CN103816927A - 一种用于合成乙撑亚胺的催化剂、制备方法及应用 - Google Patents
一种用于合成乙撑亚胺的催化剂、制备方法及应用 Download PDFInfo
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- CN103816927A CN103816927A CN201310698874.4A CN201310698874A CN103816927A CN 103816927 A CN103816927 A CN 103816927A CN 201310698874 A CN201310698874 A CN 201310698874A CN 103816927 A CN103816927 A CN 103816927A
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- Prior art keywords
- catalyst
- carrier
- ethylenimine
- ion
- ions
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- -1 iron ions Chemical class 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001414 amino alcohols Chemical class 0.000 claims abstract description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 6
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000011148 porous material Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000009938 salting Methods 0.000 description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229940102253 isopropanolamine Drugs 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Chemical compound O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- WGAOZGUUHIBABN-UHFFFAOYSA-N 1-aminopentan-1-ol Chemical compound CCCCC(N)O WGAOZGUUHIBABN-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- 125000004807 2-methylethylene group Chemical group [H]C([H])([H])C([H])([*:2])C([H])([H])[*:1] 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KRUMYKPXYLURIT-UHFFFAOYSA-N aziridin-2-ylmethanol Chemical compound OCC1CN1 KRUMYKPXYLURIT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052796 boron Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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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
- B01J23/78—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 alkali- or alkaline earth metals
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- B01J27/182—Phosphorus; Compounds thereof with silicon
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- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Thermal Sciences (AREA)
- Catalysts (AREA)
- Nanotechnology (AREA)
Abstract
本发明涉及一种用于合成乙撑亚胺的催化剂、制备方法及应用。所涉及的催化剂包括载体和负载在载体上的金属离子，所述载体为含钛、硅和磷元素的复合氧化物；所述金属离子为镁离子、铁离子和铯离子，且镁离子、铁离子、铯离子的摩尔比为：1～10:1:0.1，所有金属离子的质量为载体质量的0.5%～10%。所涉及的制备方法是将催化剂前驱体在350℃～650℃下，焙烧制得催化剂，所述催化剂前驱体为载体、镁的可溶性盐、铁的可溶性盐与铯的可溶性盐的混合物。本发明还提供了上述催化剂用于以氨基醇为原料合成乙撑亚胺中的应用。本发明的催化剂，与一般要求温度高于400℃相比降低显著降低了反应温度。制得的催化剂能够催化氨基醇分子内脱水反应，并具有较优的选择性。
Description
技术领域
本发明属于化工技术领域，具体涉及一种合成乙撑亚胺用的催化剂、制备方法及应用。
背景技术
乙撑亚胺，又称氮丙啶，是一种重要的精细化工产品，在医药、农药、高能燃料、键合剂等领域有着广泛的用途。
乙撑亚胺最初的工业制法为液相法，以单乙醇胺为原料，采用浓硫酸为脱水剂，反应中需要加入浓碱，成本较高且产生无用的无机盐副产，造成了严重的环境污染。
US4301036公开了钨氧化物及硅氧化物组成的催化剂，及其在合成乙撑亚胺中的应用。
US4488591中公开了使用铌/钽氧化物与碱土金属和（或）铁/铬氧化物作为催化剂合成乙撑亚胺的方法。
US433717公开了一种用Nb或Ta氧化物与碱土金属氧化物(BaO)的复合氧化物催化剂生产乙撑亚胺的方法。先将Nb或Ta的氯化物制成负载所用浸渍溶液，负载于载体(0.1m2/g～1.0m2/g)表面，经450～550℃焙烧处理2～4h，制得催化剂。反应温度400℃，乙醇胺转化率13.87(mol)%，乙撑亚胺选择性82.09(mol)%，并有少量乙醛、乙胺、吡嗪及烷基吡嗪生成。
CN2007100109625公开了一种用于合成乙撑亚胺类化合物的催化剂。该催化剂组成为：XaYbOc(HZSM-5)d，其中X选自碱金属，Y选自磷或硼元素，O为氧元素，a、b、c、d是X、Y、O、ZSM-5沸石的摩尔比，当d=1时，a=0.01～0.1，b=0.001～0.1，c值取决于a、b。反应温度420℃，乙醇胺转化率84(mol)%，乙撑亚胺选择性84(mol)%。
乙撑亚胺催化剂比表面积和酸碱强度与催化剂活性、选择性密切相关。一般比表面积较大时，负载的催化剂才具有较高催化活性，而该类催化剂的制备需经过高温（≥600℃）焙烧步骤，由于强烈放热反应形成的局部高温，使催化剂烧结后比表面积大幅度降低，导致催化剂活性和选择性降低。考虑工业过程中的经济性因素，通常追求催化剂的更高选择性和更长寿命比物料转化率更重要，以保证物料转化成尽可能多的所需目标产品而减少不必要副产物的生成。
现有技术中，氨基醇的分子内脱水反应在较低温度（～370℃）下，催化剂活性和选择性较低，反应温度高，一般要求温度高于400℃反应才能较快地进行，但容易发生脱氨基及分子间缩合反应的发生而使副产物增多，导致乙撑亚胺选择性降低，一般重量选择性低于65%，且使用寿命短。
发明内容
针对现有技术的缺陷或不足，本发明的目的之一在于提供一种比表面积大、孔容大、低温活性高、使用寿命长的用于合成乙撑亚胺的催化剂。
为此，本发明提供的催化剂包括载体和负载在载体上的金属离子，所述载体为含钛、硅和磷元素的复合氧化物；所述金属离子为镁离子、铁离子和铯离子，且镁离子、铁离子、铯离子的摩尔比为：1～10:1:0.1，所有金属离子的质量为载体质量的0.5%～10%。
本发明的另一目的在于提供上述载体的制备方法及催化剂的制备方法。
为此，所述提供的载体的制备方法包括：
（1）将二氧化硅、二氧化钛、磷酸铵盐混合，以氧化物形式计SiO2:TiO2:P2O5重量比为5～20:80:15～5，再加入粘结剂，捏合，挤条成形，干燥，600～900℃焙烧，制得含钛、硅和磷元素的复合氧化物；
所述磷酸铵盐为磷酸铵、磷酸氢二铵或磷酸二氢铵；
所述粘结剂为硅溶胶或拟薄水铝石；
（2）在无氧、100℃～200℃条件下，步骤（1）所得复合氧化物与氟化氢进行氟化反应制得催化剂载体。
优选的，所述粘结剂的用量为二氧化钛的质量的10%～30%。
所提供的催化剂的制备方法包括：
将催化剂前驱体在350℃～650℃下，焙烧制得催化剂，所述催化剂前驱体为载体、镁的可溶性盐、铁的可溶性盐与铯的可溶性盐的混合物。
针对现有技术缺陷或不足，本发明还提供了上述催化剂用于以氨基醇为原料合成乙撑亚胺中的应用。
优选的，在上述催化剂存在条件下，以氨基醇为原料合成乙撑亚胺时，反应温度为370℃～385℃。
与现有技术相比，本发明的有益效果在于：
（1）本发明的合成乙撑亚胺催化剂，采用在100℃～200℃温度下，选用SiO2作为造孔剂，利用载体中的SiO2链型结构及易与HF反应形成挥发性氟化硅化合物的特点，一经被氟化除去后就会流下连续孔道结构，从而增加比表面积和孔容，制备具有高的比表面积和大孔容的催化剂，比表面积≥40m2/g，孔容≥0.20mL/g，平均孔径≤9nm，改善了反应原料及产品在催化剂孔内的扩散效果。
（2）本发明的合成乙撑亚胺催化剂，与一般要求温度高于400℃相比降低显著降低了反应温度。制得的催化剂能够催化氨基醇分子内脱水反应，并具有最佳的选择性，在370℃时单乙醇胺转化率可达38%，乙撑亚胺选择性可达95%。
（3）本发明的催化剂使用寿命长，活性基本维持稳定，1000h内单乙醇胺转化率可达32%，乙撑亚胺选择性可达96%。
（4）本发明的催化剂能用于多种氨基醇分子内脱水反应中。
具体实施方式
为了实现上述任务，本发明采取如下的技术解决方案：采用在100℃～200℃温度下，选用SiO2作为造孔剂，利用载体中的SiO2链型结构及易与HF反应形成挥发性氟化硅化合物的特点，一经被氟化除去后就会流下连续孔道结构，从而增加比表面积和孔容，具有高的比表面积和大孔容。再经浸渍步骤浸渍活性组分，制得催化剂。
本发明粘结剂的用量根据步骤（1）中的混合物能够挤条成形确定。其中所用硅溶胶为二氧化硅质量百分含量为20%～30%的水溶液。
本发明所使用的镁的可溶性盐优选硝酸盐或氯化物，铁的可溶性盐优选硝酸盐或氯化物，铯的可溶性盐优选硝酸盐或氯化物。
本发明制备的合成乙撑亚胺催化剂，其活性评价装置可在普通固定床管式反应器中进行，反应器尺寸为
将催化剂装填进反应器，加热至反应温度，通过计量泵进料，反应后取样分析，分析仪器为GC-930气相色谱仪。
本发明所述的乙醇胺转化率、乙撑亚胺选择性定义如下：
乙醇胺转化率CMEA，%=1－产物液中乙醇胺的色谱面积百分数
产物选择性S，%=产物液中乙撑胺的色谱面积百分数/产物液中扣除乙醇胺的色谱面积百分数
本发明合成乙撑亚胺用的催化剂，包括用于其它的氨基醇的分子内脱水反应中，氨基醇为具有邻位结构的氨基醇类化合物，其结构为：
R1为氢、甲基、乙基或羟甲基，R2为氢、甲基、乙基或羟甲基，A为羟基或氨基，B为羟基或氨基，且A和B不同时为羟基或氨基；其中氨基醇为乙醇胺、异丙醇胺、3-氨基-1,2-丙二醇、2-氨基-2-甲基-1-丙醇，也可以是其它氨基丁醇、氨基戊醇。优选3-氨基-1,2-丙二醇、2-氨基-2-甲基-1-丙醇。
以下是发明人给出的实施例，这些实施例是较优的例子，主要用于解释和进一步理解本发明的技术方案，本发明不限于这些实施例。
实施例1：
按照以氧化物计SiO2:TiO2:P2O5重量比为5:80:15化学计量比配置。
将白炭黑10g，二氧化钛160g,磷酸氢二铵55.7g混合均匀后，再加入硅溶胶，硅溶胶加入量为二氧化钛的质量的20%，捏合，挤条成形，120℃干燥6h，在马弗炉中350℃焙烧6h，在1℃/min程序升温至650℃焙烧6h，制得钛、硅、磷组成的复合氧化物。
将钛、硅、磷组成的复合氧化物冷却后装入管式反应器，升温至150℃，然后用体积比为HF:N2=1:5的混合物氟化2h，得到催化剂载体。该载体用低温氮吸附法测定其比表面积42m2/g，孔容0.22mL/g，平均孔径5.6nm。
按照镁离子、铁离子、铯离子的摩尔比为10：1：0.1负载，取硝酸镁29.6g、硝酸铁4.84g、硝酸铯0.4g配置成溶液，将得到的催化剂载体浸渍8h，取出后干燥，在450℃下用空气焙烧制得催化剂。
将上述催化剂装填进反应器，装填量30mL，加热至反应温度370℃，氮气作为保护气体，氮气与单乙醇胺气体体积比16，以标准状态计气体总空速：3600h-1，反应在常压或真空条件下进行，反应8h后，反应气体水吸收后取样分析，单乙醇胺转化率38%，乙撑亚胺选择性95%，反应1000h后，单乙醇胺转化率32%，乙撑亚胺选择性96%。
实施例2：
实施例2与实施例1中制备过程基本相同，不同的是按照SiO2:TiO2:P2O5重量比为10:80:10化学计量比配置。催化剂载体用低温氮吸附法测定其比表面积43.2m2/g，孔容0.21mL/g，平均孔径5.8nm。
按照金属离子为载体质量的5.3%负载，镁离子、铁离子、铯离子的摩尔比为8:1:0.1，配置可溶性金属盐溶液，将得到的催化剂载体浸渍8h，取出后干燥，在350℃下氮气中焙烧制得催化剂。
将上述催化剂装填进反应器，装填量30mL，加热至反应温度380℃，氮气作为保护气体，氮气与单乙醇胺气体体积比16，以标准状态计气体总空速：3000h-1，反应在常压或真空条件下进行，反应8h后，反应气体水吸收后取样分析，单乙醇胺转化率68%，乙撑亚胺选择性96%，反应1000h后，单乙醇胺转化率56%，乙撑亚胺选择性94%。
实施例3：
实施例2与实施例1中制备过程基本相同，不同的是按照SiO2:TiO2:P2O5重量比为15:80:5化学计量比配置。催化剂载体用低温氮吸附法测定其比表面积46.8m2/g，孔容0.25mL/g，平均孔径6.1nm。
按照金属离子为载体质量的0.5%负载，镁离子、铁离子、铯离子的摩尔比为1:1:0.1，配置可溶性金属盐溶液，将得到的催化剂载体浸渍8h，取出后干燥，在650℃下用空气焙烧制得催化剂。
将上述催化剂装填进反应器，装填量30mL，加热至反应温度380℃，氮气作为保护气体，氮气与单乙醇胺气体体积比16，以标准状态计气体总空速：3200h-1，反应在常压或真空条件下进行，反应8h后，反应气体水吸收后取样分析，单乙醇胺转化率86%，乙撑亚胺选择性92%。
实施例4：
实施例4操作与实施例1基本相同，所不同的是按照金属离子为载体质量的10.0%负载，镁离子、铁离子、铯离子的摩尔比为5:1:0.1，配置可溶性金属盐溶液，将得到的催化剂载体浸渍8h，取出后干燥，在650℃下用空气焙烧制得催化剂。
采用异丙醇胺为反应原料，催化反应条件及分析条件同实施例1。异丙醇胺转化率52%，2-甲基乙撑亚胺选择性86%。
实施例5：
实施例5操作与实施例2基本相同，所不同的是按照金属离子为载体质量的8.5%负载，镁离子、铁离子、铯离子的摩尔比为3:1:0.1，配置可溶性金属盐溶液，将得到的催化剂载体浸渍8h，取出后干燥，在650℃下用空气焙烧制得催化剂。
采用3-氨基-1,2-丙二醇为反应原料，反应温度为385℃。催化反应条件及分析条件同实施例1。3-氨基-1,2-丙二醇转化率62%，3-羟基-1-氮杂环丁烷选择性53.2%，2-羟甲基乙撑亚胺选择性24.7%，3-氨基环氧丙烷选择性9.1%，其它13.0%。
实施例6：
实施例6操作与实施例3基本相同，所不同的是采用2-氨基-2-甲基-1-丙醇为反应原料，反应温度为379℃。催化反应条件及分析条件同实施例1。2-氨基-2-甲基-1-丙醇转化率47%，2,2-二甲基乙撑亚胺选择性87.5%。
Claims (6)
1.一种用于合成乙撑亚胺的催化剂，其特征在于，该催化剂包括载体和负载在载体上的金属离子，所述载体为含钛、硅和磷元素的复合氧化物；所述金属离子为镁离子、铁离子和铯离子，且镁离子、铁离子、铯离子的摩尔比为：1～10:1:0.1，所有金属离子的质量为载体质量的0.5%～10%。
2.如权利要求1所述的用于合成乙撑亚胺的催化剂，其特征在于，所述载体的制备包括：
（1）将二氧化硅、二氧化钛、磷酸铵盐混合，以氧化物形式计SiO2:TiO2:P2O5重量比为5～20:80:15～5，再加入粘结剂，捏合，挤条成形，干燥，600～900℃焙烧，制得含钛、硅和磷元素的复合氧化物；
所述磷酸铵盐为磷酸铵、磷酸氢二铵或磷酸二氢铵；
所述粘结剂为硅溶胶或拟薄水铝石；
（2）在无氧、100℃～200℃条件下，步骤（1）所得复合氧化物与氟化氢进行氟化反应制得催化剂载体。
3.如权利要求2所述的用于合成乙撑亚胺的催化剂，其特征在于，所述粘结剂的用量为二氧化钛的质量的10%～30%。
4.如权利要求2所述的用于合成乙撑亚胺的催化剂，其特征在于，该催化剂的制备方法包括：
将催化剂前驱体在350℃～650℃下，焙烧制得催化剂，所述催化剂前驱体为载体、镁的可溶性盐、铁的可溶性盐与铯的可溶性盐的混合物。
5.权利要求1-4任一权利要求所述的催化剂用于以氨基醇为原料合成乙撑亚胺中的应用。
6.如权利要求5所述的应用，其特征在于，反应温度为370℃～385℃。
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| WO2015090084A1 (zh) * | 2013-12-18 | 2015-06-25 | 西安近代化学研究所 | 一种用于合成乙撑亚胺的催化剂、制备方法及应用 |
| CN106890666A (zh) * | 2017-02-09 | 2017-06-27 | 西安近代化学研究所 | 一种氯化氢高效转化制氯气的催化剂 |
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| WO2015090084A1 (zh) * | 2013-12-18 | 2015-06-25 | 西安近代化学研究所 | 一种用于合成乙撑亚胺的催化剂、制备方法及应用 |
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| CN104475144A (zh) * | 2014-11-28 | 2015-04-01 | 西安近代化学研究所 | 一种氨基醇类化合物分子内脱水用催化剂的原位再生方法 |
| CN106890666A (zh) * | 2017-02-09 | 2017-06-27 | 西安近代化学研究所 | 一种氯化氢高效转化制氯气的催化剂 |
| CN106890666B (zh) * | 2017-02-09 | 2019-06-28 | 西安近代化学研究所 | 一种氯化氢高效转化制氯气的催化剂 |
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| Publication number | Publication date |
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| US9920008B2 (en) | 2018-03-20 |
| CN103816927B (zh) | 2015-12-30 |
| WO2015090084A1 (zh) | 2015-06-25 |
| US20160318863A1 (en) | 2016-11-03 |
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