-UHFFFAOYSA-N 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C=C(Cl)C(F)(F)F JRENXZBKMHPULY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- JDCMOHAFGDQQJX-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octafluoronaphthalene Chemical compound FC1=C(F)C(F)=C(F)C2=C(F)C(F)=C(F)C(F)=C21 JDCMOHAFGDQQJX-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- WBCLXFIDEDJGCC-UHFFFAOYSA-N hexafluoro-2-butyne Chemical compound FC(F)(F)C#CC(F)(F)F WBCLXFIDEDJGCC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—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
- 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
- B01J23/864—Cobalt and chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J37/02—Impregnation, coating or precipitation
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Abstract
本发明公开了一种1,1,1,2,4,4,4‑七氟‑2‑丁烯的制备方法。该方法是以六氯丁二烯与氟化氢作为原料,在气相条件下,以铬基催化剂为氟氯交换催化剂,通过多次气相催化反应生成1,1,1,2,4,4,4‑七氟‑2‑丁烯。与现有技术相比,本发明提供的1,1,1,2,4,4,4‑七氟‑2‑丁烯的制备方法具有以下优点:1.本发明采用的气相氟化法为循环氟化,工业三废较少,大大降低了生产成本;2.本发明可实现快速多次循环氟化,提高产品收率,产物分离提纯简单;3.具有原料廉价、来源便利、操作简单的优点,适合于工业化生产。
Description
技术领域
本发明属于有机化学合成技术领域,特别是涉及一种含氟有机化合物的合成方法。
背景技术
由于氢氟烯烃(HFO)具有优异的工作性能和环境性能,因此目前已逐渐成为新一代反相色谱柱(ODS)的替代品,并在制冷、灭火、发泡、刻蚀、清洗等领域得到了广泛的应用。而1,1,1,2,4,4,4-七氟-2-丁烯是HFO中的一种重要化合物,不仅可以应用于制冷、发泡、干燥或脱脂用溶剂等领域,还可以作为制备六氟-2-丁炔的中间体。但是合成1,1,1,2,4,4,4-七氟-2-丁烯的方法还较少,目前关于1,1,1,2,4,4,4-七氟-2-丁烯的合成方法主要有以下两种:
(1)John T.Maynard[Journal of Organic Chemistry,1963,28(1):112-115]采用六氯丁二烯为原料,以氟化钾为催化剂,N-甲基吡咯烷酮为溶剂,在加热条件下制备1,1,1,2,4,4,4-七氟-2-丁烯,产率可以达到65%。该方法的主要问题是溶剂消耗较大,并且产生大量废弃物,不利于工业化生产;
(2)专利[WO 98/55429]采用六氯丁二烯为原料,以氟化钾为催化剂,全氟化萘和环丁砜为溶剂,在加热条件下制备1,1,1,2,4,4,4-七氟-2-丁烯,产率可以达到60%。虽然该方法可以减少溶剂的消耗,但是同样会产生大量废弃物,同样不利于工业化生产;
由此可以看出,以上合成1,1,1,2,4,4,4-七氟-2-丁烯的方法主要采用液相催化方法,而液相催化方法除了要消耗大量有机溶剂外,还会产生大量废弃物,容易造成环境污染,不利于工业化生产。
发明内容
为了解决上述问题,本发明的目的在于提供了一种工艺简单、成本低、绿色环保、易于工业化的1,1,1,2,4,4,4-七氟-2-丁烯的制备方法。
为了达到上述目的,本发明提供的1,1,1,2,4,4,4-七氟-2-丁烯的制备方法是以六氯丁二烯与氟化氢作为原料,在气相条件下,以铬基催化剂为氟氯交换催化剂,通过多次气相催化反应生成1,1,1,2,4,4,4-七氟-2-丁烯。
所述的六氯丁二烯与氟化氢的摩尔比为1:7~40。
所述的气相催化反应的温度为280-500℃。
所述的气相催化反应的接触时间为3-20s。
所述的铬基催化剂是由主剂、助剂和碳材料通过共沉淀及活化方法制备而成;
其中,主剂选自CrCl3、Cr(NO3)3中的至少一种;
助剂选自Ni(NO3)3、Cu(NO3)2、Zn(NO3)2、Mg(NO3)2、Co(NO3)2、In(NO3)3、FeCl3、CaCl2、Al(NO3)3、Mn(NO3)2中的至少一种;
碳材料选自石墨烯、碳纳米管、乙炔黑、活性炭、气相生长炭纤维(VGCF)、科琴黑(KB)中的至少一种;
制备方法包括以下步骤:
(1)将主剂和助剂溶于均匀分散的碳材料水溶液中,通过共沉淀方法使主剂和助剂中的氢氧化物均匀沉积于碳材料的表面,将得到的固体在高温条件下进行焙烧,得到铬基催化剂前体;
(2)将上述铬基催化剂前体在氮气与氟化氢的混合气体中进行初步活化,再在纯氟化氢环境下进行深度活化,从而制成所述的铬基催化剂;
所述的铬基催化剂中主剂、助剂和碳材料的摩尔比为75~98:0.1~10:1~15。
在步骤(1)中,所述的焙烧温度为300-600℃。
在步骤(2)中,所述的氟化温度为200-500℃。
与现有技术相比,本发明提供的1,1,1,2,4,4,4-七氟-2-丁烯的制备方法具有以下优点:
1.本发明采用的气相氟化法为循环氟化,工业三废较少,大大降低了生产成本;
2.本发明可实现快速多次循环氟化,提高产品收率,产物分离提纯简单;
3.具有原料廉价、来源便利、操作简单的优点,适合于工业化生产。
具体的实施方式
以下通过具体实施方式的描述对本发明作进一步说明,但这并非是对本发明的限制,本领域技术人员根据本发明的基本思想,可以做出各种修改或改进,但是只要不脱离本发明的基本思想,均在本发明的范围之内。
实施例1
本实施例提供的1,1,1,2,4,4,4-七氟-2-丁烯的制备方法包括下列步骤:
(1)铬基催化剂前体的制备:采用共沉淀法,步骤如下,将摩尔比为85:5:10的CrCl3、Zn(NO3)2和石墨烯溶液混合均匀,室温下超声处理30分钟,将30wt.%的氨水缓慢滴加到上述混合溶液中,调节溶液pH=9.0,经过4小时沉淀老化,过滤沉淀物,用去离子水洗涤沉淀物并在400℃下焙烧,压制成型,从而得到铬基催化剂前体。
铬基催化剂的活化:将10ml铬基催化剂前体装入固定床反应器,用开启式管子加热炉加热固定床反应器,在速度为50ml/min的氮气保护以及300℃温度下对铬基催化剂进行干燥10小时;再通入速度为80ml/min的氟化氢,300℃温度下活化铬基催化剂4小时,由此完成铬基催化剂的活化。
1,1,1,2,4,4,4-七氟-2-丁烯的合成:将摩尔比为1:7的六氯丁二烯和氟化氢混合气体以250ml/min的速度通过380℃铬基催化剂固定床反应器,之后,通过缓冲瓶、水洗瓶、浓碱吸收器、冷却收集器。实验结束后,产物主要分布在冷却收集器中。将收集到的产物进行GC分析。GC结果显示,收集产物中主要含有12%1,1,1,2,4,4,4-七氟-2-丁烯(分子式CF3-CF=CH-CF3),29%二氯六氟-2-丁烯(分子式CF3-CCl=CCl-CF3),39%1,1,1,4,4,4-六氟-2-氯-2-丁烯(分子式CF3-CCl=CH-CF3),9%二氯四氟环丁烯(分子式cycle-CF2-CCl=CCl-CF2-cycle)。将该反应混合产物继续多次循环氟化,最终获得纯度为90%以上的1,1,1,2,4,4,4-七氟-2-丁烯。
实施例2
本实施例提供的1,1,1,2,4,4,4-七氟-2-丁烯的制备方法包括下列步骤:
(1)铬基催化剂前体的制备:采用共沉淀法,步骤如下,将摩尔比为85:5:10的CrCl3、Co(NO3)2和活性炭溶液混合均匀,室温下超声处理30分钟,将30wt.%的氨水缓慢滴加到上述混合溶液中,调节溶液pH=9.0,经过4小时沉淀老化,过滤沉淀物,用去离子水洗涤沉淀物并在400℃下焙烧,压制成型,从而得到铬基催化剂前体。
铬基催化剂的活化:将10ml铬基催化剂前体装入固定床反应器,用开启式管子加热炉加热固定床反应器,在速度为50ml/min的氮气保护以及300℃温度下对铬基催化剂进行干燥10小时;再通入速度为80ml/min的氟化氢,300℃温度下活化铬基催化剂4小时,由此完成铬基催化剂的活化。
1,1,1,2,4,4,4-七氟-2-丁烯的合成:将摩尔比为1:20的六氯丁二烯和氟化氢混合气体以250ml/min的速度通过380℃铬基催化剂固定床反应器,之后,通过缓冲瓶、水洗瓶、浓碱吸收器、冷却收集器。实验结束后,产物主要分布在冷却收集器中。将收集到的产物进行GC分析。GC结果显示,收集产物中主要含有18%1,1,1,2,4,4,4-七氟-2-丁烯(分子式CF3-CF=CH-CF3),21%二氯六氟-2-丁烯(分子式CF3-CCl=CCl-CF3),42%1,1,1,4,4,4-六氟-2-氯-2-丁烯(分子式CF3-CCl=CH-CF3),7%二氯四氟环丁烯(分子式cycle-CF2-CCl=CCl-CF2-cycle)。将该反应混合产物继续多次循环氟化,最终获得纯度为90%以上的1,1,1,2,4,4,4-七氟-2-丁烯。
实施例3
本实施例提供的1,1,1,2,4,4,4-七氟-2-丁烯的制备方法包括下列步骤:
(1)铬基催化剂前体的制备:采用共沉淀法,步骤如下,将摩尔比为82:5:13的Cr(NO3)3、Ni(NO3)3和碳纳米管溶液混合均匀,室温下超声处理30分钟,将30wt.%的氨水缓慢滴加到上述混合溶液中,调节溶液pH=9.0,经过4小时沉淀老化,过滤沉淀物,用去离子水洗涤沉淀物并在400℃下焙烧,压制成型,从而得到铬基催化剂前体。
铬基催化剂的活化:将10ml铬基催化剂前体装入固定床反应器,用开启式管子加热炉加热固定床反应器,在速度为50ml/min的氮气保护以及350℃温度下对铬基催化剂进行干燥10小时;再通入速度为80ml/min的氟化氢,350℃温度下活化铬基催化剂4小时,由此完成铬基催化剂的活化。
1,1,1,2,4,4,4-七氟-2-丁烯的合成:将摩尔比为1:30的六氯丁二烯和氟化氢混合气体以250ml/min的速度通过380℃铬基催化剂固定床反应器,之后,通过缓冲瓶、水洗瓶、浓碱吸收器、冷却收集器。实验结束后,产物主要分布在冷却收集器中。将收集到的产物进行GC分析。GC结果显示,收集产物中主要含有12%1,1,1,2,4,4,4-七氟-2-丁烯(分子式CF3-CF=CH-CF3),29%二氯六氟-2-丁烯(分子式CF3-CCl=CCl-CF3),38%1,1,1,4,4,4-六氟-2-氯-2-丁烯(分子式CF3-CCl=CH-CF3),13%二氯四氟环丁烯(分子式cycle-CF2-CCl=CCl-CF2-cycle)。将该反应混合产物继续多次循环氟化,最终获得纯度为90%以上的1,1,1,2,4,4,4-七氟-2-丁烯。
Claims (6)
1.一种1,1,1,2,4,4,4-七氟-2-丁烯的制备方法,其特征在于:所述的1,1,1,2,4,4,4-七氟-2-丁烯的制备方法是以六氯丁二烯与氟化氢作为原料,在气相条件下,以铬基催化剂为氟氯交换催化剂,通过多次气相催化反应生成1,1,1,2,4,4,4-七氟-2-丁烯;
其中,铬基催化剂是由主剂、助剂和碳材料通过共沉淀及活化方法制备而成;主剂选自CrCl3、Cr(NO3)3中的至少一种;助剂选自Ni(NO3)3、Cu(NO3)2、Zn(NO3)2、Mg(NO3)2、Co(NO3)2、In(NO3)3、FeCl3、CaCl2、Al(NO3)3、Mn(NO3)2中的至少一种;碳材料选自石墨烯、碳纳米管、乙炔黑、活性炭、气相生长炭纤维、科琴黑中的至少一种;
铬基催化剂制备方法包括以下步骤:
(1)将主剂和助剂溶于均匀分散的碳材料水溶液中,通过共沉淀方法使主剂和助剂中的氢氧化物均匀沉积于碳材料的表面,将得到的固体在高温条件下进行焙烧,得到铬基催化剂前体;
(2)将上述铬基催化剂前体在氮气与氟化氢的混合气体中进行初步活化,再在纯氟化氢环境下进行深度活化,从而制成所述的铬基催化剂;
在铬基催化剂制备步骤(1)中,所述的焙烧温度为300-600℃。
2.根据权利要求1所述的方法,其特征在于:所述的六氯丁二烯与氟化氢的摩尔比为1:7~40。
3.根据权利要求1所述的方法,其特征在于:所述的气相催化反应的温度为280-500℃。
4.根据权利要求1所述的方法,其特征在于:所述的气相催化反应的接触时间为3-20s。
5.根据权利要求1所述的方法,其特征在于:所述的铬基催化剂中主剂、助剂和碳材料的摩尔比为75~98:0.1~10:1~15。
6.根据权利要求1所述的方法,其特征在于:在铬基催化剂制备步骤(2)中,所述的初步活化或深度活化温度为200-500℃。
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