CN109499589B - 气相氟化合成1,1,1,3,3,3-六氟-2-丁烯用无铬环保催化剂 - Google Patents
气相氟化合成1,1,1,3,3,3-六氟-2-丁烯用无铬环保催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 title claims description 11
- 230000015572 biosynthetic process Effects 0.000 title claims description 10
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 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
- 238000003756 stirring Methods 0.000 claims description 4
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004338 Dichlorodifluoromethane Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 claims description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 3
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 239000007864 aqueous solution Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- NLOLSXYRJFEOTA-OWOJBTEDSA-N (e)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C\C(F)(F)F NLOLSXYRJFEOTA-OWOJBTEDSA-N 0.000 claims 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 4
- 239000012025 fluorinating agent Substances 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052804 chromium Inorganic materials 0.000 abstract description 8
- 239000011651 chromium Substances 0.000 abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
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- 238000006243 chemical reaction Methods 0.000 description 7
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 239000000306 component Substances 0.000 description 2
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- 239000004088 foaming agent Substances 0.000 description 2
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- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
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- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
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- 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
本发明公开一种气相催化CF3CHClCH2CCl3与无水氟化氢反应合成1,1,1,3,3,3‑六氟‑2‑丁烯用无铬环保催化剂及其制备方法。是为了解决传统铬基氟化催化剂存在环境问题，大量使用重金属铬会引起一系列严重的污染、健康等问题，以及传统铁基催化剂性能差的难题。本发明公开的催化剂组成为M/MgF2，其中基体MgF2为具有金红石相及纳米球形结构、比表面积大于120m2/g、500℃内抗烧结性能优越的高稳定性MgF2，活性组分M选自Co3+、Ni2+、Fe3+、Zn2+、La3+、Al3+、Ga3+、Mn4+、Cu2+中的一种或几种。催化剂制备包括以下步骤：(1)制备含镁源及掺杂金属离子的多元醇溶液，在150～240℃下滴加氟化试剂获得催化剂干凝胶；(2)将干凝胶在300～500℃下焙烧，最后在150～400℃下氟化处理制得无铬高性能催化剂。
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CF3CHClCH2CCl3与氟化氢反应合成1,1,1,3,3,3-六氟-2-丁烯用无铬环保催化剂。
背景技术
1,1,1,3,3,3-六氟-2-丁烯，简称HFO-1336，分子中不含氯原子，臭氧损耗潜值(ODP)为零，又因其含有双键，排入大气后能很快与OH自由基反应而降解，大气寿命较短(≤20d)，GWP值仅为9，因此使用时对环境影响小。此外，HFO-1336的物化性能与现有含氟发泡剂HCFC-141b、HFC-245fa相当，发泡、隔热性能优异，已被认为是新一代绿色发泡剂，具有良好的市场前景和经济效益。
迄今，在已知的众多合成路线中，以CF3CHClCH2CCl3及无水氟化氢为原料经气相氟化合成HFO-1336是核心步骤，受工业界的广泛关注，其中核心技术为相应的氟化催化剂。中国专利CN102884030B公开了一种以氧化铬为催化剂有效促进CF3CHClCH2CCl3及HF的气相氟化反应制得HFO-1336。中国专利CN104370690B公开了一种在Fe基气相氟化催化剂存在下使CF3CHClCH2CCl3及HF发生反应制得HFO-1336。
上述报道的气相氟化反应用催化剂使用到铬为核心组分，然而铬作为一种重金属元素，大量排放会对生态环境造成严重污染；尤其六价铬是一种剧毒物质对动物、人类健康构成极大的威胁。而Fe基气相氟化催化剂采用了传统的浸渍法、共沉淀法及共混法制备，颗粒尺寸大、热稳定性差、比表面积小导致催化剂活性低、选择性差。基于此，为应对日益严峻的环保形势和严格的法律法规，迫切需要设计、制备高性能无铬催化剂用于气相氟化CF3CHClCH2CCl3合成HFO-1336反应。
发明内容
针对现有技术存在的缺陷与不足，本发明的目的是提供一种不含铬、环境友好、活性高的气相氟化反应用催化剂。本发明的这种催化剂具有不含重金属、绿色环保、比表面积大、纳米球形结构、高温抗烧结能力好的特点，从而获得高活性、高稳定性的气相催化氟化反应性能。
传统铬基氟化催化剂比表面积大，一般在80～150m2/g，高比表面积创造出大量反应活性位，因而实现了气相氟化反应的高效转化。鉴于此，通过设计、构建在高温含氟气氛下同样可以稳定存在的高比表面积MgF2，进而通过掺杂其他金属离子实现其表面酸中心及织构特性的调控，即可同样获得具备催化气相氟化反应所需活性位。此外，通过控制MgF2尺寸在纳米尺度及球形结构，可大为改善传质效率，使得多相催化过程中宏观动力学反应行为得以改善并有效降低积碳速率。上述多重独特织构、结构的建立使得绿色环保型无铬高性能气相氟化催化剂的制备得以实现。
为了实现上述技术任务，本发明采用如下技术方案予以实现：
一种气相氟化合成1,1,1,3,3,3-六氟-2-丁烯用无铬环保催化剂，其特征在于所述催化剂组成为M/MgF2，其中基体MgF2为具有金红石相及纳米球形结构、比表面积大于120m2/g、500℃内抗烧结性能优越的高稳定性MgF2，活性组分M选自Co3+、Ni2+、Fe3+、Zn2+、La3 +、Al3+、Ga3+、Mn4+、Cu2+中的一种或几种，M质量占催化剂总质量的5％～20％；
该催化剂制备方法如下：
(1)在150～240℃下向含Mg2+及M的多元醇溶液中滴加氟化试剂，滴加完毕后继续搅拌6～12h，获得M/MgF2干凝胶；
所用Mg2+选自硝酸镁、氯化镁、硫酸镁、甲醇镁、乙醇镁、乙酸镁中的一种；
所用M选自硝酸盐、氯化物、硫酸盐中的一种或几种；
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几种；
所用氟化试剂选自氟化氢的水溶液、醇溶液、醚溶液中的一种；
Mg2+与氟化氢的摩尔比为1:3～12；
(2)在300～500℃下对(1)中所制干凝胶进行热处理，随后再于150～400℃下对热处理后干凝胶进行氟化处理制得M/MgF2催化剂；
热处理气氛选自空气、氮气、氢气气氛中的一种进行；
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、一氯三氟甲烷中的一种；
进一步所述气相氟化合成1,1,1,3,3,3-六氟-2-丁烯用无铬环保催化剂，其特征在于M为Fe3+、Cu2+的组合，Fe3+与Cu2+的摩尔比为1:0.2～1。
进一步所述气相氟化合成1,1,1,3,3,3-六氟-2-丁烯用无铬环保催化剂的制备方法，其特征在于所述氟化试剂的浓度为20wt.％～70wt.％。
进一步所述无铬环保催化剂，其特征在于催化剂用于CF3CHClCH2CCl3与氟化氢进行的气相催化氟化合成1,1,1,3,3,3-六氟-2-丁烯反应。
本发明的有益效果：本发明与现有技术相比，具有如下有益的技术效果：
①与传统铬基氟化催化剂相比，本发明提供了一种不含铬及其他重金属、环境友好的比表面积大、纳米球形结构、高温抗烧结能力好的MgF2基氟化催化剂及其制备方法；②与传统铁基氟化催化剂相比，本发明提供的制备方法可很容易实现对所制催化剂织构、结构及表面酸性的调变，可制得比表面积大于120m2/g、500℃内抗烧结性能优越的氟化镁基催化剂；③本发明对所用镁源无特别要求，适用性广，成本低；④本发明所制备的纳米球形氟化镁基催化剂，有助于物料在催化剂表面吸脱附、改善传质，进而提高反应效率、抑制积碳。
附图说明
图1为M/MgF2催化剂的代表性TEM图
具体实施方式
下面给出本发明的具体实施例，但并不限制本发明的范围。
催化剂性能评价如下：量取30mL催化剂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CF3CHClCH2CCl3，氟化氢与CF3CHClCH2CCl3的摩尔比为15:1，接触时间为6秒，运行12h后产物经水、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CF3CHClCH2CCl3的转化率及目标产物HFO-1336选择性。
实施例1：制备M/MgF2催化剂
将1.0M镁源及0.01～0.1M改性金属离子溶于50mL多元醇溶剂中，在150～240℃搅拌下将氟化试剂滴加到上述溶液中，滴加时间为15min，滴加完毕后再搅拌6～12h，得到M/MgF2干凝胶；然后在空气氛或氢气氛300～500℃下焙烧5h以上，最后在150～400℃程序升温对焙烧后材料进行氟化处理获得催化剂，氟试剂选用气体氟化氢、二氯二氟甲烷、一氯二氟甲烷、一氯三氟甲烷中任意一种。不同镁源、多元醇溶剂、促凝剂、氟化试剂、焙烧温度下制得的氟化镁织构性能见表1所示。
表1实施例1的氟化镁基催化剂的物化性质结果
实施例2
采用实施例1中相同方法制备M/MgF2催化剂，将其应用到气相氟化CF3CHClCH2CCl3合成HFO-1336反应中去，运行12h后，反应结果如下表：
表2实施例2的氟化镁基催化剂的反应评价结果
实施例3
采用实施例1中相同方法制备M/MgF2催化剂，将其应用到气相氟化CF3CHClCH2CCl3合成HFO-1336反应中去，运行12h后，反应结果如下表：
表3实施例3的氟化镁基催化剂的反应评价结果
Claims (4)
1.一种气相氟化合成1,1,1,4,4,4-六氟-2-丁烯用无铬环保催化剂，其特征在于所述催化剂组成为M/MgF2，其中基体MgF2为具有金红石相及纳米球形结构、比表面积大于120m2/g、500℃内抗烧结性能优越的高稳定性MgF2，活性组分M选自Co3+、Ni2+、Fe3+、Zn2+、La3+、Al3+、Ga3+、Mn4+、Cu2+中的一种或几种，M质量占催化剂总质量的5％～20％；
该催化剂制备方法如下：
(1)在150～240℃下向含Mg2+及M的多元醇溶液中滴加氟化试剂，滴加完毕后继续搅拌6～12h，获得M/MgF2干凝胶；
所用Mg2+选自硝酸镁、氯化镁、硫酸镁、甲醇镁、乙醇镁、乙酸镁中的一种；
所用M选自硝酸盐、氯化物、硫酸盐中的一种或几种；
所用多元醇选自乙二醇、丙二醇、丙三醇、二缩 乙二醇中的一种或几种；
所用氟化试剂选自氟化氢的水溶液、醇溶液、醚溶液中的一种；
Mg2+与氟化氢的摩尔比为1:3～1:12；
(2)在300～500℃下对(1)中所制干凝胶进行热处理，随后再于150～400℃下对热处理后干凝胶进行氟化处理制得M/MgF2催化剂；
热处理气氛选自空气、氮气、氢气气氛中的一种进行；
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、一氯三氟甲烷中的一种。
2.根据权利要求1所述气相氟化合成1,1,1,4,4,4-六氟-2-丁烯用无铬环保催化剂，其特征在于M为Fe3+、Cu2+的组合，Fe3+与Cu2+的摩尔比为1:1～1:0.2。
3.根据权利要求1所述气相氟化合成1,1,1,4,4,4-六氟-2-丁烯用无铬环保催化剂的制备方法，其特征在于所述氟化试剂的浓度为20wt.％～70wt.％。
4.权利要求1所述无铬环保催化剂，用于CF3CHClCH2CCl3与氟化氢进行的气相催化氟化合成1,1,1,4,4,4-六氟-2-丁烯反应。
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