CN112452345B - 气相氟化合成反式-1-氯-3,3,3-三氟丙烯用催化剂及合成方法 - Google Patents
气相氟化合成反式-1-氯-3,3,3-三氟丙烯用催化剂及合成方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 16
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 238000003786 synthesis reaction Methods 0.000 title claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
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- 239000012025 fluorinating agent Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 claims description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 claims 1
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- 229910018084 Al-Fe Inorganic materials 0.000 description 5
- 229910018192 Al—Fe Inorganic materials 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
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- 239000011651 chromium Substances 0.000 description 4
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- 238000002791 soaking Methods 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
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- ARPHZKDALCEJAD-UHFFFAOYSA-N 1,1,1,2,3,3-hexachloropropane Chemical compound ClC(Cl)C(Cl)C(Cl)(Cl)Cl ARPHZKDALCEJAD-UHFFFAOYSA-N 0.000 description 1
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 description 1
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- LDTMPQQAWUMPKS-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=CCl LDTMPQQAWUMPKS-UHFFFAOYSA-N 0.000 description 1
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
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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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Abstract
本发明公开了气相氟化合成反式‑1‑氯‑3,3,3‑三氟丙烯用催化剂及合成方法。所公开的催化剂由活性组分M和载体MgF2组成,其中活性组分M选自Co3+、Ni2+、Fe3+、Zn2+、La3+、Al3+、Ga3+、Mn4+和Cu2+中的一种或两种以上,所述活性组分质量占催化剂总质量的5%~20%。所公开合成方法是以HCC‑240fa和氟化氢为原料采用气相氟化法合成反式‑1‑氯‑3,3,3‑三氟丙烯,所用催化剂为本发明的催化剂。本发明的催化剂具有较好的寿命和较高的催化活性,在气相催化HCC‑240fa一步氟化高选择性合成E‑HCFO‑1233zd反应中,催化剂连续运行1000h,HCC‑240fa转化率大于99%。
Description
技术领域
本发明涉及一种催化剂,具体涉及一种气相催化1,1,1,3,3-五氯丙烷一步氟化高选择性合成反式-1-氯-3,3,3-三氟丙烯用环保催化剂。
背景技术
近年来,研究表明采用反式-1-氯-3,3,3-三氟丙烯(E-HCFO-1233zd)发泡体系合成的PU硬泡综合性能良好,绝热性能优异,能够满足绝热保温行业的需求。更重要的是,E-HCFO-1233zd的ODP仅为0.00024,GWP只有5.0,毒性低,常态下不燃,使用安全,因此被公认为最新一代环保含氟发泡剂。此外,E-HCFO-1233zd还可用作高温热泵工质、离心机制冷剂、溶剂和含氟中间体等。
近年来,E-HCFO-1233zd合成技术已成为国内外氟化工领域最为活跃的研究课题之一。已报道的E-HCFO-1233zd合成路线有十多条,起始原料有1,1,1,3,3-五氯丙烷(HCC-240fa)、1,1,3,3-四氯-2-丙烯、1,1,1,2,3,3-六氯丙烷、1,1,1-三氟-2,3-二氯丙烷、1,1,1,3,3-五氟丙烷、1,1,1,3-四氟丙烯、三氟氯丙烯和三氟甲烷等。综合考虑原料来源、生产工艺和三废等因素,在实际工业化生产中被采用的合成路线主要是以HCC-240fa为原料,无水氟化氢为氟源,经液相或气相氟化反应合成E-HCFO-1233zd。
中国专利CN107652160中以TiCl4与KF的组合物为催化剂,反应温度范围80~130℃,液相反应压力1.25~2.0MPa。目前,采用液相氟化法合成E-HCFO-1233zd存在催化剂稳定性差、难回收利用的问题,且该工艺设备腐蚀严重、三废多、污染大。气相法是以Cr2O3/Al2O3为催化剂,在150~300℃条件下,HCC-240fa在气相中与氟化氢反应生成E-HCFO-1233zd。气相法污染小,产率高,易于连续化生产,是最具前景的工业化工艺。但是由于铬是具有强毒性的致癌物质,由此产生的潜在铬污染与环境友好要求相背离,这使整个工业链面临巨大的环保压力。除此以外,铬系催化剂的表面酸性较强,在合成E-HCFO-1233zd反应中选择性差、极易积碳失活。
发明内容
针对现有技术存在的问题与不足,本发明首先提供了一种气相氟化合成反式-1-氯-3,3,3-三氟丙烯用催化剂。
为此,本发明所提供的催化剂由活性组分M和载体MgF2组成,其中活性组分M选自Co3+、Ni2+、Fe3+、Zn2+、La3+、Al3+、Ga3+、Mn4+和Cu2+中的一种或两种以上,所述活性组分质量占催化剂总质量的5%~20%。
进一步,所述载体MgF2具有金红石相、具有纳米结构、比表面积大于120m2/g、500℃以下抗烧结。
可选的,M选自Fe3+和Al3+的组合。进一步可选的,所述Fe3+与Al3+的摩尔比为5:1~20:1。
同时,本发明提供了上述催化剂的制备方法。为此,所提供的制备方法包括:
(1)在150~240℃下镁盐的多元醇溶液与氟化试剂反应制备MgF2载体;所用镁盐选自硝酸镁、氯化镁、硫酸镁、甲醇镁、乙醇镁和乙酸镁中的一种;所用多元醇选自乙二醇、丙二醇、丙三醇、二縮乙二醇中的一种或两种以上组合;所用氟化试剂选自氟化氢的水溶液、氟化氢的醇溶液或氟化氢的醚溶液;
(2)通过分步浸渍、等体积浸渍或共浸渍的方法,将含M的盐溶液负载到MgF2载体上,接着老化后在300-500℃进行焙烧处理获得催化剂前驱体;所述含M的盐选自硝酸盐、氯化物和硫酸盐中的一种或两种以上组合;
(3)在150~400℃下对催化剂前驱体进行氟化处理制得M/MgF2催化剂;氟化处理所用氟试剂选自氟化氢、二氯二氟甲烷、一氯二氟甲烷或一氯三氟甲烷。
可选的,所述步骤(1)中Mg2+与氟化氢的摩尔比为1:3~12。
进一步,本发明提供了反式-1-氯-3,3,3-三氟丙烯的合成方法。所提供的方法以HCC-240fa和氟化氢为原料采用气相氟化法合成反式-1-氯-3,3,3-三氟丙烯,气相氟化法所用催化剂为上述催化剂。
可选的,本发明的反式-1-氯-3,3,3-三氟丙烯的合成方法中反应温度为200-260℃,反应物料与催化剂接触时间为4-20s,氟化氢与HCC-240fa的摩尔比范围是(5-40):1。
与现有技术相比,本发明的催化剂具有较大的比表面积及抗烧结性能,400℃焙烧后氟化镁载体的比表面积大于120m2/g,掺杂活性组分后比表面积大于250m2/g;并且具有较好的寿命和较高的催化活性,在气相催化HCC-240fa一步氟化高选择性合成E-HCFO-1233zd反应中,催化剂连续运行1000h,HCC-240fa转化率大于99%;同时具有高选择性,E-HCFO-1233zd选择性维持大于90.0%,且E/Z比大于12。
附图说明
图1为实施例2制得的MgF2载体的X射线粉末衍射图;
图2为实施例2制得的催化剂中MgF2载体的高倍透射电镜图;
图3为实施例2不同焙烧温度得到催化剂中MgF2载体的N2吸附脱附等温曲线及相应比表面积;
图4为实施例3中得到Al-Fe/MgF2催化剂的N2吸附脱附等温曲线及相应比表面积。
具体实施方式
除非另有说明,本文中的术语根据相关领域技术人员的常规认识理解。
下面给出本发明的具体实施例,但并不限制本发明的范围。
以下实施例中所用试剂、反应原料、设备等均为市售产品。
实施例1:
将128g Mg(NO3)2·6H2O溶解在500ml乙二醇溶液中,180℃下滴加50g的氢氟酸水溶液(40wt%),滴加完毕后继续搅拌10小时,得到MgF2载体;
将氟化镁载体常温老化10h后在400℃焙烧处理5h获得MgF2前驱体;最后在400℃下对MgF2前驱体在氟化氢气氛中进行氟化处理获得MgF2催化剂。
取MgF2催化剂20mL,转入固定床管式反应器中,升温至260℃并干燥2h后通入氟化氢气体,然后通入HCC-240fa,氟化氢与HCC-240fa的摩尔比为5:1,接触时间为20s,运行12h后产物经水、KOH或NaOH碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析,采用面积归一化法计算HCC-240fa的转化率及目标产物E-HCFO-1233zd选择性。经分析,HCC-240fa转化率为89.5%,E-HCFO-1233zd的选择性为82.0%,Z-HCFO-1233zd的选择性为11.4%,E/Z比为7.2。
实施例2:
将128g Mg(NO3)2·6H2O溶解在500ml丙二醇溶液中,150℃下滴加50g的氢氟酸醚溶液(40wt%),滴加完毕后继续搅拌12小时,得到MgF2载体;
将10.0g Fe(NO3)3·9H2O溶解到适量去离子水中得到浸渍液,然后将上述溶液等体积浸渍到90.0g MgF2载体上,之后常温老化8h后在相应温度焙烧处理5h获得Fe/MgF2前驱体;最后在150℃下对Fe/MgF2前驱体在氟化氢气氛中进行氟化处理获得Fe/MgF2催化剂;所得催化剂中MgF2载体具有金红石相(参见图1所示)及纳米球形结构(参见图2所示)、比表面积大于120m2/g,且500℃内抗烧结性能优越(参见图3所示,该图中所示温度为相应焙烧温度)。
取Fe/MgF2催化剂20mL,转入固定床管式反应器中,升温至245℃并干燥2h后通入氟化氢气体,然后通入HCC-240fa,氟化氢与HCC-240fa的摩尔比为25:1,接触时间为12s,运行12h后产物经水、KOH或NaOH碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析,采用面积归一化法计算HCC-240fa的转化率及目标产物E-HCFO-1233zd选择性。经分析,HCC-240fa转化率为99.9%,E-HCFO-1233zd的选择性为99.9%,Z-HCFO-1233zd的选择性为9.4%,E/Z比为9.5。
实施例3:
将128g Mg(NO3)2·6H2O溶解在500ml二縮乙二醇溶液中,240℃下滴加50g的氢氟酸醇溶液(40wt%),滴加完毕后继续搅拌6小时,得到MgF2载体;
将10.0g Fe(NO3)3·9H2O、3.0g Al(NO3)3·9H2O溶解到适量去离子水中得到浸渍液,然后将上述溶液等体积浸渍到所制MgF2载体上,之后常温老化12h后在400℃焙烧处理5h获得Al-Fe/MgF2前驱体;最后在400℃下对Al-Fe/MgF2前驱体在氟化氢气氛中进行氟化处理获得Al-Fe/MgF2催化剂。所制备催化剂的比表面大于250m2/g,具体参见图4。
取Al-Fe/MgF2催化剂20mL,转入固定床管式反应器中,升温至200℃并干燥2h后通入氟化氢气体,然后通入HCC-240fa,氟化氢与HCC-240fa的摩尔比为40:1,接触时间为4s,运行12h后产物经水、KOH或NaOH碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析,采用面积归一化法计算HCC-240fa的转化率及目标产物E-HCFO-1233zd选择性。经分析,HCC-240fa转化率为100%,E-HCFO-1233zd的选择性为91.2%,Z-HCFO-1233zd的选择性为7.5%,E/Z比为12.2。
实施例4:
在实施例4基础上,采用实施例3制备的Al-Fe/MgF2催化剂,进行不同时长的反应,相应效果见表1。
表1寿命试验
Claims (4)
1.一种反式-1-氯-3,3,3-三氟丙烯的合成方法,方法以HCC-240fa和氟化氢为原料采用气相氟化法合成反式-1-氯-3,3,3-三氟丙烯,其特征在于,气相氟化法所用催化剂由活性组分M和载体MgF2组成,其中活性组分M选自Fe3+或Fe3+和Al3+的组合,所述活性组分质量占催化剂总质量的5%~20%;
所述载体MgF2具有金红石相、具有纳米结构、比表面积大于120m2/g,500℃以下抗烧结;
所述催化剂的合成方法包括:
(1)在150~240℃下镁盐的多元醇溶液与氟化试剂反应制备MgF2载体;
所用镁盐选自硝酸镁、氯化镁、硫酸镁、甲醇镁、乙醇镁和乙酸镁中的一种;
所用多元醇选自乙二醇、丙二醇、丙三醇、二缩 乙二醇中的一种或两种以上组合;
所用氟化试剂选自氟化氢的水溶液、氟化氢的醇溶液或氟化氢的醚溶液;
(2)通过分步浸渍、等体积浸渍或共浸渍的方法,将含M的盐溶液负载到MgF2载体上,接着老化后在300-500℃进行焙烧处理获得催化剂前驱体;所述含M的盐选自硝酸盐、氯化物和硫酸盐中的一种或两种以上组合;
(3)在150~400℃下对催化剂前驱体进行氟化处理制得M/MgF2催化剂;氟化处理所用氟试剂选自氟化氢、二氯二氟甲烷、一氯二氟甲烷或一氯三氟甲烷。
2.根如权利要求1所述反式-1-氯-3,3,3-三氟丙烯的合成方法,其特征在于,所述Fe3+与Al3+的摩尔比为5:1~20:1。
3.如权利要求1所述反式-1-氯-3,3,3-三氟丙烯的合成方法,其特征在于,所述步骤(1)中Mg2+与氟化氢的摩尔比为1:(3~12)。
4.如权利要求1所述的反式-1-氯-3,3,3-三氟丙烯的合成方法,其特征在于,反应温度为200-260℃,反应物料与催化剂接触时间为4-20s,氟化氢与HCC-240fa的摩尔比范围是(5-40):1。
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