CN111715229A - Method for catalyzing methyl laurate hydrodeoxygenation by sulfur-free nickel-based catalyst - Google Patents
Method for catalyzing methyl laurate hydrodeoxygenation by sulfur-free nickel-based catalyst Download PDFInfo
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- CN111715229A CN111715229A CN202010741699.2A CN202010741699A CN111715229A CN 111715229 A CN111715229 A CN 111715229A CN 202010741699 A CN202010741699 A CN 202010741699A CN 111715229 A CN111715229 A CN 111715229A
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- hydrodeoxygenation
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 239000003054 catalyst Substances 0.000 title claims abstract description 152
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000002551 biofuel Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003921 oil Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 73
- 239000010936 titanium Substances 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012075 bio-oil Substances 0.000 claims description 8
- 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 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000003993 interaction Effects 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 230000001965 increasing effect Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 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 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 3
- 238000012512 characterization method Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims description 2
- 238000001467 acupuncture Methods 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical compound O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 claims description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 230000006324 decarbonylation Effects 0.000 claims description 2
- 238000006606 decarbonylation reaction Methods 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 claims description 2
- 239000003574 free electron Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000005012 migration Effects 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- FAHUKNBUIVOJJR-UHFFFAOYSA-N 1-(4-fluorophenyl)-1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazine Chemical compound C1=CC(F)=CC=C1C1C2=CC=CN2CCN1 FAHUKNBUIVOJJR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000221089 Jatropha Species 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
- B01J23/83—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 rare earths or actinides
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Abstract
The invention discloses a sulfur-free nickel-based catalyst Ni/CeO2‑TiO2The catalyst has the advantages of simple preparation method, high catalytic activity and stability, and easy reactionThe preparation method has the advantages of strong system separation, strong carbon deposition resistance, good reusability and the like, when the mass ratio of the catalyst to the reaction raw material methyl laurate is 0.1:1, the reaction temperature is 300 ℃, and the hydrogen pressure is 2.5MPa, the reaction is carried out for 4 hours, the mass yield of the prepared hydrodeoxygenation bio-fuel oil product is 96%, and the mass percentage of the product containing the n-undecane is 98%.
Description
Technical Field
The invention belongs to the field of biomass energy catalysis, and relates to a sulfur-free nickel-based catalyst Ni/CeO2-TiO2A method for preparing biofuel oil by catalyzing the hydrodeoxygenation of methyl laurate.
Background
The bio-oil extracted from the biomass has high viscosity and oxygen content, and can become the bio-fuel oil with high calorific value only by further reducing the O/C ratio and improving the H/C ratio. Currently, one of the most effective upgrading methods is the catalytic hydrogenation of bio-oil. In recent years, the Ni-based catalyst has high activity and low price, and is widely used for catalytic hydrodeoxygenation of bio-oil. For example, Sharma et al, catalyzed the hydrodeoxygenation of jatropha oil by sulfided Ni Mo/MTS, the reaction conversion rate was nearly 100%, and the molar yield of diesel alkane as the reaction product was 80% (Catalysis Today,2012,198: 314-. Senol et Al, at 250 ℃ under 1.5MPa hydrogen pressure, with sulfided NiMo/gamma-Al2O3And CoMo/gamma-Al2O3Catalyzing methyl heptanoate to perform hydrodeoxygenation, wherein the reaction conversion rate is nearly 100 percent, and vulcanized NiMo/gamma-Al2O3Catalytic hydrodeoxygenation product heptane selectivity near 100%, while sulfided CoMo/γ -Al2O3It was only 75% (journal of Molecular Catalysis A: Chemical 268,2007: 1-8). In the hydrodeoxygenation reaction of these nickel-based catalysts, a vulcanized Ni-based catalyst is mostly used for improving the catalytic activity of the nickel-based catalysts, sulfur is introduced to be beneficial to preventing catalyst poisoning, reducing carbon deposition on the surface of the catalyst, enhancing the acid strength of the catalyst B and promoting decarboxylation reaction, but because sulfur components in the catalyst are easy to lose in the reaction process, H is continuously added in the reduction stage of the catalyst to keep the sulfidization state of the catalyst2S or CS2Sulfuration, so the sulfur pollution of products can be caused after the use. Therefore, there is a need to prepare high performance sulfur-free Ni-based catalysts with strong stability against carbon deposition.
Chen et Al Ni/gamma-Al2O3Catalyzing methyl laurate to carry out hydrodeoxygenation reaction for 1.5h at 400 ℃ and under the hydrogen pressure of 2MPa, wherein the reaction conversion rate is 91 percent, and obtaining a hydrodeoxygenation product C11Quality recovery of alkanesThe rate is 62%, but after the catalyst reacts for a certain time at high temperature, the active component nickel crystal grains grow gradually and are aggregated into large crystal grains from small crystal grains gradually, so that the active surface of the catalyst is reduced, the pore channels in the catalyst are blocked, the catalytic activity is obviously reduced after the catalyst is repeatedly used twice, the reaction conversion rate is only 53.1%, and the product C is11The mass yield of alkanes dropped dramatically to 14.9% (Applied Catalysis A, General,2019,569: 35-44). Zhang et al at 300 ℃ under 4MPa of hydrogen pressure using Ni/TiO2-ZrO2The guaiacol is catalyzed and hydrogenated for 8 hours, the reaction conversion rate is nearly 100 percent, the selectivity of the reaction product cyclohexane is 86.4 percent, but a large amount of carbon deposition is generated on the surface of the catalyst in the reaction process, and the reaction conversion rate is reduced to 90.2 percent after the catalyst is repeatedly used twice (Energy)&Fuels,2014,28(4): 2562-. Laurent et al catalyzed a bio-oil model compound phenol with 10% Ni/HZSM-5 at 240 ℃ under 4MPa hydrogen pressure for 3 hours, after four cycles of catalyst use, the conversion of phenol decreased from 87.5% (third cycle data) to 57.7%, the water solvent in the reaction system also caused leaching of the nickel component, and 89mg/L Ni was present in the solution after the reaction (Journal of Catalysis,1994,146(1): 281-. Therefore, the nickel-based catalyst is generally faced with the problems of catalyst sintering, carbon deposition, metal leaching, short service life and the like in the catalytic hydrogenation process.
Aiming at the problems that the sulfur component of the Ni-based catalyst is easy to lose, the Ni active site is agglomerated and deposited with carbon, the reusability of the catalyst is poor and the like in the catalytic hydrodeoxygenation process, the invention provides a sulfur-free nickel-based catalyst Ni/CeO2-TiO2Method for preparing biofuel by catalyzing methyl laurate to perform hydrodeoxygenation, and sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2The catalyst has the advantages of high catalytic hydrodeoxygenation activity, good reusability, strong carbon deposition resistance and high product yield.
Disclosure of Invention
Objects of the invention
The invention aims to provide a sulfur-free nickel-based catalyst Ni/CeO2-TiO2A method for catalyzing methyl laurate to carry out hydrodeoxygenation to generate biofuel oil.
Technical scheme of the invention
A method for catalyzing methyl laurate hydrodeoxygenation by a sulfur-free nickel-based catalyst comprises the following steps:
(1) the sulfur-free nickel-based catalyst is Ni/CeO2-TiO2In which Ni and CeO2-TiO2The mass ratio of the composite metal oxide carrier is 0.1-0.2: 1;
the CeO2-TiO2In the carrier, Ce element provides an oxygen cavity, Ti element provides an acid site, and the molar ratio of Ce to Ti is 1-1.5: 1;
the sulfur-free nickel-based catalyst Ni/CeO2-TiO2Is in a spherical granular structure, the diameter of the pores is 7-12 nm, and the pore volume is 0.15-0.27 cm3A specific surface area of 61-122 m2/g；
(2) The sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2In the method, NiO on the surface of the catalyst is reduced into simple substance Ni through hydrogen, and metal defects on the surface of the simple substance Ni activate H in the hydrodeoxygenation reaction2And CeO2The catalyst plays a role of an electron assistant, improves the electron density around Ni on the surface of the catalyst, and promotes the reduction of NiO species;
the CeO2-TiO2Ce in composite metal oxide support4+Is reduced to Ce by hydrogen3+，Ce3+Oxygen defect sites and Ti4+The oxophilic site and carbonyl oxygen in the methyl laurate generate stronger interaction, the energy required by decarbonylation/carboxyl in the methyl laurate is reduced, and meanwhile, Ce4+Reduction to Ce3+The generated oxygen vacancies rich in electrons have stronger adsorption effect on oxygen atoms in methyl laurate, the electron transfer in the catalytic methyl laurate hydrodeoxygenation reaction process is accelerated, the catalytic activity of the catalyst is enhanced, the released free electrons are transferred to Ni active sites, the outer electrons of metal Ni are attracted, the Ni has partial positive charges, the electron-withdrawing capability of the active component Ni is enhanced, the interaction between the active component Ni and a carrier is improved, the dispersion degree of the active metal Ni is improved, and the Ni/TiO shown in the attached figure 2 of the specification has stronger adsorption effect on the oxygen atoms in the methyl laurate2、Ni/CeO2-TiO2The TEM characterization of CeO is compared and shown2Then, Ni/CeO2-TiO2The dispersity of the medium active metal Ni is improved;
the sulfur-free nickel-based catalyst Ni/CeO2-TiO2In the middle, pure ceria has poor thermal stability and is easily sintered at high temperature to reduce oxygen storage capacity, and a transition metal element Ti is introduced into CeO2In the cubic structure, since Ti4+The ionic radius of 0.065nm is less than Ce4+Ion radius of 0.097nm, Ti4+Partially permeate to Ce4+Substitution of Ce in the crystal lattice4+Thus, on the one hand, CeO is increased2On the other hand CeO2Lattice distortion occurs, more oxygen empty acupuncture points are generated, a larger movement space is provided for lattice oxygen, and the movement transmission capability of the lattice oxygen in the catalyst and the catalytic hydrodeoxygenation performance of the catalyst are improved;
the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2In (CeO)2The release of lattice oxygen is beneficial to accelerating the migration of carbon-containing substances adsorbed on the surface, so that the accumulation of the carbon-containing substances on the surface of the catalyst is slowed down, the carbon deposition resistance of the catalyst is improved, and the catalyst shows better stability;
(3) compared with the reaction time of preparing the biofuel oil by catalyzing methyl laurate through hydrodeoxygenation by using a common Ni-based catalyst for 6-8 hours, the sulfur-free nickel-based catalyst Ni/CeO2-TiO2The reaction time for preparing the bio-fuel oil by catalyzing the hydrogenation and deoxidation of the methyl laurate is shortened to 4 hours, and the quality yield of the product bio-oil is improved from less than 90 percent to 96 percent;
compared with the common Ni-based catalyst which is recycled for 3-4 times and used for catalyzing the hydrodeoxygenation activity of methyl laurate, the activity of the catalyst is greatly reduced, and the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2The catalyst still has good catalytic activity after being directly dried, recovered and recycled for 6 times, and the mass yield of the biofuel prepared by catalyzing the hydrogenation and deoxidation of the methyl laurate is 84 percent;
the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2Warp H2After reduction at N2The catalytic activity of the catalyst can be effectively maintained for 30-50 days in the atmosphere;
(4) the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2Is prepared by the following method: with TiO having good chemical stability2Doping CeO with active physical and chemical properties, unstable structure, easy electron removal and rich surface defects2Forming a spherical granular composite metal oxide carrier CeO with weak acid and medium strong acid sites by coprecipitation and roasting2-TiO2Further impregnated with Ni (CH)3COO)2·4H2Roasting the O solution at high temperature, and reducing with hydrogen to make the active metal Ni phase uniformly distributed in CeO2-TiO2The Ni/CeO of the sulfur-free nickel-based hydrodeoxygenation catalyst is obtained on the surface of a carrier2-TiO2The method comprises the following specific steps:
the first step is as follows: dissolving a cerium source and a titanium source in a proper amount of deionized water according to a molar ratio of 1.0-1.5: 1 to form a mixed solution with a total molar concentration of 0.15-0.25 mol/L, and stirring and mixing for 4-6 hours at 40-45 ℃. Then slowly dropwise adding ammonia water into the mixed solution to control the pH value of the mixed solution within the range of 10-11 to obtain a purple yellow precipitate, continuously stirring for 8-10 h at the same temperature, aging the obtained suspension for 2-3 h at 90 ℃, cooling to room temperature, carrying out suction filtration on the obtained precipitate, and washing with deionized water and absolute ethyl alcohol for several times respectively until the filter cake is neutral. And (3) drying the mixture in a constant-temperature drying box at the temperature of 80-90 ℃ for 8-9 h. Then placing the mixture in a box-type muffle furnace, raising the temperature to 400-500 ℃ at the heating rate of 2-5 ℃/min, roasting for 4-5 h, and cooling to obtain yellow solid powder which is the CeO2-TiO2A carrier;
the second step is that: a nickel source and the CeO prepared above2-TiO2Adding a carrier and an impregnant into a 50ml eggplant-shaped bottle according to a mass ratio of 0.1-0.2: 1: 10-15, soaking and stirring for 6-12 h at 40-50 ℃, then placing the bottle at 40-50 ℃ and recovering the impregnant by using a rotary evaporator, drying the obtained yellow-green powdery solid at 70-90 ℃ for 6-8 h at constant temperature, then placing the dried yellow-green powdery solid in a box-type muffle furnace, raising the temperature to 400-500 ℃ at a heating rate of 2-3 ℃/min, roasting for 4-6 h, cooling to room temperature to obtain yellow solid powder, namely the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2Precursor of (2)A body;
the third step: mixing the prepared Ni/CeO2-TiO2Placing the catalyst precursor in a tube furnace, controlling the hydrogen flow rate to be 35-45 ml/min, raising the temperature to 450-500 ℃ at the temperature rise rate of 3-5 ℃/min, keeping the temperature for 2h, and loading the catalyst precursor on a carrier CeO at the temperature2-TiO2The NiO phase on the catalyst is reduced into an active component simple substance Ni phase, and CeO is simultaneously added2-TiO2Part of CeO in the carrier2Is reduced to Ce2O3So that CeO on the surface of the catalyst carrier2The lattice oxygen is lost to form positively charged oxygen vacancy, which is favorable for improving H in catalytic hydrodeoxygenation reaction2And the adsorption of carbonyl in the methyl laurate, and the catalytic hydrogenation deoxidation reaction of the methyl laurate is carried out;
the cerium source is at least one of cerium nitrate hexahydrate, ammonium cerium nitrate and cerium (III) acetate hydrate;
the titanium source is at least one of titanium n-propoxide, tetraisopropyl titanate and tetrabutyl titanate;
the impregnant is one of absolute methanol or absolute ethanol;
the nickel source is one of nickel nitrate hexahydrate and nickel acetate tetrahydrate;
(5) the sulfur-free nickel-based catalyst Ni/CeO2-TiO2The method for catalyzing the hydrodeoxygenation of methyl laurate to generate the bio-oil comprises the following steps: based on sulfur-free Ni/CeO catalyst2-TiO2Mixing reaction raw materials, namely methyl laurate according to a mass ratio of 0.1-0.15: 1, reacting for 2-4 hours under the conditions of a hydrogen pressure of 2.0-2.5 MPa and a reaction temperature of 280-300 ℃, cooling to room temperature after the reaction is finished, centrifuging to separate out a lower layer catalyst, filtering the centrifuged colorless transparent liquid by using a 0.45 mu m filter head, cooling to room temperature to obtain the target product, namely the biofuel oil, wherein the mass yield of the biofuel oil is 90-96%, the mass percentage of the biofuel oil is 95-98%, filtering the centrifuged lower layer catalyst, washing the centrifuged lower layer catalyst for several times by using n-hexane, drying the washed catalyst for 2-4 hours in a vacuum drying oven at the temperature of 70-80 ℃, and then repeatedly using the biofuel oil.
Technical features and effects of the invention
1. The invention is sulfur-free nickelBased on Ni/CeO2-TiO2The catalyst has the advantages of simple preparation method, high catalytic activity and stability, easy separation from a reaction system, strong carbon deposition resistance and good reusability, and can be used for catalyzing the hydrodeoxygenation of methyl laurate to prepare the biofuel oil.
2. When Ni/CeO2-TiO2The catalyst and the reaction raw material methyl laurate are 0.1-0.15: 1, the reaction temperature is 300 ℃, the reaction hydrogen pressure is 2.5MPa, and the reaction time is 4 hours, the methyl laurate is catalyzed to be hydrogenated and deoxidized to obtain the biofuel oil product, the mass yield is 90-96%, the mass percentage of the n-undecane is 95-98%, the mass yield of the catalytic methyl laurate is improved to 96% from the current prior art which is lower than 90%, and the reaction time is shortened to 4 hours from 6-8 hours.
3. The recovered catalyst is recycled for 6 times after being dried, still has good catalytic activity, the mass yield of the biofuel oil product prepared by catalyzing the hydrogenation and deoxidation of the methyl laurate is 84%, the mass percent of the n-undecane in the product is 85%, and the catalyst is greatly improved compared with the prior art that the Ni-based catalyst is generally reused for 3-4 times.
Drawings
FIG. 1(a) and (b) are respectively a carrier CeO2-TiO2Catalyst Ni/CeO2-TiO2(Ni and carrier CeO)2-TiO2Mass ratio 0.1:1), the molar ratio of Ce to Ti in these samples was 1: 1. FIG. 1(a) shows a metal oxide carrier CeO2-TiO2Presenting spherical granular structures of varying sizes. Comparing FIGS. 1(a) and (b), it was found that when CeO was used2-TiO2After the active component Ni is loaded on the carrier, the appearance of the catalyst is basically kept unchanged, but the surface becomes rougher, and more fine particles appear, which indicates that the active component Ni is successfully loaded.
FIG. 2(a) and (b) are Ni/TiO with active component Ni of 10 wt%2、Ni/CeO2-TiO2(molar ratio of Ce to Ti 1:1) TEM representation of the sample. From FIG. 2(a), Ni/TiO was observed2 Medium TiO 22The metal Ni particles loaded by the carrier have a relatively agglomeration phenomenon, so that Ni particles with relatively dense and large particle size are generated. CeO was observed from FIG. 2(b)2-TiO2The metal Ni particles loaded on the (Ce/Ti ═ 1:1) carrier have good dispersibility, and the agglomeration phenomenon of the active component Ni is obviously improved. Comparing fig. 2(a) and (b) shows that: to TiO 22Introduction of CeO into carrier2Obviously improves the interaction between the active component Ni and the carrier and improves the dispersion degree of the active metal Ni.
FIGS. 3(b), (c), (d) and (e) are Ni/CeO containing Ni in amounts of 5%, 10%, 15% and 20%, respectively2-TiO2XRD pattern of catalyst sample, (a) pure carrier CeO2-TiO2XRD patterns of the samples, the molar ratio of Ce to Ti in these samples was 1: 1. As can be seen from fig. 3, the crystal plane having a diffraction peak of 25.4 ° with 2 θ is anatase TiO2The (101) crystal plane (PDF # 21-1272). CeO of face centered cubic fluorite structure with crystal planes (111), (200), (220), (311), (222), (400), (331) and (420) at 2 theta of 28.58 °, 33.11 °, 47.51 °, 56.39 °, 59.1 °, 69.7 °, 76.6 ° and 79.2 ° mainly2(PDF # 01-075-. The diffraction peak appearing at 44.5 ° 2 θ corresponds to the (111) crystal face of the face-centered cubic phase metal Ni (PDF # 01-070-. Comparing FIGS. 3(a), (b), (c), (d), and (e), it can be seen that: the XRD diffraction peak positions of the five catalyst samples are almost the same, which indicates that the load of the active metal Ni does not destroy CeO2-TiO2The carrier has a crystal structure. When the loading of nickel is 5%, no diffraction peaks characteristic of the elemental nickel crystalline phase appear, probably due to the high dispersion of this phase on the support surface or too low a Ni content to be detected by XRD. When the loading of nickel was increased to 10%, a characteristic diffraction peak thereof appeared at 44.5 °. The Ni characteristic peak intensity increases with increasing nickel loading.
FIG. 4(a) CeO2-TiO2(Ce/Ti molar ratio 1:1), (b) CeO2-TiO2(Ce/Ti molar ratio 1:2), (c) CeO2-TiO2(Ce to Ti molar ratio 1:3), (d) CeO2-TiO2(Ce/Ti molar ratio 2:1), (e) CeO2-TiO2(molar ratio of Ce to Ti 3:1) XRD pattern of the sample. As can be seen from fig. 4, anatase TiO was found to correspond to 25.4 ° 2 θ2(101) The crystal plane (PDF #21-1272) shows, in comparison with FIGS. 4(a), (b), (c), (d), (e): with CIncrease in e content, anatase TiO2Diffraction peak intensity gradually decreases, face-centered cubic fluorite structure CeO2The diffraction peak intensity gradually increased. Anatase TiO in the catalyst sample when Ce/Ti molar ratio is 2:12The diffraction peak of the crystal phase almost disappears, and the face-centered cubic fluorite structure CeO2The diffraction peak is enhanced greatly, which indicates that Ce and Ti do not form Ce-O-Ti solid solution with amorphous structure to reduce the oxygen vacancy on the surface of the catalyst. At higher Ce contents, TiO2The diffraction peak almost disappears because the introduction of the transition element Ti into cerium oxide results in the generation of oxygen vacancies, which leads to a decrease in the cerium oxide lattice constant and thus to a decrease in the crystallite size, hindering TiO2And (5) growing crystals. Anatase TiO with increasing titanium content2The diffraction peak gradually became sharp, indicating anatase type TiO2The degree of crystallization gradually increases.
FIGS. 5(a) and (b) are respectively a carrier CeO2-TiO2Catalyst Ni/CeO2-TiO2(Ni and carrier CeO)2-TiO2H in a mass ratio of 0.1:1)2TPR plot, the molar ratio of Ce to Ti in these samples is 1: 1. As shown in FIG. 5(b), the catalysts Ni/CeO2-TiO2H of (A) to (B)2Two major reduction peaks appear in the TPR curve, representing two different reducible NiO species. The reduction peak in the 200-300 deg.c region is assigned to the catalyst carrier CeO2-TiO2The easy-reduction α -NiO species exists weak interaction force or is free on the surface of the carrier, the reduction peak in the 350-450 ℃ region corresponds to β -NiO species, and the carrier is compared with α -NiO species2-TiO2Has stronger acting force, so that the alloy is difficult to be reduced. The reduction peak in FIG. 5(a) in the region of 450 ℃ to 550 ℃ was attributed to the carrier CeO2-TiO2Surface Ce4+Reduction to Ce3+And releasing lattice oxygen to form oxygen vacancy, so that the carbonyl oxygen in the fatty acid methyl ester organic matter serving as the reaction raw material has a stronger adsorption effect, the electron transfer in the reaction process is accelerated, and the hydrogenation and deoxidation reaction of the fatty acid methyl ester raw material is promoted.
FIGS. 6(a) and (b) are Ni/CeO2-TiO2(Ni and carrier CeO)2-TiO2Mass ratio of 0.1:1), CeO2-TiO2NH of (2)3TPD plot, the Ce to Ti molar ratio in these samples is 1: 1. As can be seen from FIG. 6(b), the carrier CeO2-TiO2Two obvious desorption peaks appear between 100-200 ℃ and 300-400 ℃ respectively. The former corresponds to the weak acid position of the catalyst and the latter corresponds to the medium-strong acid position of the catalyst. Comparing fig. 6(a) and (b) shows that: with carrier CeO2-TiO2In contrast, Ni/CeO2-TiO2The position and the peak intensity of a desorption peak of the catalyst are obviously changed, the introduction of the active component Ni weakens the peak intensity of a weak acid position of the catalyst, reduces the peak area, enhances the peak intensity of a medium-strong acid position, increases the peak area, and moves the desorption peak corresponding to the medium-strong acid position to a high-temperature area, which shows that the introduction of nickel reduces the weak acid amount of the catalyst, greatly improves the medium-strong acid amount, and a new acid position appears at about 750 ℃ and corresponds to the strong acid position of the catalyst.
Detailed Description
The technical solutions and embodiments of the present invention will be described below with reference to examples, but the technical solutions and embodiments of the present invention are not limited to the following examples.
Example 1
1. Sulfur-free nickel-based catalyst Ni/CeO2-TiO2Preparation of
The first step is as follows: cerium nitrate hexahydrate Ce (NO)3)3·6H2Dissolving O and tetrabutyl titanate (TBOT) in a molar ratio of 1:1 in a proper amount of deionized water to form a mixed solution with the total concentration of 0.20mol/L, stirring and mixing for 6 hours at 40 ℃, and then slowly dropwise adding ammonia water into the mixed solution until the pH value of the mixed solution is 10 to obtain a purple yellow precipitate. Stirring was continued at the same temperature for 10h, after which the resulting suspension was aged at 90 ℃ for 3 h. Cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with deionized water and absolute ethyl alcohol for several times respectively until the filter cake is neutral, and drying in a constant-temperature drying oven at 90 ℃ for 8 h. Then placing the mixture in a box-type muffle furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting for 4h, and coolingThe obtained yellow solid powder is the CeO2-TiO2A carrier;
the second step is that: mixing Ni (CH)3COO)2·4H2O and CeO prepared as described above2-TiO2Adding a carrier and an impregnant into a 50ml eggplant-shaped bottle according to the mass ratio of 0.1:1:10, soaking and stirring for 6h at 40 ℃, then placing the bottle at 40 ℃ and recovering the impregnant by using a rotary evaporator, drying the obtained yellow green powdery solid for 8h at the constant temperature of 90 ℃, then placing the dried yellow green powdery solid into a box-type muffle furnace, raising the temperature to 500 ℃ at the heating rate of 2 ℃/min, roasting for 4h, cooling to room temperature to obtain yellow solid powder, namely the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2A precursor of (a);
the third step: mixing the prepared Ni/CeO2-TiO2The catalyst precursor is placed in a tube furnace, the hydrogen flow rate is controlled to be 45ml/min, and the temperature is raised to 500 ℃ at the temperature rise rate of 5 ℃/min and kept for 2 h. Cooling to room temperature to obtain black solid powder which is the Ni/CeO of the sulfur-free nickel-based hydrodeoxygenation catalyst2-TiO2Wherein the molar ratio of Ce to Ti is 1:1, Ni and carrier CeO2-TiO2In a mass ratio of 0.1: 1.
The Ni/CeO of the sulfur-free nickel-based catalyst is measured by SEM/TEM2-TiO2Is of spherical granular structure, passing through N2-adsorption and desorption of the Ni/CeO catalyst2-TiO2Pore diameter of 12nm and pore volume of 0.24cm3Specific surface area of 75 m/g2/g。
2. Preparation of biofuel oil by catalyzing hydrogenation and deoxidation of methyl laurate
The sulfur-free nickel-based hydrodeoxygenation catalyst prepared by the method 1 is 10 percent of Ni/CeO2-TiO2Adding a reaction raw material methyl laurate into a reaction kettle according to the mass ratio of 0.1-0.15: 1, pressurizing the reaction, adding initial hydrogen pressure of 2.5MPa, reacting at 300 ℃, reacting for 4 hours, cooling to room temperature after the reaction is finished, centrifugally separating out a lower layer catalyst, filtering the centrifuged colorless transparent liquid by using a 0.45 mu m filter head, cooling to room temperature to obtain the target product biofuel oil, wherein the mass yield is 96%, and the product contains n-undecane by massThe percentage is 98%. Filtering the lower layer catalyst after centrifugal separation, washing with n-hexane for several times, and drying in a vacuum drying oven at 80 ℃ for 4h to obtain the catalyst for next reuse.
Example 2 the operation steps are the same as example 1, but the reaction time is 10h, the yield of the biofuel product is 87%, and the product contains 90% of n-undecane by mass.
Example 3 the procedure is the same as example 1, but the reaction time is 8h, the yield of the biofuel product is 90%, and the product contains 95% of n-undecane.
Example 4 the operation steps are the same as example 1, but the reaction time is 6h, the yield of the biofuel product is 89% by mass, and the product contains 94% by mass of n-undecane.
Example 5 the procedure is the same as example 1, but the reaction time is 2 hours, the yield of the biofuel product is 80%, and the product contains 85% of n-undecane by mass.
Example 6 the procedure is the same as example 1, but the reaction hydrogen pressure is 3.5MPa, the biofuel product mass yield is 85%, and the product contains 89% of n-undecane by mass.
Example 7 the procedure is the same as example 1, but the reaction hydrogen pressure is 3.0MPa, the biofuel product quality yield is 88%, and the product contains 93% by weight of n-undecane.
Example 8 the procedure is the same as example 1, but the reaction hydrogen pressure is 2.0MPa, the biofuel product mass yield is 90%, and the product contains 95% of n-undecane by mass.
Example 9 the procedure is the same as example 1, but the reaction hydrogen pressure is 1.5MPa, the biofuel product mass yield is 86%, and the product contains 92% of n-undecane by mass.
Example 10 the procedure is the same as example 1, but the reaction hydrogen pressure is 1MPa, the biofuel product mass yield is 85%, and the product contains 88% of n-undecane by mass.
Example 11 the procedure is the same as example 1, but the reaction hydrogen pressure is 0.5MPa, the biofuel product mass yield is 27%, and the product contains 29% of n-undecane by mass.
Example 12 the procedure is the same as example 1, but the reaction temperature is 320 ℃, and the biofuel product mass yield is 85%, and the product contains 88% of n-undecane by mass.
Example 13 the procedure of example 1 was followed, but the reaction temperature was 280 ℃ to give a biofuel product with a yield of 83% by mass and a content of n-undecane of 86% by mass.
Example 14 the procedure is the same as example 1, but the reaction temperature is 260 ℃, so that the biofuel oil product mass yield is 66%, and the product contains 68% of n-undecane by mass.
Example 15 the procedure is the same as example 1, but the reaction temperature is 240 ℃, and the biofuel product mass yield is 33%, and the product contains 49% of n-undecane by mass.
EXAMPLE 16 the procedure of example 1 was followed, except that the catalyst was CeO2-TiO2The mass yield of the biofuel oil product is 10 percent, the product contains 22 percent of n-undecane and CeO2-TiO2The carrier is spherical granular structure with pore diameter of 7nm and pore volume of 0.27cm3Specific surface area of 122 m/g2/g。
EXAMPLE 17 the procedure is as in example 1, except that the catalysts Ni/CeO2-TiO2In the presence of Ni and CeO2-TiO2The mass ratio of the catalyst is 0.05:1, the mass yield of the biofuel oil product is 86 percent, the mass percent of the product contains 88 percent of n-undecane, and at the moment, the catalyst Ni/CeO is used2-TiO2Pore diameter of 7nm and pore volume of 0.20cm3Specific surface area of 92 m/g2/g。
EXAMPLE 18 the procedure is as in example 1, except that the catalysts Ni/CeO2-TiO2In the presence of Ni and CeO2-TiO2The mass ratio of the catalyst is 0.15:1, the mass yield of the biofuel oil product is 88 percent, the mass percentage of the product containing n-undecane is 94 percent, and at the moment, the catalyst Ni/CeO2-TiO2Pore diameter of 7nm and pore volume of 0.16cm3Specific surface area 67 m/g2/g。
EXAMPLE 19 the procedure of example 1 was followed except that the catalyst was 20% Ni/CeO2-TiO2In the presence of Ni and CeO2-TiO2In a mass ratio of 0.20:1，The mass yield of the obtained biofuel oil product is 85 percent, the mass percent of the obtained product contains 90 percent of n-undecane, and the Ni/CeO catalyst is used at the moment2-TiO2Pore diameter of 8nm and pore volume of 0.15cm3Specific surface area of 61 m/g2/g。
EXAMPLE 20 procedure as in example 1, except that Ce (NO) as a catalyst raw material was prepared3)3·6H2The molar ratio of O to tetrabutyl titanate is 1:2, the mass yield of the biofuel oil product is 77%, and the mass percentage of the n-undecane in the product is 81%.
EXAMPLE 21 procedure as in example 1, except that Ce (NO) as a catalyst raw material was prepared3)3·6H2The molar ratio of O to tetrabutyl titanate is 1:3, the mass yield of the biofuel oil product is 78%, and the mass percentage of the n-undecane in the product is 84%.
EXAMPLE 22 the procedure of example 1 was followed, except that the catalyst raw material Ce (NO) was prepared3)3·6H2The molar ratio of O to tetrabutyl titanate is 2:1, the mass yield of the biofuel oil product is 81%, and the mass percentage of n-undecane in the product is 90%.
EXAMPLE 23 the procedure of example 1 was followed, but the catalyst raw material Ce (NO) was prepared3)3·6H2The molar ratio of O to tetrabutyl titanate is 3:1, the mass yield of the obtained biofuel oil product is 77%, and the mass percentage of the product containing n-undecane is 83%.
EXAMPLE 24 procedure as in example 1, but preparation of catalyst feedstock without addition of Ce (NO)3)3·6H2And O, obtaining the biofuel oil product with the mass yield of 71 percent, wherein the product contains 76 percent of n-undecane by mass percent.
Example 25 the procedure is the same as example 1, but tetrabutyl titanate is not added in the raw material for preparing the catalyst, so that the mass yield of the biofuel oil product is 74%, and the mass percentage of the n-undecane in the product is 81%.
Example 26 the procedure is the same as example 1, but the catalyst is recycled for the 1 st time, the biofuel product mass yield is 95%, and the product contains 97% of n-undecane by mass.
Example 27 the procedure is the same as example 1, but the catalyst is recycled for the 2 nd time, the biofuel product mass yield is 94%, and the product contains 96% of n-undecane by mass.
Example 28 the procedure is the same as example 1, but the catalyst is recycled for the 3 rd time, the biofuel product mass yield is 93%, and the product contains 95% of n-undecane by mass.
Example 29 the procedure is the same as example 1, but the catalyst is recycled for the 4 th time, the biofuel product mass yield is 91%, and the product contains 93% of n-undecane by mass.
Example 30 the procedure is the same as example 1, but the catalyst is recycled for the 5 th time, the yield of the biofuel product is 89% by mass, and the product contains 90% by mass of n-undecane.
The operation steps of the embodiment 31 are the same as those of the embodiment 1, but the catalyst is recycled for the 6 th time, the quality yield of the biofuel oil product is 84 percent, and the mass percent of the n-undecane in the product is 85 percent.
TABLE 1 operating conditions and reaction results for examples 1-31
Note: in examples 26, 27, 28, 29, 30 and 31, the recovered catalyst after the reaction was recycled for 1, 2, 3, 4, 5 and 6 times, respectively.
TABLE 2 physical characterization data for different Ni loading catalyst samples
Note: sBET a: BET specific surface area; vp b: pore volume; dp c: the diameter of the hole.
Claims (1)
1. A method for catalyzing methyl laurate hydrodeoxygenation by a sulfur-free nickel-based catalyst is characterized by comprising the following steps:
(1) the sulfur-free nickel-based catalyst is Ni/CeO2-TiO2In which Ni and CeO2-TiO2The mass ratio of the composite metal oxide carrier is 0.1: 1;
the CeO2-TiO2In the carrier, Ce element provides an oxygen cavity, Ti element provides an acid site, and the molar ratio of Ce to Ti is 1: 1;
the sulfur-free nickel-based catalyst Ni/CeO2-TiO2Is spherical granular structure with pore diameter of 12nm and pore volume of 0.24cm3Specific surface area of 75 m/g2/g；
The sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2In the method, NiO on the surface of the catalyst is reduced into simple substance Ni through hydrogen, and metal defects on the surface of the simple substance Ni activate H in the hydrodeoxygenation reaction2And CeO2The catalyst plays a role of an electron assistant, improves the electron density around Ni on the surface of the catalyst, and promotes the reduction of NiO species;
the CeO2-TiO2Ce in composite metal oxide support4+Is reduced to Ce by hydrogen3+，Ce3+Oxygen defect sites and Ti4+The oxophilic site and carbonyl oxygen in the methyl laurate generate stronger interaction, the energy required by decarbonylation/carboxyl in the methyl laurate is reduced, and meanwhile, Ce4+Reduction to Ce3+The generated oxygen vacancies rich in electrons have stronger adsorption effect on oxygen atoms in methyl laurate, the electron transfer in the catalytic methyl laurate hydrodeoxygenation reaction process is accelerated, the catalytic activity of the catalyst is enhanced, the released free electrons are transferred to Ni active sites, the outer electrons of metal Ni are attracted, the Ni has partial positive charges, the electron-withdrawing capability of the active component Ni is enhanced, the interaction between the active component Ni and a carrier is improved, the dispersion degree of the active metal Ni is improved, and the Ni/TiO shown in the attached figure 2 of the specification has stronger adsorption effect on the oxygen atoms in the methyl laurate2、Ni/CeO2-TiO2The TEM characterization of CeO is compared and shown2Then, Ni/CeO2-TiO2The dispersity of the medium active metal Ni is improved;
the sulfur-free nickel-based catalyst Ni/CeO2-TiO2In the middle, pure ceria has poor thermal stability and is easily sintered at high temperature to reduce oxygen storage capacity, and a transition metal element Ti is introduced into CeO2In the cubic structure, since Ti4+The ionic radius of 0.065nm is less than Ce4+Ion radius of 0.097nm, Ti4+Partially permeate to Ce4+Substitution of Ce in the crystal lattice4+Thus, on the one hand, CeO is increased2On the other hand CeO2Lattice distortion occurs, more oxygen empty acupuncture points are generated, a larger movement space is provided for lattice oxygen, and the movement transmission capability of the lattice oxygen in the catalyst and the catalytic hydrodeoxygenation performance of the catalyst are improved;
the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2In (CeO)2The release of lattice oxygen is beneficial to accelerating the migration of carbon-containing substances adsorbed on the surface, so that the accumulation of the carbon-containing substances on the surface of the catalyst is slowed down, the carbon deposition resistance of the catalyst is improved, and the catalyst shows better stability;
compared with the reaction time of preparing the biofuel oil by catalyzing methyl laurate through hydrodeoxygenation by using a common Ni-based catalyst for 6-8 hours, the sulfur-free nickel-based catalyst Ni/CeO2-TiO2The reaction time for preparing the bio-fuel oil by catalyzing the hydrogenation and deoxidation of the methyl laurate is shortened to 4 hours, and the quality yield of the product bio-oil is improved from less than 90 percent to 96 percent;
compared with the common Ni-based catalyst which is recycled for 3-4 times and used for catalyzing the hydrodeoxygenation activity of methyl laurate, the activity of the catalyst is greatly reduced, and the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2The catalyst still has good catalytic activity after being directly dried, recovered and recycled for 6 times, and the mass yield of the biofuel prepared by catalyzing the hydrogenation and deoxidation of the methyl laurate is 84 percent;
the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2Warp H2After reduction at N2The catalytic activity of the catalyst can be effectively maintained for 50 days in the atmosphere;
(4) the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2Is obtained byPrepared by the following method: with TiO having good chemical stability2Doping CeO with active physical and chemical properties, unstable structure, easy electron removal and rich surface defects2Forming a spherical granular composite metal oxide carrier CeO with weak acid and medium strong acid sites by coprecipitation and roasting2-TiO2Further impregnated with Ni (CH)3COO)2·4H2Roasting the O solution at high temperature, and reducing with hydrogen to make the active metal Ni phase uniformly distributed in CeO2-TiO2The Ni/CeO of the sulfur-free nickel-based hydrodeoxygenation catalyst is obtained on the surface of a carrier2-TiO2The method comprises the following specific steps:
the first step is as follows: dissolving a cerium source and a titanium source in a proper amount of deionized water according to a molar ratio of 1:1 to form a mixed solution with a total molar concentration of 0.2mol/L, stirring and mixing for 4h at 40 ℃, then slowly dropwise adding ammonia water into the mixed solution to control the pH =10 of the mixed solution to obtain a purple yellow precipitate, continuously stirring for 10h at the same temperature, aging the obtained suspension for 3h at 90 ℃, cooling to room temperature, leaching the obtained precipitate, respectively washing with deionized water and absolute ethyl alcohol for several times until a filter cake is neutral, drying in a constant-temperature drying oven at 90 ℃ for 8h, then placing in a box-type muffle furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting for 4h, and cooling to obtain yellow solid powder which is the CeO2-TiO2A carrier;
the second step is that: a nickel source and the CeO prepared above2-TiO2Adding a carrier and an impregnant into a 50ml eggplant-shaped bottle according to the mass ratio of 0.1:1:10, impregnating and stirring for 6h at 40 ℃, then placing the bottle at 50 ℃ and recovering the impregnant by using a rotary evaporator, drying the obtained yellow green powdery solid at a constant temperature of 90 ℃ for 8h, then placing the dried yellow green powdery solid in a box-type muffle furnace, raising the temperature to 500 ℃ at the rate of 2 ℃/min, roasting for 4h, cooling to room temperature, and obtaining yellow solid powder, namely the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-TiO2A precursor of (a);
the third step: mixing the prepared Ni/CeO2-TiO2The catalyst precursor is placed in a tube furnace, and the hydrogen flow rate is controlledAt 45ml/min, with a flow rate of 5oThe temperature rise rate of C/min is increased to 500 ℃ and kept for 2h, and the CeO carrier is loaded at the temperature2-TiO2The NiO phase on the catalyst is reduced into an active component simple substance Ni phase, and CeO is simultaneously added2-TiO2Part of CeO in the carrier2Is reduced to Ce2O3So that CeO on the surface of the catalyst carrier2The lattice oxygen is lost to form positively charged oxygen vacancy, which is favorable for improving H in catalytic hydrodeoxygenation reaction2And the adsorption of carbonyl in the methyl laurate, and the catalytic hydrogenation deoxidation reaction of the methyl laurate is carried out;
the cerium source is at least one of cerium nitrate hexahydrate, ammonium cerium nitrate and cerium (III) acetate hydrate;
the titanium source is at least one of titanium n-propoxide, tetraisopropyl titanate and tetrabutyl titanate;
the impregnant is one of absolute methanol or absolute ethanol;
the nickel source is one of nickel nitrate hexahydrate and nickel acetate tetrahydrate;
(5) the sulfur-free nickel-based catalyst Ni/CeO2-TiO2The method for catalyzing the hydrodeoxygenation of methyl laurate to generate the bio-oil comprises the following steps: based on sulfur-free Ni/CeO catalyst2-TiO2Mixing reaction raw materials with methyl laurate according to the mass ratio of 0.1:1, reacting for 4 hours under the conditions of hydrogen pressure of 2.5MPa and reaction temperature of 300 ℃, cooling to room temperature after the reaction is finished, centrifugally separating out the lower-layer catalyst, filtering the centrifuged colorless transparent liquid by using a 0.45-micrometer filter head, cooling to room temperature to obtain the target product biofuel oil, wherein the mass yield of the biofuel oil is 96%, the mass percentage of the biofuel oil contains 98% of n-undecane, filtering the centrifugally separated lower-layer catalyst, washing the centrifuged lower-layer catalyst for several times by using n-hexane, and drying the centrifuged lower-layer catalyst in a vacuum drying box at 80 ℃ for 4 hours so as to be repeatedly used.
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