CN106268861B - 一种磁性加氢脱氧催化剂及其制备方法 - Google Patents
一种磁性加氢脱氧催化剂及其制备方法 Download PDFInfo
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- CN106268861B CN106268861B CN201610868705.4A CN201610868705A CN106268861B CN 106268861 B CN106268861 B CN 106268861B CN 201610868705 A CN201610868705 A CN 201610868705A CN 106268861 B CN106268861 B CN 106268861B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 230000005389 magnetism Effects 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 48
- 229910018516 Al—O Inorganic materials 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 12
- 229960001545 hydrotalcite Drugs 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000006392 deoxygenation reaction Methods 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 14
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 12
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000011549 displacement method Methods 0.000 description 6
- -1 installs device Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000002459 sustained effect Effects 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000012075 bio-oil Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCPATDQUAFZMLI-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Pt+2].N.[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Pt+2].N.[N+](=O)([O-])[O-] QCPATDQUAFZMLI-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/007—Mixed salts
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种磁性加氢脱氧催化剂及其制备方法，催化剂由Pt、Fe、Ni、Al、O共五种元素组成，其中Pt的质量分数含量为1%~5%，Fe3O4的质量分数含量为5%~20%，NiO的质量分数含量为40~80%，Al2O3的质量分数含量为14~54%。制备工艺步骤如下：先采用碱沉淀法制备磁性溶胶；再将磁性溶胶加入到制备Ni‑Al水滑石溶液中，获得Fe3O4‑Ni‑Al水滑石；然后依次经浸渍负载、氢气还原制备出具有磁性的Pt/Fe‑Ni‑Al‑O加氢脱氧催化剂。该催化剂具有很好的加氢脱氧活性和较好的脱氢活性，可以减少脱氧反应中氢能源的消耗，且利用磁场大大简化催化剂的后续分离或回收操作。
Description
技术领域
本发明属于油品精制领域，是一种磁性加氢脱氧催化剂及其制备方法。
背景技术
生物质油因其原料来源广泛，又具有可再生性，被认为是一类最具潜力的石油替代能源。然而，生物油中含有酚、呋喃、醛、酮等多种含氧化合物，其含氧量高达50％，导致燃烧热值低、化学稳定性差等不足，阻碍了它作为能源的广泛应用，必须进行催化加氢脱氧（简称HDO）精制降低其含氧量，而该技术的关键在于催化剂的构筑。
贵金属负载型催化剂是一种活性好，寿命长的高效催化剂，被广泛应用于生物质油中含氧化合物的HDO反应中。但该类催化剂的活性组分价格昂贵，非均相催化反应后催化剂的分离回收凸显重要，而且催化剂具有很强的加氢活性，致使在催化含有不饱和基团含氧化合物的加氢脱氧反应中消耗大量宝贵的氢能源，尤其是在酚类化合物中。目前，主要采用活性炭、氧化铝、氧化铈及复合氧化物等为载体，通过浸渍和氢气还原获得。所制备的催化剂中活性组分分散不均匀，催化剂活性有待于进一步增强。在非均相操作中，催化剂回收需经过离心或过滤分离催化剂，操作较复杂。若能通过优化活性组分组成和制备方法等对催化剂进行改进，制备出具有磁性加氢脱氧催化剂，将可提高催化剂的活性，简化非均相情况下催化剂的分离操作，最大程度减少催化剂在分离过程中的损失，降低成本。
Raul F. Lobo等[Green Chem., 2012, 14: 1388]采用浸渍-还原法将Pt–Ni双金属负载在γ-Al2O3上，发现所制催化剂具有较好的活性，催化间甲基苯酚加氢脱氧反应后产物中环烷烃的选择性达99%，氢气消耗量大。由于贵金属的成本昂贵，活性组分的分散对催化性能也很重要。近年来文献报道[J. Catal., 2015, 331: 193]水滑石的层状结构有利于提高贵金属活性组分的分散，被选为复合氧化物前体来提高催化剂的活性。专利1[申请号200510011996.7]发明了一种均匀大粒径磁性水滑石的制备方法，即先采用共沉淀法制备纳米级磁性核，再利用尿素法令水滑石在磁性核周围生长。近年来，专利2[申请号201310181964.6]发明了一种磁性水滑石负载纳米钯催化剂（Pd/Fe3O4-Mg-Al水滑石）的制备方法，使得反应后的催化剂在磁场作用下容易分离。
发明内容
本发明的目的在于提供一种磁性加氢脱氧催化剂及其制备方法，该催化剂具有活性高，脱氧过程氢气消耗量低、且利用磁性可容易将催化剂分离等优点。
本发明的技术方案：
一种磁性加氢脱氧催化剂，由Pt、Fe、Ni、Al、O共5种元素组成，Pt的质量百分数含量为1~5，Fe3O4的质量百分数含量为5~20，NiO的质量百分数含量为40~80，Al2O3的质量百分数含量为14~54。
一种磁性加氢脱氧催化剂的制备方法，工艺步骤如下：
(1) 制备磁性溶胶(A)：按一定比例称取可溶性亚铁盐和铁盐溶于去离子水中，在65℃下，滴加氨水至上述溶液中，调节pH=9～11，即得到磁性溶胶。
(2) 制备磁性Fe3O4-Ni-Al水滑石：取磁性溶胶(A)，镍盐和铝盐放入去离子水中配制成金属盐混合溶液(B)，再配制NaOH和Na2CO3的碱混合溶液(C)，在室温下剧烈搅拌，用恒压滴定漏斗滴加混合溶液(B)至三口烧瓶中，同时也滴加溶液(C)，并保证反应液的pH值在9.5~10.5范围内，滴加完毕后继续反应一段时间，然后倒入水热反应釜中晶化，最后将沉淀物抽滤、洗涤、干燥，即得到磁性Fe3O4-Ni-Al水滑石。
(3) 制备磁性Pt/Fe-Ni-Al-O催化剂：取1g磁性Fe3O4-Ni-Al水滑石，加入Pt盐溶液和去离子水进行浸渍负载，经干燥、焙烧和氢气还原，得到磁性Pt/Fe-Ni-Al-O催化剂。
所述磁性Pt/Fe-Ni-Al-O催化剂制备中，磁性溶胶制备中的亚铁盐为氯化亚铁或硫酸亚铁，铁盐为氯化铁或硫酸铁，亚铁盐和铁盐的摩尔比为0.2~3，优选0.2~1。
所述磁性Pt/Fe-Ni-Al-O催化剂制备中，磁性Fe3O4-Ni-Al水滑石制备中的镍盐为氯化镍、硫酸镍或硝酸镍之中的一种或多种，铝盐为氯化铝、硫酸铝或硝酸铝之中的一种或多种。
所述磁性Pt/Fe-Ni-Al-O催化剂中，先将磁性Fe3O4-Ni-Al水滑石浸渍吸附含Pt离子，然后在500~600℃下焙烧得到复合氧化物前体，再进一步还原制备Pt/Fe-Ni-Al-O催化剂。
本发明中采用在Ni-Al水滑石的制备过程中加入磁性溶胶制备出具有磁性的载体前体，利用水滑石的双层结构有利于分散活性组分的特点，将磁性载体前体Fe3O4-Ni-Al水滑石负载吸附Pt盐后再焙烧，得到复合氧化物，再经氢气还原得到Pt/Fe-Ni-Al-O催化剂。所制催化剂具有很好的加氢脱氧活性，同时具有较好的脱氢活性，催化加氢脱氧反应中可以减少氢能源的消耗，尤其是在酚类化合物的加氢脱氧反应中，还能提高产物的辛烷值。此外，该磁性加氢脱氧催化剂容易分离，利用磁场容易实现将非均相反应后的催化剂分离或回收。该方法还可以通过改变活性组分制备其他磁性贵金属催化剂用于加氢等催化反应中。
附图说明
图1为本发明制备的磁性Pt/Fe-Ni-Al-O催化剂的X-射线粉末衍射图。
图2为Pt/Ni-Al-O和本发明制备的Pt/Fe-Ni-Al-O的磁性对比图。在磁铁的作用下，图中左侧Pt/Fe-Ni-Al-O的黑色催化剂全部被磁铁吸住在瓶壁上而不落下来，而右侧Pt/Ni-Al-O催化剂则全部沉在瓶底，对比说明本发明制备的Pt/Fe-Ni-Al-O具有较好的磁性，在磁场的作用下，容易实现分离。
具体实施方式
下面通过具体实施例对本发明作进一步说明。
实施例中所用的试剂均为分析纯，水为超纯水。
实施例1：
称取二氯化亚铁1.075g、三氯化铁2.95g置于100mL三口烧瓶中，倒入50mL去离子水，搅拌溶解。在65℃下，滴加氨水至pH=10，持续搅拌反应60min后，得到磁性溶胶(A)。
取上述磁性溶胶(A) 5 mL，4.37g硝酸镍和1.88g硝酸铝放入40 mL去离子水中配制成金属盐混合溶液(B)，再取 2.40g NaOH和0.4 g无水Na2CO3溶于50 mL去离子水中配成碱混合溶液(C)，在室温下剧烈搅拌，用恒压滴定漏斗以4mL/min的速度滴加(B) 至三口烧瓶中，同时也滴加溶液(C)，并保证反应液的pH值在9.5～10.5范围内，滴加完毕后继续反应30 min，然后倒入水热反应釜中在95 ℃下晶化10 h，最后将沉淀物抽滤、洗涤与干燥，即得到磁性Fe3O4-Ni-Al水滑石载体。
取1g Fe3O4-Ni-Al水滑石载体，加入硝酸铂氨溶液进行浸渍负载，在120℃烘箱干燥10 h后，再在500℃下煅烧4 h，得到PtO2/Fe3O4-NiO-Al2O3，然后在氢气气氛350 ℃下还原，即得到Pt/Fe-Ni-Al-O，其中其中Pt的质量百分数含量为2%，Fe3O4的质量百分数含量为10，NiO的质量百分数含量为61，Al2O3的质量百分数含量为27。
在高压反应釜中加入25.0g 正十二烷、3.61 g对乙基苯酚和0.06 g上述制备的Pt/Fe-Ni-Al-O催化剂，装好装置，采用置换法排除釜内空气，然后以10 ℃/min的速率从室温升至300 ℃，调整转速为900 r/min，氢气压力为2.0 MPa，反应1.5 h后，对乙基苯酚的转化率达99.4%，含氧产物的选择性为0，反应8 h后，产物中乙苯的选择性达71.4%。
实施例2：
将实施例1磁性Fe3O4-Ni-Al水滑石载体的制备中磁性溶胶的改为2.5 mL，其他条件和操作都不变，制备出Fe3O4的质量分数含量为5%的磁性Pt/Fe-Ni-Al-O催化剂，其中Pt的质量分数含量为2%，Fe3O4的质量分数含量为5%，NiO的质量分数含量为64%，Al2O3的质量分数含量为24%。
在高压反应釜中加入25.0g 正十二烷、3.61 g对乙基苯酚和0.06 g上述制备的Pt/Fe-Ni-Al-O催化剂，装好装置，采用置换法排除釜内空气，然后以10 ℃/min的速率从室温升至300 ℃，调整转速为900 r/min，氢气压力为2.0 MPa，反应1.5 h后，对乙基苯酚的转化率达99.8%，含氧产物的选择性为0，反应8 h后，产物中乙苯的选择性达70.1%。
实施例3：
将实施例1中磁性Fe3O4-Ni-Al水滑石载体的制备中磁性溶胶的改为10 mL，其他条件和操作都不变，制备出Fe3O4的质量分数含量为20%的磁性Pt/Fe-Ni-Al-O催化剂其中，Pt的质量分数含量为2%，Fe3O4的质量分数含量为20%，NiO的质量分数含量为52%，Al2O3的质量分数含量为26%。
在高压反应釜中加入25.0g 正十二烷、3.61 g对乙基苯酚和0.06 g上述制备的Pt/Fe-Ni-Al-O催化剂，装好装置，采用置换法排除釜内空气，然后以10 ℃/min的速率从室温升至300 ℃，调整转速为900 r/min，氢气压力为2.0 MPa，反应1.5 h后，对乙基苯酚的转化率达99.1%，含氧产物的选择性为0，反应8 h后，产物中乙苯的选择性达80.8%。
实施例4：
将实施例1中磁性Fe3O4-Ni-Al水滑石载体的制备中Ni盐与Al盐的摩尔比改为1:1，其他条件和操作都不变，制备出磁性Pt/Fe-Ni-Al-O催化剂，其中Pt的质量分数含量为2%，Fe3O4的质量分数含量为10%，NiO的质量分数含量为52.8%，Al2O3的质量分数含量为35.2 %。
在高压反应釜中加入25.0g 正十二烷、3.61 g对乙基苯酚和0.06 g上述制备的Pt/Fe-Ni-Al-O催化剂，装好装置，采用置换法排除釜内空气，然后以10℃/min的速率从室温升至300 ℃，调整转速为900 r/min，氢气压力为2.0 MPa，反应1.5 h后，对乙基苯酚的转化率达99.4%，含氧产物的选择性为0，反应8 h后，产物中乙苯的选择性达75.6%。
实施例5：
将实施例1中磁性Fe3O4-Ni-Al水滑石载体的制备中Ni盐与Al盐的摩尔比改为4:1，其他条件和操作都不变，制备出磁性Pt/Fe-Ni-Al-O催化剂，其中Pt的质量分数含量为2%，Fe3O4的质量分数含量为10%，NiO的质量分数含量为75%，Al2O3的质量分数含量为13 %。
在高压反应釜中加入25.0g 正十二烷、3.61 g对乙基苯酚和0.06 g上述制备的Pt/Fe-Ni-Al-O催化剂，装好装置，采用置换法排除釜内空气，然后以10 ℃/min的速率从室温升至300 ℃，调整转速为900 r/min，氢气压力为2.0 MPa，反应1.5 h后，对乙基苯酚的转化率达99.9%，含氧产物的选择性为0，反应8 h后，产物中乙苯的选择性达68.9%。
实施例6：
将实施例1中Pt/Fe-Ni-Al-O前体的制备过程中，Pt负载量改为5%，其他条件和操作都不变，制备出磁性Pt/Fe-Ni-Al-O催化剂。
在高压反应釜中加入25.0g 正十二烷、3.61 g对乙基苯酚和0.06 g上述制备的Pt/Fe-Ni-Al-O催化剂，装好装置，采用置换法排除釜内空气，然后以10 ℃/min的速率从室温升至300 ℃，调整转速为900 r/min，氢气压力为2.0 MPa，反应0.5 h后，对乙基苯酚的转化率达99.9%，含氧产物的选择性为0，反应8 h后，产物中乙苯的选择性达78.4%。
实施例 7：
将实施例1中Pt/Fe-Ni-Al-O前体的制备过程中，Pt负载量改为1%，其他条件和操作都不变，制备出磁性Pt/Fe-Ni-Al-O催化剂。
在高压反应釜中加入86.75 g正十二烷、13.25 g苯甲醛和0.20 g上述制备的Pt/Fe-Ni-Al-O催化剂，装好装置，排除釜内空气，然后以10 ℃/min的速率从室温升至250℃，调整转速为900 r/min，氢气压力为1.0 MPa，持续反应1 ｈ后，苯甲醛的转化率达100 %，甲苯选择性达89.7%。
实施例 8：
在高压反应釜中加入85 g正十二烷、15 g苯乙酮和0.10 g实施例1制备的催化剂，装好装置，排除釜内空气，然后以10 ℃/min的速率从室温升至225℃，调整转速为900 r/min，氢气压力为1.0 MPa，持续反应1 ｈ后，苯乙酮的转化率达100 %，乙苯的选择性达94.7%。
实施例 9：
在高压反应釜中加入87.49 g正十二烷、12.51 g环己醇和0.20 g实施例1制备的催化剂，装好装置，排除釜内空气，然后以10 ℃/min的速率从室温升至275℃，调整转速为900 r/min，氢气压力为1.0 MPa，持续反应1 ｈ后，环己醇的转化率达100%，含氧产物的选择性为0，反应8 h后，苯的选择性达82.5%。
Claims (7)
1.一种磁性加氢脱氧催化剂，其特征在于：由Pt、Fe、Ni、Al、O共五种元素组成，其中Pt的质量百分数含量为1~5，Fe3O4的质量百分数含量为5~20，NiO的质量百分数含量为40~80，Al2O3的质量百分数含量为14~54。
2.一种磁性加氢脱氧催化剂的制备方法，其特征在于采用如下工艺步骤：
(1) 按一定比例称取可溶性亚铁盐和铁盐溶于去离子水中，在65℃下滴加氨水至上述溶液中，调节pH=9～11，即得到磁性溶胶(A)；
(2) 取磁性溶胶(A)、镍盐和铝盐放入去离子水中配制成金属盐混合溶液(B)，再配制NaOH和Na2CO3的碱混合溶液(C)，在室温下剧烈搅拌，用恒压滴定漏斗滴加混合溶液(B)至三口烧瓶中，同时也滴加溶液(C)，并保证反应液的pH值在9.5～10.5范围内；滴加完毕后继续反应0.5～2小时，然后倒入水热反应釜中晶化；最后将沉淀物抽滤、洗涤、干燥，即得到磁性Fe3O4-Ni-Al水滑石；
(3) 取1g磁性Fe3O4-Ni-Al水滑石，加入Pt盐溶液和去离子水进行浸渍负载Pt离子，经干燥、500~600℃下焙烧和氢气还原，得到磁性Pt/Fe-Ni-Al-O催化剂。
3.根据权利要求2所述的一种磁性加氢脱氧催化剂的制备方法，其特征在于：所述步骤（1）磁性溶胶(A)制备中，亚铁盐为氯化亚铁或硫酸亚铁，铁盐为氯化铁或硫酸铁，其中亚铁盐和铁盐的摩尔比为0.2~3。
4.根据权利要求3所述的一种磁性加氢脱氧催化剂的制备方法，其特征在于：所述步骤（1）磁性溶胶(A)制备中，其中亚铁盐和铁盐的摩尔比为0.2~1。
5.根据权利要求2所述的磁性加氢脱氧催化剂的制备方法，其特征在于：所述步骤（2）磁性Fe3O4-Ni-Al水滑石制备中，镍盐为氯化镍、硫酸镍或硝酸镍之中的一种或多种，铝盐为氯化铝、硫酸铝或硝酸铝之中的一种或多种，其中Ni/Al摩尔比为1:1~4:1。
6.根据权利要求2所述的磁性加氢脱氧催化剂的制备方法，其特征在于：所述步骤（2）磁性Fe3O4-Ni-Al水滑石制备中，Fe3O4的质量百分数含量为5~20。
7.根据权利要求2所述的磁性加氢脱氧催化剂的制备方法，其特征在于：所述步骤（3）磁性Pt/Fe-Ni-Al-O催化剂中，Pt的质量百分数含量为1~10。
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