CN113019379A - Catalyst for liquid-phase hydrogenation of olefine aldehyde and preparation method and application thereof - Google Patents
Catalyst for liquid-phase hydrogenation of olefine aldehyde and preparation method and application thereof Download PDFInfo
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- CN113019379A CN113019379A CN202110291957.6A CN202110291957A CN113019379A CN 113019379 A CN113019379 A CN 113019379A CN 202110291957 A CN202110291957 A CN 202110291957A CN 113019379 A CN113019379 A CN 113019379A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 239000007791 liquid phase Substances 0.000 title claims abstract description 24
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 4
- 238000002360 preparation method Methods 0.000 title abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 241000219782 Sesbania Species 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910001679 gibbsite Inorganic materials 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 150000002972 pentoses Chemical class 0.000 claims description 4
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 150000003641 trioses Chemical class 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 150000001299 aldehydes Chemical class 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- 238000001354 calcination Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 239000012018 catalyst precursor Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- GADNZGQWPNTMCH-NTMALXAHSA-N (z)-2-propylhept-2-enal Chemical compound CCCC\C=C(C=O)\CCC GADNZGQWPNTMCH-NTMALXAHSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- MMFCJPPRCYDLLZ-CMDGGOBGSA-N (2E)-dec-2-enal Chemical compound CCCCCCC\C=C\C=O MMFCJPPRCYDLLZ-CMDGGOBGSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- MMFCJPPRCYDLLZ-UHFFFAOYSA-N dec-2-enal Natural products CCCCCCCC=CC=O MMFCJPPRCYDLLZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000008093 supporting effect Effects 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/78—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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for liquid-phase hydrogenation of olefine aldehyde, a preparation method and application thereof, wherein the catalyst comprises the following components in percentage by mass: NiO 10-30 wt%, MgO 0.5-15 wt%, TiO20.5-15%, and the balance of gamma Al2O3(ii) a Wherein the carrier is MgO-TiO2‑γAl2O3The active component is Ni element. The catalyst has high activity and high selectivity, the preparation method is simple, and the catalyst is prepared byThe material has low price, is suitable for the liquid phase hydrogenation of olefine aldehyde, and is particularly suitable for producing plasticizer alcohol with high molecular weight.
Description
Technical Field
The invention relates to the field of preparing alcohol by aldehyde hydrogenation, in particular to a catalyst for liquid-phase hydrogenation of olefine aldehyde and a preparation method and application thereof.
Background
The phthalate plasticizer is an important chemical product additive, and the main production raw materials are phthalic anhydride and plasticizer alcohol. The plasticizer alcohol mainly refers to C4-C13 saturated fatty alcohol, wherein 2-propyl heptanol (2-PH) adopts cheap mixed butylene as a production raw material, has higher molecular weight, can produce oil-resistant, water-resistant and low-volatility PVC products, and meets the special requirements of a plurality of application fields. 2-PH can be obtained by the complete hydrogenation of 2-propyl-2-heptenal (PBA), which is a typical α, β -unsaturated aldehyde containing both C ═ C and O bonds in the molecule. The catalyst which takes Ni as a main active component and is commonly used for the hydrogenation of olefine aldehyde in industry has the characteristics of low hydrogenation activity temperature and low operation energy consumption, but because the physicochemical properties of the bond energy of C ═ C bond and C ═ O bond are different, competitive hydrogenation reaction can occur, and the obtained product is often C ═ C bond or C ═ O bond and the mixture of the C ═ C bond and the C ═ O bond which are both subjected to hydrogenation saturation. Therefore, the development of catalysts with high activity and selectivity for hydrogenation of both C ═ C bonds and C ═ O bonds is the focus of research on catalytic systems for the hydrogenation of olefins.
The aldehyde hydrogenation process is divided into gas phase hydrogenation and liquid phase hydrogenation. The volume of the gas phase hydrogenation process reactor is large, when the boiling point of the reaction raw material is higher, the energy consumption is correspondingly increased, and the actual load often cannot meet the design requirement. And the liquid phase hydrogenation adopts a low-temperature high-pressure process, overcomes the defect of gas phase hydrogenation, and is suitable for producing high-carbon alcohol.
CN104971733A proposes a catalyst for synthesizing 2-propyl-1-heptanol, which is prepared by combining hydrothermal synthesis and kneading methods by taking Ni, Mo, Zn and Cu as active components, and prepares the 2-propyl-1-heptanol by hydrogenating 2-propyl-2-heptenal, and has higher conversion rate and selectivity.
CN107486207A proposes an aldehyde liquid phase hydrogenation catalyst. The mass content of nickel in the catalyst is 15-30%, and the catalyst is prepared by adopting a coprecipitation method. The preparation process is simple and easy to realize, and the problem of unstable catalyst performance caused by unstable control of the previous catalyst production process is solved.
CN104513135A proposes a method for preparing decanol by liquid phase hydrogenation of decenal, which uses at least two reactors, the first reactor uses Ni-based or Cu-based catalyst supported by oxide, and the second reactor uses raney Ni catalyst supported by organic polymer. Although the method can obtain the hydrogenation product with less residual olefine aldehyde and high product yield, the operation is complicated by adopting a plurality of reactors, and the second reactor uses a Raney Ni catalyst, so the cost is higher and the storage condition is harsh.
CN104513131A discloses a method for preparing decanol by liquid-phase hydrogenation of decenal. The catalyst adopts organic polymer as a carrier, the active metal is Raney alloy particles, and the loading capacity is 40-80 wt%. The catalyst has high activity and good selectivity, but the catalyst is expensive and has great danger in storage and transportation.
CN100398202C discloses a preparation method of a Cu-Zn-Al vapor phase aldehyde hydrogenation catalyst, which comprises 10-60% of CuO, 20-80% of ZnO and 0.1-20% of Al as active components2O3And tabletting and molding the graphite serving as a carrier to obtain the catalyst. The method of stepwise continuous coprecipitation is adopted, the intermittent feeding mode which is performed stepwise is changed into the continuous feeding mode, the prepared catalyst has large specific surface and pore volume, the dispersion degree of the active metal copper is high, and the activity of the catalyst is greatly improved. However, the gas phase reaction mode needs to gasify the raw material aldehyde, and for some unsaturated aldehydes, the unsaturated aldehydes are easy to polymerize in the gasification phase change process, so that the selectivity of the target product alcohol is reduced.
CN111282560A provides a coked wax oil hydrogenation catalyst and a preparation method thereof, wherein a titanium modified alumina carrier is used, and a hydrogenation catalyst which has large specific surface pore volume, concentrated pore diameter and uniform metal active component distribution is prepared by changing the introduction mode and the addition amount of titanium, and shows higher hydrodenitrogenation activity in the coked wax oil hydrogenation treatment.
As can be seen from the above patents, for the hydrogenation of long carbon alkenals of high molecular weight, the catalyst is required to have the characteristics of large specific surface, large pore volume and concentrated pore diameter; the current olefine aldehyde hydrogenation production process has defects, the two-step process is complex, and the use of noble metals and imported catalysts increases the production cost; the liquid phase hydrogenation process has low production energy consumption and universal applicability; although Mg has a positive effect on the coking resistance of a hydrotreating catalyst, the existing research shows that the effect which can be actually exerted is not very obvious because the Mg in the modified alumina carrier is not uniformly distributed due to the capillary condensation phenomenon, so that the catalyst has high activity and high selectivity, and also meets the economic and efficient production indexes, which is a serious difficulty in developing the olefine aldehyde hydrogenation catalyst.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a catalyst for liquid-phase hydrogenation of olefine aldehyde, a preparation method and application thereof, wherein the catalyst has high activity and high selectivity, the preparation method is simple, the raw materials for preparing the catalyst are low in price, and the catalyst is suitable for liquid-phase hydrogenation of olefine aldehyde and is particularly suitable for producing high-molecular-weight plasticizer alcohol.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst for liquid-phase hydrogenation of olefine aldehyde, wherein the catalyst comprises the following components by mass percent: NiO 10-30 wt%, MgO 0.5-15 wt%, TiO20.5-15%, and the balance of gamma Al2O3；
Wherein the carrier is MgO-TiO2-γAl2O3The active component is Ni element.
The catalyst provided by the invention has the advantages that by introducing magnesium and titanium and adopting water-soluble organic matters in the preparation process, the anti-coking performance of the catalyst in the hydrogenation process is improved, the distribution of Mg is more uniform, and the service life of the catalyst is effectively prolonged.
In the present invention, NiO in the catalyst may be contained in an amount of 10 to 30% by mass, for example, 10%, 15%, 20%, 25%, or 30%, but is not limited to the values listed above, and other values not listed above are also applicable.
In the present invention, the amount of MgO in the catalyst is 0.5 to 15% by mass, and may be, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, TiO in the catalyst2The content of the organic solvent is 0.5 to 15% by mass, and may be, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15% by mass, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Are preferred techniques of the present inventionThe catalyst comprises the following components in percentage by mass: NiO 15-20 wt%, MgO 5-10 wt%, and TiO28-12% of gamma Al2O3。
In a second aspect, the present invention provides a process for preparing a catalyst as defined in the first aspect, the process comprising the steps of:
(1) mixing gamma alumina powder, a titanium source, a magnesium source and a water-soluble organic matter, and sequentially carrying out solid-liquid separation, first drying and first roasting to obtain an intermediate carrier;
(2) mixing the intermediate carrier obtained in the step (1), an alumina precursor and an additive, and then sequentially carrying out molding, second drying and second roasting to obtain a carrier;
(3) and (3) carrying out impregnation treatment on the carrier obtained in the step (2) by using a nickel-containing solution, carrying out solid-liquid separation, and then sequentially carrying out third drying and third roasting to obtain the catalyst.
According to the preparation method of the catalyst, the carbon remained after the water-soluble organic solvent is introduced and roasted in the preparation process can be uniformly distributed on the surface of the gamma alumina forming the pore channel as much as possible, the carbon has a supporting effect on the pore channel of the gamma alumina, the pore channel collapse is prevented in the carrier forming process, and the performance of the catalyst is further improved.
As a preferred technical solution of the present invention, the titanium source in step (1) includes 1 or a combination of at least 2 of isopropyl titanate solution, titanium sulfate solution, titanium tetrachloride solution, tetrabutyl titanate solution or titanium isopropoxide solution, and is preferably titanium sulfate solution and/or tetrabutyl titanate solution.
Preferably, the magnesium source of step (1) comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate or magnesium chloride.
Preferably, the water-soluble organic substance in step (1) comprises 1 or a combination of at least 2 of ethylene glycol, glycerol, polyethylene glycol 1000, lactic acid, sucrose, triose or pentose, preferably ethylene glycol.
Preferably, the amount of the titanium source added in the mixing in step (1) is 1 to 30% by mass of the γ -alumina powder, and may be, for example, 1%, 5%, 10%, 15%, 20%, 25%, or 30%, but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the amount of the magnesium source added in the mixing in step (1) is 1 to 30% by mass of the γ -alumina powder, and may be, for example, 1%, 5%, 10%, 15%, 20%, 25%, or 30%, but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the amount of the water-soluble organic substance added in the mixing in the step (1) is 5 to 20% by mass of the γ -alumina powder, and may be, for example, 5%, 10%, 15%, 20% or the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
In a preferred embodiment of the present invention, the mixing time in the step (1) is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
Preferably, the temperature of the first drying in step (1) is 100-.
Preferably, the first drying time in step (1) is 1-3h, such as 1h, 1.5h, 2h, 2.5h or 3h, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the first calcination of step (1) is carried out under a protective atmosphere.
Preferably, the protective atmosphere comprises a nitrogen atmosphere and/or an inert atmosphere.
Preferably, the temperature of the first calcination in step (1) is 150-.
Preferably, the first calcination in step (1) is carried out for 2-5h, such as 2h, 3h, 4h or 5h, but not limited to the recited values, and other values not recited in the range are also applicable.
In a preferred embodiment of the present invention, the mass ratio of the intermediate carrier to the alumina precursor in the mixing in the step (2) is (1-4):1, and may be, for example, 1:1, 2:1, 3:1 or 4:1, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
Preferably, the alumina precursor of step (2) comprises 1 or a combination of at least 2 of pseudo-boehmite, gibbsite or amorphous alumina, preferably pseudo-boehmite.
Preferably, the additive in step (2) comprises sesbania powder and nitric acid.
Preferably, the sesbania powder is added in the mixing in the step (2) in an amount of 1 to 8% by mass, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8% by mass, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the amount of nitric acid added in the mixing in step (2) is 1 to 4% by mass of the γ -alumina powder, and may be, for example, 1%, 2%, 3%, or 4%, but is not limited to the recited values, and other values not recited in this range are also applicable.
As a preferred embodiment of the present invention, the temperature of the second drying in step (2) is 100-150 ℃, and may be, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the second drying time in step (2) is 1-3h, such as 1h, 2h or 3h, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the temperature of the second calcination in step (2) is 400-.
Preferably, the second calcination time in step (2) is 2-8h, such as 2h, 3h, 4h, 6h, 7h or 8h, but not limited to the recited values, and other values not recited in the range are also applicable.
In a preferred embodiment of the present invention, the time for the immersion treatment in step (3) is 1 to 10 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In the present invention, the nickel-containing solution used in the impregnation treatment is a nickel salt solution, and the nickel salt may be 1 or a combination of at least 2 of nickel nitrate, nickel acetate, nickel carbonate or basic nickel carbonate. The concentration of the nickel-containing solution in the present invention is determined depending on the nickel content in the catalyst. The concentration of nickel in the solution and the solid-to-liquid ratio of the mixture during the impregnation treatment are determined according to the content of nickel in the catalyst and the water absorption of the carrier (water absorption determination: if 5g of the carrier is weighed and put into a beaker, a proper amount of deionized water is added into the beaker to ensure that the carrier is 1-5cm higher than the carrier, the soaking is carried out for 0.5-3 hours, the excessive water on the surface of the carrier is absorbed by water absorption filter paper, the weight of the carrier is measured to be X, and the water absorption of the carrier is ((X-5)/5) multiplied by 100%), but the invention is not particularly limited.
Preferably, the temperature of the third drying in step (3) is 100-.
Preferably, the third drying time in step (3) is 1-3h, such as 1h, 2h or 3h, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the temperature of the third calcination in step (3) is 200-.
Preferably, the third calcination time in step (3) is 3-6h, such as 3h, 4h, 5h or 6h, but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing gamma alumina powder, a titanium source, a magnesium source and a water-soluble organic matter, and sequentially carrying out solid-liquid separation, first drying and first roasting to obtain an intermediate carrier;
(2) mixing the intermediate carrier obtained in the step (1), an alumina precursor and an additive, and then sequentially carrying out molding, second drying and second roasting to obtain a carrier;
(3) carrying out dipping treatment on the carrier obtained in the step (2) by using a nickel-containing solution, carrying out solid-liquid separation, and then sequentially carrying out third drying and third roasting to obtain the catalyst;
the titanium source in the step (1) comprises 1 or the combination of at least 2 of isopropyl titanate solution, titanium sulfate solution, titanium tetrachloride solution, tetrabutyl titanate solution or titanium isopropoxide solution; the magnesium source comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate or magnesium chloride; the water-soluble organic matter comprises 1 or at least 2 of ethylene glycol, glycerol, polyethylene glycol 1000, lactic acid, sucrose, triose or pentose; the addition amount of the titanium source in the mixing is 1-30% of the mass of the gamma alumina powder; the adding amount of the magnesium source in the mixing is 1-30% of the mass of the gamma alumina powder; the addition amount of the water-soluble organic matters in the mixture is 5-20% of the mass of the gamma alumina powder; the mixing time is 1-3 h; the first roasting is carried out in a protective atmosphere, and the roasting temperature is 150-350 ℃;
the mass ratio of the intermediate carrier to the alumina precursor in the mixing in the step (2) is (1-4) to 1; the alumina precursor comprises 1 or the combination of at least 2 of pseudo-boehmite, gibbsite or amorphous alumina; the additive comprises sesbania powder and nitric acid, wherein the addition amount of the sesbania powder is 1-8% of the mass of the gamma alumina powder, and the addition amount of the nitric acid is 1-4% of the mass of the gamma alumina powder; the temperature of the second roasting is 400-800 ℃;
the time of the dipping treatment in the step (3) is 1-10 h; the temperature of the third roasting is 200-600 ℃.
In a third aspect, the present invention provides the use of a catalyst as described in the first aspect for the liquid phase catalytic hydrogenation of an enal to produce a plasticizer alcohol.
In the invention, the impregnation and the calcination in the preparation process can be alternately carried out for multiple times under the same condition, such as impregnation-calcination, re-impregnation-calcination under the same condition, and the like, or the impregnation is directly carried out for one time, and then the calcination is carried out, thereby obtaining the catalyst.
The nitric acid is used as an analytical reagent. The obtained catalyst needs to be activated before use to achieve the applied catalytic effect, and can be carried out by referring to the conventional means in the prior art. If the reaction pressure is controlled to be 0.5-2MPa, the reaction temperature is controlled to be 250-.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the preparation method of the olefine aldehyde liquid phase hydrogenation catalyst, water-soluble organic matters are introduced in the preparation process, and carbon remained after roasting can enable Mg to be uniformly distributed on the surface of gamma alumina forming pore channels as much as possible, so that the coking resistance of the catalyst is enhanced. The carbon has a supporting effect on the pore channels of the gamma alumina, so that the collapse of the pore channels is prevented in the carrier forming process, the attachment area of the active metal is increased, and the number of active sites of the catalyst is increased; by adding titanium, the dispersity of the catalytic active component nickel is obviously improved, the interaction between the metal active component and the carrier is improved, and the prepared catalyst has higher activity and selectivity when being used for liquid-phase hydrogenation of olefine aldehyde.
(2) According to the preparation method disclosed by the invention, through the design of the catalyst components and the introduction of a water-soluble organic matter in the preparation process, the improvement of the performance of the catalyst is realized, the anti-coking performance and the service life of the catalyst are improved, the conversion rate of PBA (poly (butylene adipate/terephthalate)) is more than or equal to 97.02% when the catalyst is used for olefine aldehyde hydrogenation, and the 2-PH selectivity is more than or equal to 96.15%.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a catalyst for liquid-phase hydrogenation of olefine aldehyde, which comprises the following components in percentage by mass: NiO 16%, MgO 4%, TiO26.7 percent, and the balance being gamma Al2O3；
Wherein the carrier is MgO-TiO2-γAl2O3The active component is Ni element.
The preparation method comprises the following steps:
(1) placing a proper amount of pseudo-boehmite powder in a muffle furnace, and roasting for 3 hours at 600 ℃ in air atmosphere to obtain gamma-alumina. 27g of Ti (SO) was taken4)2、35gMg(NO3)2·6H2And placing O and 20g of glycerol into 120mL of water, stirring for 2 hours, fully mixing and dissolving, adding 100g of gamma alumina powder into the mixed solution, uniformly mixing, drying at 100 ℃ for 2 hours, and roasting at 215 ℃ for 3 hours under a nitrogen atmosphere.
(2) Weighing 71.43g of pseudo-boehmite, 10g of sesbania powder and 100g of mixture obtained by roasting, uniformly mixing, measuring 6.5mL of nitric acid (analytically pure), adding deionized water to a constant volume of 142mL, adding the solution into the mixed powder under stirring for kneading, extruding into strips, drying for 2h at 150 ℃, and roasting for 3h at 600 ℃ to obtain the carrier.
(3) Take 55gNi (NO)3)2·6H2Adding 90mL of deionized water into O to prepare a solution, soaking 90g of a carrier, drying at 150 ℃ for 3h, and then roasting at 325 ℃ for 3h to obtain a catalyst precursor 1; take 10gNi (NO)3)2·6H2Adding 75mL of deionized water into O to prepare a solution, soaking 100g of the catalyst precursor 1, drying at 150 ℃ for 1h, and roasting at 325 ℃ for 3h to obtain the catalyst C1.
Example 2
The embodiment provides a catalyst for liquid-phase hydrogenation of olefine aldehyde, which comprises the following components in percentage by mass: NiO 30%, MgO 1.47%, TiO22.7 percent, and the balance being gamma Al2O3；
Wherein the carrier is MgO-TiO2-γAl2O3The active component is Ni element.
The preparation method comprises the following steps:
(1) placing a proper amount of pseudo-boehmite powder in a muffle furnace, and roasting for 3 hours at 600 ℃ in air atmosphere to obtain gamma-alumina. Taking 35g of Ti (SO)4)2、40g Mg(NO3)2·6H2And placing O and 23g of glycol in 240mL of water, stirring for 2 hours, fully mixing and dissolving, adding 200g of gamma alumina powder into the mixed solution, uniformly mixing, drying at 120 ℃ for 3 hours, and roasting at 150 ℃ for 4 hours under a nitrogen atmosphere.
(2) Weighing 71.43g of pseudo-boehmite, 4g of sesbania powder and 100g of mixture obtained by roasting, uniformly mixing, measuring 8mL of nitric acid (analytically pure), adding deionized water to a constant volume of 142mL, adding the solution into the mixed powder under stirring for kneading, extruding into strips, drying for 2h at 140 ℃, and roasting for 2h at 800 ℃ to obtain the carrier.
(3) 80g of Ni (NO) was taken3)2·6H2Adding 70.5mL of deionized water into O to prepare a solution, soaking 90g of a carrier, drying at 100 ℃ for 2h, and roasting at 200 ℃ for 5h to obtain a catalyst precursor 1; 60g of Ni (NO)3)2·6H2Adding 65mL of deionized water into O to prepare a solution, soaking 100g of the catalyst precursor 1, drying at 120 ℃ for 3h, and roasting at 200 ℃ for 1h to obtain the catalyst C2.
Example 3
The embodiment provides a catalyst for liquid-phase hydrogenation of olefine aldehyde, which comprises the following components in percentage by mass: NiO 25%, MgO 1.8%, TiO21.9 percent and the balance of gamma Al2O3；
Wherein the carrier is MgO-TiO2-γAl2O3The active component is Ni element.
The preparation method comprises the following steps:
(1) placing a proper amount of pseudo-boehmite powder in a muffle furnace, and roasting for 3 hours at 600 ℃ in an air atmosphere to obtain gamma alumina. 25g of Ti (SO) was taken4)2、50g Mg(NO3)2·6H2And placing O and 25g of glycol in 240mL of water, stirring for 2 hours, fully mixing and dissolving, adding 200g of gamma alumina powder into the mixed solution, uniformly mixing, drying for 2 hours at 100 ℃, and roasting for 3 hours at 250 ℃ under a nitrogen atmosphere.
(2) Weighing 71.43g of pseudo-boehmite, 6g of sesbania powder and 100g of mixture obtained by roasting, uniformly mixing, weighing 4mL of nitric acid (analytically pure), adding deionized water to a constant volume of 142mL, adding the solution into the mixed powder under stirring for kneading, extruding into strips, drying for 1h at 200 ℃, and roasting for 2h at 800 ℃ to obtain the carrier.
(3) 127.1g of Ni (NO) was taken3)2·6H2Adding 112.5mL of deionized water into O to prepare a solution, soaking 168g of a carrier, drying, and roasting at 800 ℃ for 1 hour to obtain a catalyst precursor 1; taking 95.32g of Ni (NO)3)2·6H2Adding 110mL of deionized water into O to prepare a solution, soaking 200g of the catalyst precursor 1, drying at 140 ℃ for 1h, and roasting at 800 ℃ for 3h to obtain the catalyst C3.
Example 4
The embodiment provides a catalyst for liquid-phase hydrogenation of olefine aldehyde, which comprises the following components in percentage by mass: NiO 24%, MgO 2.28%, TiO22.28%, the balance being gamma Al2O3；
Wherein the carrier is MgO-TiO2-γAl2O3The active component is Ni element.
The preparation method comprises the following steps:
(1) placing a proper amount of pseudo-boehmite powder in a muffle furnace, and roasting for 3 hours at 600 ℃ in an air atmosphere to obtain gamma alumina. Taking 15g of Ti (SO)4)2、31.8g Mg(NO3)2·6H2And placing O and 12.5g of glycol into 120mL of water, stirring for 1 hour, fully mixing and dissolving, adding 100g of gamma alumina powder into the mixed solution, uniformly mixing, drying for 2 hours at 120 ℃, and roasting for 3 hours at 300 ℃ under a nitrogen atmosphere.
(2) Weighing 70g of pseudo-boehmite, 8g of sesbania powder and 100g of mixture obtained by roasting, uniformly mixing, measuring 6mL of nitric acid (analytically pure), adding deionized water to a constant volume of 142mL, adding the solution into the mixed powder under stirring, kneading, extruding into strips, drying for 1h at 120 ℃, and roasting for 3h at 500 ℃ to obtain the carrier.
(3) 59.6g of Ni (NO) was taken3)2·6H2Adding 55mL of deionized water into O to prepare a solution, soaking 90g of carrier, drying, and roasting at 400 ℃ for 3 hours to obtain a catalyst precursor 1; 53g of Ni (NO)3)2·6H2Adding 64mL of deionized water into O to prepare a solution, soaking 100g of the catalyst precursor 1, drying, and roasting at 400 ℃ for 1 hour to obtain the catalyst C4.
Comparative example 1
The only difference from example 4 is that no magnesium source and no water-soluble organic substance were added during the preparation, and catalyst D1 was obtained.
Comparative example 2
The only difference from example 4 was that no titanium source was added during the preparation, catalyst D2 was obtained.
Comparative example 3
The only difference from example 4 was that no water-soluble organic substance was added during the preparation, and catalyst D3 was obtained.
The catalyst samples prepared in the examples and the comparative examples were firstly activated (activation conditions: 100g of catalyst was subjected to reductive activation using a moving bed reactor at a reaction pressure of 1.2MPa, a reduction temperature of 380 ℃ for 6 hours, and an actual/theoretical volume ratio of hydrogen of 800:1), 20mL of the activated catalyst was then loaded into a fixed bed reactor, and at a reaction temperature of 130 ℃ and a reaction pressure of 2.5MPa, a mixture of 2-propylheptanol (2-PH) and 2-propyl-2-heptenal (PBA) was used as a starting material for the experiment, and a volume space velocity of the starting material was 0.75h-1The hydrogen/liquid volume ratio was 400: 1. The activity of each catalyst was stable for 1000h under the reaction conditions, and the liquid product was analyzed by gas chromatography, the results are shown in table 1.
TABLE 1 catalytic Properties of catalysts in examples and comparative examples
| Catalyst numbering | PBA conversion/% | 2-pH selectivity/%) | |
| Example 1 | C1 | 97.02 | 96.15 |
| Example 2 | C2 | 97.52 | 95.94 |
| Example 3 | C3 | 98.84 | 96.62 |
| Example 4 | C4 | 99.85 | 98.84 |
| Comparative example 1 | D1 | 94.30 | 93.39 |
| Comparative example 2 | D2 | 96.52 | 94.02 |
| Comparative example 3 | D3 | 96.07 | 93.86 |
The results of the above examples and comparative examples show that, in the preparation method of the liquid-phase hydrogenation catalyst for olefine aldehyde, by introducing the water-soluble organic substance, Mg can be more uniformly distributed on the surface of the gamma alumina forming the pore channel, so that the anti-coking performance and activity of the catalyst are enhanced, the collapse of the pore channel in the carrier forming process can be prevented, the attachment area of the active metal is increased, and the active sites are increased; by adding titanium, the dispersity of the catalytic active component nickel is obviously improved, the interaction between the metal active component and the carrier is improved, and the prepared hydrogenation catalyst has higher activity and selectivity. Meanwhile, the catalyst of the invention still keeps higher activity and selectivity after running for a long time of 1000 h.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A catalyst for liquid-phase hydrogenation of olefine aldehyde is characterized by comprising the following components in percentage by mass: NiO 10-30 wt%, MgO 0.5-15 wt%, TiO20.5-15%, and the balance of gamma Al2O3；
Wherein the carrier is MgO-TiO2-γAl2O3The active component is Ni element.
2. The catalyst according to claim 1, comprising by mass percent: NiO 15-20 wt%, MgO 5-10 wt%, and TiO28-12% of gamma Al2O3。
3. The method for preparing the catalyst according to claim 1 or 2, comprising the steps of:
(1) mixing gamma alumina powder, a titanium source, a magnesium source and a water-soluble organic matter, and sequentially carrying out solid-liquid separation, first drying and first roasting to obtain an intermediate carrier;
(2) mixing the intermediate carrier obtained in the step (1), an alumina precursor and an additive, and then sequentially carrying out molding, second drying and second roasting to obtain a carrier;
(3) and (3) carrying out impregnation treatment on the carrier obtained in the step (2) by using a nickel-containing solution, carrying out solid-liquid separation, and then sequentially carrying out third drying and third roasting to obtain the catalyst.
4. The method according to claim 3, wherein the titanium source of step (1) comprises 1 or a combination of at least 2 of isopropyl titanate solution, titanium sulfate solution, titanium tetrachloride solution, tetrabutyl titanate solution, or titanium isopropoxide solution, preferably titanium sulfate solution and/or tetrabutyl titanate solution;
preferably, the magnesium source of step (1) comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate or magnesium chloride;
preferably, the water-soluble organic substance in step (1) comprises 1 or a combination of at least 2 of ethylene glycol, glycerol, polyethylene glycol 1000, lactic acid, sucrose, triose or pentose, preferably ethylene glycol;
preferably, the addition amount of the titanium source in the mixing in the step (1) is 1-30% of the mass of the gamma alumina powder;
preferably, the addition amount of the magnesium source in the mixing in the step (1) is 1-30% of the mass of the gamma alumina powder;
preferably, the addition amount of the water-soluble organic matters in the mixing in the step (1) is 5-20% of the mass of the gamma alumina powder.
5. The method of claim 3 or 4, wherein the mixing of step (1) is carried out for a time of 1 to 3 hours;
preferably, the temperature of the first drying in the step (1) is 100-150 ℃;
preferably, the first drying time in the step (1) is 1-3 h;
preferably, the first firing of step (1) is carried out under a protective atmosphere;
preferably, the protective atmosphere comprises a nitrogen atmosphere and/or an inert atmosphere;
preferably, the temperature of the first roasting in the step (1) is 150-350 ℃;
preferably, the time of the first roasting in the step (1) is 2-5 h.
6. The method according to any one of claims 3 to 5, wherein the mass ratio of the intermediate carrier to the alumina precursor in the mixing in the step (2) is (1-4: 1;
preferably, the alumina precursor of step (2) comprises 1 or a combination of at least 2 of pseudo-boehmite, gibbsite or amorphous alumina, preferably pseudo-boehmite;
preferably, the additive in the step (2) comprises sesbania powder and nitric acid;
preferably, the addition amount of the sesbania powder in the mixing in the step (2) is 1-8% of the mass of the gamma alumina powder;
preferably, the adding amount of the nitric acid in the mixing in the step (2) is 1-4% of the mass of the gamma alumina powder.
7. The method according to any one of claims 3 to 6, wherein the temperature of the second drying in step (2) is 100 ℃ to 150 ℃;
preferably, the second drying time in the step (2) is 1-3 h;
preferably, the temperature of the second roasting in the step (2) is 400-800 ℃;
preferably, the time of the second roasting in the step (2) is 2-8 h.
8. The production method according to any one of claims 3 to 7, wherein the time for the impregnation treatment in step (3) is 1 to 10 hours;
preferably, the temperature of the third drying in the step (3) is 100-150 ℃;
preferably, the third drying time in the step (3) is 1-3 h;
preferably, the temperature of the third roasting in the step (3) is 200-600 ℃;
preferably, the time of the third roasting in the step (3) is 3-6 h.
9. The method of any one of claims 3 to 8, comprising the steps of:
(1) mixing gamma alumina powder, a titanium source, a magnesium source and a water-soluble organic matter, and sequentially carrying out solid-liquid separation, first drying and first roasting to obtain an intermediate carrier;
(2) mixing the intermediate carrier obtained in the step (1), an alumina precursor and an additive, and then sequentially carrying out molding, second drying and second roasting to obtain a carrier;
(3) carrying out dipping treatment on the carrier obtained in the step (2) by using a nickel-containing solution, carrying out solid-liquid separation, and then sequentially carrying out third drying and third roasting to obtain the catalyst;
the titanium source in the step (1) comprises 1 or the combination of at least 2 of isopropyl titanate solution, titanium sulfate solution, titanium tetrachloride solution, tetrabutyl titanate solution or titanium isopropoxide solution; the magnesium source comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate or magnesium chloride; the water-soluble organic matter comprises 1 or at least 2 of ethylene glycol, glycerol, polyethylene glycol 1000, lactic acid, sucrose, triose or pentose; the addition amount of the titanium source in the mixing is 1-30% of the mass of the gamma alumina powder; the adding amount of the magnesium source in the mixing is 1-30% of the mass of the gamma alumina powder; the addition amount of the water-soluble organic matters in the mixture is 5-20% of the mass of the gamma alumina powder; the mixing time is 1-3 h; the first roasting is carried out in a protective atmosphere, and the roasting temperature is 150-350 ℃;
the mass ratio of the intermediate carrier to the alumina precursor in the mixing in the step (2) is (1-4) to 1; the alumina precursor comprises 1 or the combination of at least 2 of pseudo-boehmite, gibbsite or amorphous alumina; the additive comprises sesbania powder and nitric acid, wherein the addition amount of the sesbania powder is 1-8% of the mass of the gamma alumina powder, and the addition amount of the nitric acid is 1-4% of the mass of the gamma alumina powder; the temperature of the second roasting is 400-800 ℃;
the time of the dipping treatment in the step (3) is 1-10 h; the temperature of the third roasting is 200-600 ℃.
10. Use of a catalyst according to claim 1 or 2 for the production of plasticiser alcohols by the liquid phase catalytic hydrogenation of alkenals.
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