CN115999564A - Ni-Mo/SiO for preparing hydrocarbon fuel by catalytic biological grease hydrodeoxygenation 2 Catalyst - Google Patents
Ni-Mo/SiO for preparing hydrocarbon fuel by catalytic biological grease hydrodeoxygenation 2 Catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 229910003296 Ni-Mo Inorganic materials 0.000 title claims abstract description 111
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 41
- 239000004519 grease Substances 0.000 title claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 17
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 14
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 title claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 269
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 32
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 31
- 239000003921 oil Substances 0.000 claims abstract description 29
- 208000012839 conversion disease Diseases 0.000 claims abstract description 20
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 claims abstract description 14
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 12
- 239000008162 cooking oil Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 241001048891 Jatropha curcas Species 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 65
- 238000001179 sorption measurement Methods 0.000 claims description 51
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 46
- 238000012512 characterization method Methods 0.000 claims description 43
- 230000009467 reduction Effects 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 239000012752 auxiliary agent Substances 0.000 claims description 24
- 239000002105 nanoparticle Substances 0.000 claims description 24
- 229910018062 Ni-M Inorganic materials 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 19
- 241000894007 species Species 0.000 claims description 19
- 230000002776 aggregation Effects 0.000 claims description 17
- 125000004429 atom Chemical group 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000005054 agglomeration Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910018502 Ni—H Inorganic materials 0.000 claims description 9
- 150000001722 carbon compounds Chemical class 0.000 claims description 9
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 claims description 9
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- 239000000203 mixture Substances 0.000 claims description 9
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- 239000002253 acid Substances 0.000 claims description 8
- 230000036961 partial effect Effects 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- 229910018553 Ni—O Inorganic materials 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 6
- 241000221089 Jatropha Species 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 230000009286 beneficial effect Effects 0.000 claims description 6
- 238000010494 dissociation reaction Methods 0.000 claims description 6
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- 238000009826 distribution Methods 0.000 claims description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 6
- 229910021385 hard carbon Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 230000002401 inhibitory effect Effects 0.000 claims description 6
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- 239000000376 reactant Substances 0.000 claims description 6
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- 239000013078 crystal Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
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- 238000004458 analytical method Methods 0.000 claims description 4
- 230000009849 deactivation Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003313 weakening effect Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 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
- 238000001237 Raman spectrum Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000003776 cleavage reaction Methods 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000007547 defect Effects 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000012154 double-distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
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- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000011943 nanocatalyst Substances 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000004611 spectroscopical analysis Methods 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000010411 cooking Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000002779 inactivation Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000013043 chemical agent Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000005640 Methyl decanoate Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 15
- 230000006324 decarbonylation Effects 0.000 description 6
- 238000006606 decarbonylation reaction Methods 0.000 description 6
- 238000006114 decarboxylation reaction Methods 0.000 description 6
- -1 Alkane hydrocarbon Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229910017299 Mo—O Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Classifications
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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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Abstract
The invention relates to a method for preparing Ni-Mo/SiO of hydrocarbon fuel by catalyzing biological grease hydrodeoxygenation 2 The catalyst has low cost, high catalytic activity and n-C N 、n‑C N‑1 Alkane product selectivity, easy separation from the reaction system. When Ni-Mo/SiO 2 The mass ratio of the catalyst to the biological oil is 0.2:1, the hydrogen pressure is 3MPa, the reaction temperature is 300 ℃, the reaction time is 4 hours, the reaction conversion rate of the catalytic methyl decanoate is 98.7%, and the reaction time is n-C 10 、n‑C 9 Alkane selectivity 81.4% and 17.3%; methyl laurate reaction conversion 97.9%, n-C 12 、n‑C 11 Alkane selectivity 79.7%, 18.2%; methyl myristate reaction conversion 98.5%, n-C 14 、n‑C 13 Selectivity 81.7%, 16.8%; methyl palmitate reaction conversion rate is 99.1%, n-C 16 、n‑C 15 Selectivity 83.4%, 15.7%; methyl stearate reaction conversion98.3％，n‑C 18 、n‑C 17 Selectivity 82.5%, 15.8%; reaction conversion of Jatropha curcas oil and n-C 13‑18 Molar yield 93.5%, 89.6%; conversion rate of hydrodeoxygenation reaction of waste cooking oil and fat and n-C 13‑18 Alkane molar yields were 86.8% and 78.5%, respectively.
Description
Technical Field
The invention belongs to the field of biomass energy catalysis, and relates to a method for preparing Ni-Mo/SiO of hydrocarbon fuel by catalyzing biological grease hydrodeoxygenation 2 A catalyst.
Background
The following reaction path for catalyzing hydrodeoxygenation reaction of biological grease (taking fatty acid methyl ester as an example), wherein R is 1 Is methyl:
the fatty acid is obtained by hydrogenolysis of lactone group of oil molecule under hydrogen atmosphere, and then is converted into n-C by Hydrodeoxygenation (HDO), decarbonylation (DCN), decarboxylation (DCX) reaction path N Or n-C N-1 Alkane (normal C) N Alkanes or normal C N-1 Alkanes) hydrocarbon fuels. In addition, the catalytic grease hydrodeoxygenation reaction temperature is higher>240 c) with some amount of isoparaffins and light paraffins present in the product. Wherein the hydrodeoxygenation HDO reaction path is that carboxyl is continuously hydrogenated and converted into C-OH, and then is converted into n-C through C-O hydrocracking and deoxygenation N Alkane hydrocarbon fuel and water, or dehydrated to produce alpha-beta and beta-gamma unsaturated olefin, and further hydrogenated to produce n-C N Alkane hydrocarbon fuel. The decarbonylation DCN reaction path and the decarboxylation DCX reaction path are all used for removing-COOH in fatty acid and removing fatty acid hydrogenation intermediate fatty aldehyde-CHO to generate n-C N-1 Alkane hydrocarbon fuel and CO byproduct 2 And CO. n-C produced by the DCN and DCX reaction paths N-1 Alkane to HDO reaction pathway generated n-C N Alkane is one less carbon, so the carbon content in the hydrocarbon fuel product is reduced.
When catalyzed by a monometal sulfur-free Ni-based catalyst, the electron-rich Ni sites in the catalyst are preferentially matched with C in the fatty acid methyl ester molecules when the fatty acid methyl ester molecules are adsorbed δ+ ＝O δ- C of (2) δ+ Combining to form carboxylate or eta 1 (C) Acyl adsorption, so that the C-C bond at the ortho position of the C=O double bond in the biological grease is stretched and activated, thereby promoting the DCN/DCX reaction route to be carried out. In contrast, η 2 The (C, O) -aldehyde group is adsorbed more stably and is easier to activate the C=O bond, so that the (C, O) -aldehyde group is dissociated by the metal active center to generate active H * Then attack the generated fatty alcohol (R-CH 2 OH), and then forming hydrocarbon fuel with high carbon content through dehydration, hydrogenation or hydrogenolysis.
The invention utilizes the close relativity of electron density on Ni atom d orbit and Ni atom surrounding environment and several adsorption configurations, and adds the oxygen-philic auxiliary agent M to finely regulate and control Ni site electron density and Ni site surrounding microenvironment, thus weakening electron-rich Ni δ- And C δ+ The strong interaction between the catalyst and the catalyst stretches the C=O bond to activate the C=O bond, so that the sulfur-free Ni-based catalyst is used for catalyzing the hydrodeoxygenation of the biological grease through an HDO reaction path to prepare the hydrocarbon fuel with high carbon content.
Disclosure of Invention
The invention aims to provide a method for preparing a hydrocarbon fuel by catalyzing biological grease hydrodeoxygenation through an HDO reaction path by catalyzing Ni-Mo/SiO 2 A catalyst.
The technical proposal of the invention
Ni-Mo/SiO for preparing hydrocarbon fuel by catalytic biological grease hydrodeoxygenation 2 The catalyst is characterized in that:
(1) The biological grease is any one of methyl caprate, methyl laurate, methyl myristate, methyl palmitate and methyl stearate, and is also from natural oil jatropha oil or waste cooking grease, and the Ni-Mo/SiO 2 The catalyst isFrom Ni, mo and SiO 2 Carrier constitution, ni, mo and SiO 2 The carrier molar ratio was 0.1:0.03:1.
TABLE 1Ni-M/SiO 2 Pore structure and composition data of the catalyst
In table 1: a the specific surface area of the material is equal to the specific surface area, b the volume of the pores is such that, c the diameter of the hole is set to be equal to the diameter of the hole, d the ICP-OES method is used for measuring, E ni particle diameter was calculated according to the half-peak width Edbye-Scherrer (Debye-Scherrer) formula of XRD, f HRTEM characterization gives Ni particle diameter, g the dispersity of the Ni nanoparticles (dispersity refers to the ratio of the number of metal atoms in the catalyst surface active to the total number of metal atoms in the catalyst, and is defined as H) 2 Calculated by pulsed chemisorption assay), h h in the temperature range of 50-300 DEG C 2 The Ni-H number of the catalyst surface determined by the TPD curve, wherein the Ni-H number represents the adsorption and dissociation H of the metal active site 2 Generating active H (H) * ) Attack of oxygen-containing functional groups (c= O, C-O, C) Ar -O(C Ar -represent benzene rings), i.e. catalytic bio-grease hydrodeoxygenation activity.
TABLE 1Ni-M/SiO 2 Acidity distribution of catalyst (mmol.g) -1 )
Weak acid @ in Table 2<300 ℃, medium acid (300-500 ℃), strong acid>500 ℃ C. Is according to NH 3 -TPD curve determination;
Ni-Mo/SiO 2 the catalyst has a mesoporous particle structure with rough surface, the pore diameter is 5.48nm, the particle diameter is 100-200nm, and the pore volume is 0.33cm 3 Per gram, specific surface area 185m 2 And/g. Tables 1 and 2 show several kinds of modified Ni-M/SiO with the oxygen-philic assistant M 2 The comparison of the pore structure, the component data, the acid distribution and the strength of the catalyst can be seen in Ni-Mo/SiO 2 Pore structure of catalystThe composition data are relatively good: the particle diameter of the nano Ni particles is smaller than 3.84-4.9 nm, the dispersity of the nano Ni particles is better than 2.35%, and the chemical adsorption Ni-H is 78.3mol/g more, so that the Ni-Mo/SiO is high 2 The catalytic activity is better, and the acid distribution and the acid strength are moderate.
(2) In Ni-Mo/SiO 2 The mass ratio of the catalyst to the biological oil and fat serving as a reaction raw material is 0.2:1, the hydrogen pressure is 3MPa, the reaction temperature is 300 ℃, the high pressure sealing reaction is carried out for 4 hours, cooling is carried out, and the catalyst is centrifugally separated to obtain a product hydrocarbon fuel, wherein the result is shown in Table 3:
TABLE 3Ni-M/SiO 2 Catalytic fatty acid methyl ester hydrodeoxygenation reaction result
Ni-Mo/SiO 2 Catalytic reaction conversion rate of methyl caprate is 98.7%, and product n-C 10 、n-C 9 Alkane selectivity was 81.4% and 17.3% respectively; catalytic conversion of methyl laurate to product n-C was 97.9% 12 、n-C 11 Alkane selectivity was 79.7% and 18.2% respectively; the reaction conversion rate of catalyzing methyl myristate is 98.5%, and the product n-C 14 、n-C 13 The selectivity was 81.7% and 16.8% respectively; catalytic conversion of methyl palmitate of 99.1%, product n-C 16 、n-C 15 The selectivity was 83.4% and 15.7% respectively; catalytic conversion rate of methyl stearate reaction is 98.3%, and product n-C 18 、n-C 17 Alkane selectivity was 82.5% and 15.8% respectively; catalytic conversion rate of natural oil and fat Jatropha curcas oil reaction and n-C 13-18 The molar yields of alkane were 89.6% of 93.5%, respectively, where n-C N 、n-C N-1 Alkane (N is 14, 16 and 18 respectively) selectivity is 80.3 percent and 15.5 percent respectively; catalytic waste cooking oil hydrodeoxygenation reaction conversion and n-C 13-18 Alkane molar yields were 86.8% and 78.5%, respectively. Table 4 lists several Ni-M/SiO under the same reaction conditions and processes as described above 2 The catalyst catalyzes the comparison result of hydrodeoxygenation of natural oil jatropha oil and waste cooking oil.
TABLE 4Ni-M/SiO 2 Catalytic jatropha oil and waste cooking oil hydrodeoxygenation reaction result
As can be seen from the reaction results of tables 3 and 4, the Ni-Mo/SiO catalytic effect was the best.
(3) The content of Ni ions in the reaction liquid after 5 continuous cycles of use of the catalyst is analyzed by ICP-AES, and the result shows that the Ni-M/SiO 2 Ni loss of 0.038%, but Ni/SiO 2 The Ni loss in the alloy is 0.48 percent.
TEM characterization of the catalyst after 5 continuous cycles of use showed Ni/SiO 2 The agglomeration of nano Ni particles is serious, ni-W/SiO 2 And Ni-Fe/SiO 2 Next, ni-Mo/SiO 2 The nano Ni particles in the catalyst only have slight agglomeration.
Raman spectrum characterization of the catalyst after 5 cycles of use was performed, and all four catalysts were 1261cm in D-band -1 G belt 1593cm -1 There is a broad peak, the former is the defect site of the high activity amorphous carbon species, the latter is the tangential vibration of C-C bond in the graphite carbon structure, i.e. hard carbon species, the intensity ratio of D band to G band I D /I G Is Ni-Mo/SiO 2 3.38 of (2)>Ni-W/SiO 2 3.15 of (3)>Ni-Fe/SiO 2 1.95 of (2)>Ni/SiO 2 1.41 of (C) indicating Ni-Mo/SiO 2 Surface-formed carbon deposits are predominantly renewable amorphous carbon species, whereas hard carbon removal typically requires calcination at temperatures above 600 ℃, but such high temperature calcination promotes Ni nanoparticle agglomeration and catalyst deactivation.
(4)Ni-Mo/SiO 2 The catalyst is prepared by the following method: 0.424 g of Ni (CH) 3 COO) 2 0.085 g (NH) 4 ) 6 Mo 7 O 24 And 2.865 g of tetraethyl orthosilicate (C) 8 H 20 O 4 Si) is dissolved in 30mL double distilled water in eggplant-shaped bottle, stirring is continuously carried out at 45 ℃ for 4 hours, 20mL of 30 wt% ammonia water solution is added, the pH value is controlled to 13, metal ions are precipitated, and tetraethyl orthosilicate is hydrolyzedContinuously stirring for 2h, rotary evaporating at 70deg.C for 1h to remove water, drying at 100deg.C in oven for 8h, heating at 2deg.C/min in muffle furnace to 500deg.C, and calcining for 6h to obtain Ni-Mo/SiO 2 Oxide of Ni-Mo/SiO 2 Oxide in hydrogen atmosphere in tubular furnace, H 2 The flow rate is 45mL/min, the heating rate is 2 ℃/min, the temperature is increased to 500 ℃ for reduction for 4 hours, and the Ni-Mo/SiO is obtained 2 Bimetallic catalysts.
Comparative catalyst Ni/SiO 2 (no auxiliary agent), ni-W/SiO 2 、Ni-Fe/SiO 2 Preparation process and preparation of Ni-Mo/SiO 2 The catalysts are similar, except that no auxiliary agent is added or the added auxiliary agents are respectively corresponding to 0.127 g of ammonium metatungstate and 0.083 g of FeCl 3 。
(5)Ni-Mo/SiO 2 The characterization characteristics of the catalyst are as follows:
for comparison of Ni-Mo/SiO 2 Characterization of the catalyst the Ni/SiO characteristics are also listed below 2 、Ni-W/SiO 2 、Ni-Fe/SiO 2 And comparing the characterization data of Ni/SiO 2 、Ni-W/SiO 2 、Ni-Fe/SiO 2 、Ni-Mo/SiO 2 Simply referred to as four catalysts.
XRD characterization of four catalysts each showed an ascribed amorphous SiO at 22.8 deg 2 Metallic Ni characteristic diffraction peaks at 44.5 degrees, 51.7 degrees and 76.1 degrees, respectively belonging to Ni (111), ni (200) and Ni (220 crystal planes), without obvious Mo, W and Fe oxide auxiliary agent characteristic diffraction peaks, which show that the auxiliary agent oxides are highly dispersed in the catalyst; ni characteristic diffraction peak diffraction intensity Ni-Mo/SiO in catalyst 2 <Ni-W/SiO 2 <Ni/SiO 2 <Ni-Fe/SiO 2 Indicating Ni-Mo/SiO 2 The Ni nano particles are well dispersed, and Mo is introduced to inhibit agglomeration of the nano Ni particles in the nano catalyst.
Characterization of field emission SEM and HRTEM field emission SEM showed that all four catalysts exhibited nearly spherical particle morphology, except at Ni-Mo/SiO 2 And Ni-W/SiO 2 Uniformly dispersed metal nanoparticles were clearly observed on the surface, while Ni-Fe/SiO 2 And Ni/SiO 2 Homogeneously dispersed metal nanoparticles were not observed above; high resolution HRTEM characterizationShows Ni-Mo/SiO 2 The minimum particle diameter of the middle nano Ni particle is 3.84nm<Ni-W/SiO 2 The grain diameter of the nano Ni particles is 5.86nm<Ni/SiO 2 The grain diameter of the nano Ni particles is 6.56nm<Ni-Fe/SiO 2 The nano Ni particles have the particle diameter of 9.53nm, which shows that the Mo auxiliary agent is more effective in promoting the dispersion of the nano Ni particles in the catalyst.
STEM-EDX Spectrometry characterization display Ni-Mo/SiO 2 And Ni-W/SiO 2 Ni, mo and W are uniformly dispersed; ni-Mo/SiO 2 And Ni-W/SiO 2 The Ni-Mo and Ni-W are closer in distance, which is more beneficial to the formation of Ni-Mo and Ni-W in the catalyst reduction process to inhibit the agglomeration of nano Ni particles.
H 2 Characterization of the catalyst by TPR at H 2 Three types of characteristic peaks appear on the TPR spectrum: (i) An alpha characteristic peak in the range of 50 to 300 ℃ which is attributed to partial reduction of the surface of the M oxide particles and accompanies the catalyst surface O V Forming species; (ii) Beta characteristic peak in 300-390 deg.C, which is attributed to amorphous NiO and SiO 2 Reduction of the carrier weakly interacting NiO; (iii) Gamma characteristic peak in 390-470 deg.c, which is attributed to Ni 2+ The reduction of NiO, which strongly interacts with the support, of the M oxide, illustrates the strong interaction between Ni and the promoter M oxide; ni-Mo/SiO 2 Has an alpha peak and a very broad gamma peak, indicating Ni-Mo/SiO 2 The Ni species in (a) mainly comes from NiO reduction of the (iii) class;
EPR characterization EPR vs. O in catalyst V Content characterization, ni-Mo/SiO 2 、Ni-W/SiO 2 、Ni-Fe>SiO 2 A sharp characteristic peak appears at the g=2.005 position, which is attributed to O V Speciation of the strength Ni-Mo/SiO 2 >Ni-W/SiO 2 >Ni-Fe>SiO 2 Indicating Ni-Mo/SiO 2 Middle O V High content, which is advantageous for adsorption and activation of c=o/C-O in the reactants.
Characterization of saturation magnetization of four catalysts, ni-Mo/SiO 2 Minimum of 0.48emu/g Ni This is consistent with the nano-Ni size variation in the four catalysts due to the different forces acting between the Ni-M oxides in the catalystsThe stronger the interaction force, the stronger the sintering resistance of the catalyst in the high temperature reduction process, and thus, small-sized nano Ni particles are formed, resulting in lower saturation magnetization.
XPS characterization the surface element valence and content of the catalyst were characterized by XPS, and the results are shown in Table 5:
TABLE 5 Ni-M/SiO 2 Surface composition data of catalyst (XPS measurement)
O in Table 5 L 、O V 、O -OH Respectively representing lattice oxygen, oxygen holes and hydroxyl on the surface of the catalyst, and the M+ oxide is derived from the partial reduction of the metal M oxide nano particles of the auxiliary agent, and the process often produces O simultaneously V ；
Ni-Mo/SiO 2 Ni 2p appeared at 852.93, 854.71, 856.24 and 861.34eV positions 3/2 Characteristic peaks of orbitals, respectively attributed to Ni 0 、Ni 2+ And its corresponding satellite peak, ni 0 Mo binding energy of up to 852.93eV, greater than bulk Ni 0 Binding energy 852.7eV, indicating Ni-Mo/SiO 2 The electrons at the Ni site are transferred from Ni to Mo oxide, so that the charge density at the Ni site is reduced, thereby inhibiting the adsorption of electron-rich Ni on high-activity amorphous carbon generated in the process of catalyzing the hydrodeoxygenation reaction of biological grease, and avoiding the deactivation of the Ni site due to the coverage of carbon deposit; ni-Mo/SiO 2 Surface nano Ni 0 The highest particle content is 36.05%, mo reduces the surface energy of Ni nano particles, so that the agglomeration of the Ni nano particles is inhibited, and the smaller the size of the Ni nano particles, the adsorption and dissociation H of the Ni nano particles 2 The stronger the activity, the more Ni-H species, the higher the catalytic activity;
the O1s spectrogram of the catalyst is subjected to peak separation by a Gaussian peak separation fitting method to obtain O L 、O V And O -OH Three peaks: (1) lattice oxygen (529.78 eV), (2) oxygen vacancies (530.76 eV), (3) chemisorbed oxygen (531.47 eV), ni-Mo/SiO 2 Catalyst O V /(O L +O V +O -OH ) Up to 32.72%, indicating a surface O V The higher the species content, the more advantageous is the adsorption and activation of c=o/C-O in the reactants, and also the more advantageous is the formation of Ni-O V -MoO x Interface sites to promote charge on Ni sites from Ni to MoO x Oxygen-up hole transfer, thereby reducing the charge density of Ni sites and the adsorption degree of the Ni sites on C atoms so as to improve the carbon deposition resistance;
further analysis of Mo 3d, W4 f, fe 2p 3/2 Rail, M oxide content Ni-Mo/SiO 2 Up to 36.09%; m is M δ+ The oxide is derived from the partial reduction of promoter metal M oxide nanoparticles, which process tends to produce O simultaneously V The method is favorable for adsorbing carbonyl oxygen in the reaction raw materials to increase the catalytic activity;
Ni-M/SiO 2 the charge density at Ni sites in the alloy is formed by M oxide and M 0 Co-decisive, ni-Mo/SiO 2 The content of Mo oxide is higher than Mo 0 Ni and Mo are similar in electronegativity, so that Ni does not abstract charge from Mo atoms, but O in Mo oxide V The sites are numerous, and the charge of abstracting Ni atoms is so much, so Ni-Mo/SiO 2 The charge density of the medium Ni is reduced;
CO adsorption in situ FT-IR spectroscopy in situ FT-IR characterizes the effect of the oxophilic promoter M on electron density at Ni sites in the catalyst, strong absorption peaks represent ni·c=o adsorption configuration, including linear adsorption of c=o (2125-1975 cm -1 Linear v CO ) And bridge adsorption (1975-1850 cm) -1 Bridge v CO ) The method comprises the steps of carrying out a first treatment on the surface of the At 2070cm -1 And 2014cm -1 The CO molecules belonging to the stretching vibration characteristic peak of the position are linearly adsorbed on Ni in a coordination mode 0 The top position, the oxygen-philic auxiliary agent M does not have obvious influence on the vibration frequency corresponding to the adsorption configuration; after introducing the oxygen-philic additive Mo, at 1947cm -1 And 1915cm -1 The new weaker CO molecule stretching vibration characteristic peak (CO bridge adsorption) appears at the position, which is attributed to the CO molecule being adsorbed on the coordination unsaturated site (such as O V A site); ni-Mo/SiO 2 The characteristic peak of the medium CO bridge adsorption is strongest, indicating O V The number of sites is large; ni-Mo/SiO 2 The characteristic peak of the mid-bridge type CO adsorption respectively shows a certain blue shift (1921-1930-1947 cm) -1 ) Indicating that Ni-Mo is oxidizedThere is a certain interaction between the substances, further weakening the electron density on Ni sites and the charge is changed from Ni-O V -MO x Interface from Ni 0 O on the surface of adjacent M oxide particles V Site transfer; ni (Ni) 0 The reduction of charge density at the sites is beneficial to the reduction of Ni 0 For C in c=o functional group in biological oil δ+ Thereby inhibiting cleavage of c=o ortho C-C bond, promoting enhancement of hydrodeoxygenation selectivity; in addition to Ni reduction 0 The charge density at the site can also weaken Ni 0 The adsorption of high-activity amorphous carbon generated in the process of catalyzing the hydrodeoxygenation reaction of the biological grease can avoid the inactivation caused by the coverage of Ni sites by carbon deposit.
Technical advantages and effects of the invention
1. The catalyst of the invention has low cost, high catalytic activity and n-C N 、n-C N-1 Alkane product selectivity, easy separation from the reaction system.
2. When Ni-Mo/SiO 2 The mass ratio of the catalyst to the biological oil is 0.2:1, the hydrogen pressure is 3MPa, the reaction temperature is 300 ℃, the reaction time is 4 hours, the reaction conversion rate of the catalytic methyl decanoate is 98.7%, and the reaction time is n-C 10 、n-C 9 Alkane selectivity 81.4% and 17.3%; methyl laurate reaction conversion 97.9%, n-C 12 、n-C 11 Alkane selectivity 79.7%, 18.2%; methyl myristate reaction conversion 98.5%, n-C 14 、n-C 13 Selectivity 81.7%, 16.8%; methyl palmitate reaction conversion rate is 99.1%, n-C 16 、n-C 15 Selectivity 83.4%, 15.7%; methyl stearate reaction conversion rate is 98.3%, n-C 18 、n-C 17 Selectivity 82.5%, 15.8%; reaction conversion of Jatropha curcas oil and n-C 13-18 Molar yield 93.5%, 89.6%; conversion rate of hydrodeoxygenation reaction of waste cooking oil and fat and n-C 13-18 Alkane molar yields were 86.8% and 78.5%, respectively.
The technical scheme and the implementation mode of the invention are described below by examples, but the technical scheme of the invention is not limited to the following examples.
Example 1 0.424 g Ni (CH) 3 COO) 2 0.085 g (NH) 4 ) 6 Mo 7 O 24 And 2.865 g of tetraethyl orthosilicate (C) 8 H 20 O 4 Si) is dissolved in a 30mL double distilled water eggplant-shaped bottle, continuously stirred for 4 hours at 45 ℃, 20mL of 30 wt% ammonia water solution is added, the pH value is controlled to 13, metal ions are precipitated, tetraethyl orthosilicate is hydrolyzed at the same time, continuously stirred for 2 hours, and then, the mixture is rotationally evaporated for 1 hour at 70 ℃ to remove water, dried for 8 hours at 100 ℃ in a drying oven, and calcined for 6 hours at 500 ℃ at a heating rate of 2 ℃/min in a muffle furnace to obtain Ni-Mo/SiO 2 Oxide of Ni-Mo/SiO 2 Oxide in hydrogen atmosphere in tubular furnace, H 2 The flow rate is 45mL/min, the heating rate is 2 ℃/min, the temperature is increased to 500 ℃ for reduction for 4 hours, and the Ni-Mo/SiO is obtained 2 Bimetallic catalysts.
Comparative catalyst Ni/SiO 2 (no auxiliary agent), ni-W/SiO 2 、Ni-Fe/SiO 2 Preparation process and Ni-Mo/SiO 2 Similarly, except that no auxiliary agent is added or the added auxiliary agents respectively correspond to 0.127 g of ammonium metatungstate and 0.083 g of FeCl 3 。
Example 2 at Ni-Mo/SiO 2 The mass ratio of the catalyst to the biological oil and fat serving as a reaction raw material is 0.2:1, the hydrogen pressure is 3MPa, the reaction temperature is 300 ℃, the high-pressure closed reaction is carried out for 4 hours, the cooling is carried out, and the catalyst is centrifugally separated, thus obtaining the product hydrocarbon fuel; catalytic reaction conversion rate of methyl caprate is 98.7%, and product n-C 10 、n-C 9 Alkane selectivity was 81.4% and 17.3% respectively; catalytic conversion of methyl laurate to product n-C was 97.9% 12 、n-C 11 Alkane selectivity was 79.7% and 18.2% respectively; the reaction conversion rate of catalyzing methyl myristate is 98.5%, and the product n-C 14 、n-C 13 The selectivity was 81.7% and 16.8% respectively; catalytic conversion of methyl palmitate of 99.1%, product n-C 16 、n-C 15 The selectivity was 83.4% and 15.7% respectively; catalytic conversion rate of methyl stearate reaction is 98.3%, and product n-C 18 、n-C 17 Alkane selectivity was 82.5% and 15.8% respectively.
Example 3 the same reaction conditions and process as in example 2, ni-Mo/SiO 2 Catalytic conversion rate of natural oil and fat Jatropha curcas oil reaction and n-C 13-18 The molar yield of alkane was 89.6% of 93.5%, respectivelyWherein n-C N 、n-C N-1 Alkane (N is 14, 16 and 18 respectively) selectivity is 80.3 percent and 15.5 percent respectively.
Example 4 the same reaction conditions and process as in example 2, ni-Mo/SiO 2 Catalytic waste cooking oil hydrodeoxygenation reaction conversion and n-C 13-18 Alkane molar yields were 86.8% and 78.5%, respectively.
Example 5 by way of comparison, under the same reaction conditions and processes as in examples 2, 3 and 4, several Ni-M/SiO are listed in Table 3 and Table 4, respectively, in the above technical scheme 2 The catalyst catalyzes hydrodeoxygenation results of fatty acid methyl ester, natural oil jatropha oil or waste cooking oil, and as can be seen from the reaction results in tables 3 and 4, the Ni-Mo/SiO catalysis effect is the best.
Example 6 analysis of Ni ion content in reaction solution after 5 continuous cycles of catalyst use by ICP-AES, the results showed Ni-M/SiO 2 Ni loading loss in the catalyst was 0.038%, but Ni/SiO 2 The catalyst Ni loading loss was 0.48%.
TEM characterization of the catalyst after 5 consecutive cycles of use showed Ni/SiO 2 The agglomeration of nano Ni particles is serious, ni-W/SiO 2 And Ni-Fe/SiO 2 Next, ni-Mo/SiO 2 The nano Ni particles in the catalyst only have slight agglomeration.
Raman spectra characterize the catalyst after 5 cycles of use, all four catalysts in the D band 1261cm -1 G belt 1593cm -1 There is a broad peak, the former is the defect site of the high activity amorphous carbon species, the latter is the tangential vibration of C-C bond in the graphite carbon structure, i.e. hard carbon species, the intensity ratio of D band to G band I D /I G Is Ni-Mo/SiO 2 3.38 of (2)>Ni-W/SiO 2 3.15 of (3)>Ni-Fe/SiO 2 1.95 of (2)>Ni/SiO 2 1.41 of (C) indicating Ni-Mo/SiO 2 Surface-formed carbon deposits are predominantly renewable amorphous carbon species, whereas hard carbon removal typically requires calcination at temperatures above 600 ℃, but such high temperature calcination promotes Ni nanoparticle agglomeration and catalyst deactivation.
EXAMPLE 7Ni-Mo/SiO 2 Characterization of the catalyst
For comparison of Ni-Mo/SiO 2 Characterization of the catalyst the Ni/SiO characteristics are also listed below 2 、Ni-W/SiO 2 、Ni-Fe/SiO 2 And comparing the characterization data of Ni/SiO 2 、Ni-W/SiO 2 、Ni-Fe/SiO 2 、Ni-Mo/SiO 2 Simply referred to as four catalysts.
XRD characterization of four catalysts each showed an ascribed amorphous SiO at 22.8 deg 2 Metallic Ni characteristic diffraction peaks at 44.5 degrees, 51.7 degrees and 76.1 degrees, respectively belonging to Ni (111), ni (200) and Ni (220 crystal planes), without obvious Mo, W and Fe oxide auxiliary agent characteristic diffraction peaks, which show that the auxiliary agent oxides are highly dispersed in the catalyst; diffraction intensity of Ni characteristic diffraction peak in catalyst Ni-Mo/SiO 2 <Ni-W/SiO 2 <Ni/SiO 2 <Ni-Fe/SiO 2 Indicating Ni-Mo/SiO 2 The Ni nano particles are well dispersed, and Mo is introduced to inhibit agglomeration of the nano Ni particles in the nano catalyst.
Characterization of field emission SEM and HRTEM field emission SEM showed that all four catalysts exhibited nearly spherical particle morphology, except at Ni-Mo/SiO 2 And Ni-W/SiO 2 Uniformly dispersed metal nanoparticles were clearly observed on the surface, while Ni-Fe/SiO 2 And Ni/SiO 2 Homogeneously dispersed metal nanoparticles were not observed above; high resolution HRTEM characterization showed Ni-Mo/SiO 2 The minimum particle diameter of the middle nano Ni particle is 3.84nm<Ni-W/SiO 2 The grain diameter of the nano Ni particles is 5.86nm<Ni/SiO 2 The grain diameter of the nano Ni particles is 6.56nm<Ni-Fe/SiO 2 The grain diameter of the nano Ni particles is 9.53nm, which further indicates that the Mo auxiliary agent is more effective for nano Ni particle dispersion; determination of Ni-Mo/SiO by HRTEM characterization 2 、Ni-W/SiO 2 Lattice spacing of 0.203 and 0.205nm, respectively, indicating that the surfaces of these catalysts expose Ni (111) crystal planes; no significant contribution to the lattice spacing of Mo, W and Fe oxides was observed due to the high dispersion of Mo, W and Fe oxides; ni-Mo/SiO 2 And Ni-W/SiO 2 The lattice spacing of the Ni (111) crystal face is slightly larger than that of Ni-Fe/SiO 2 Since part of Ni atoms in the Ni (111) lattice are replaced by Mo atoms having a larger atomic radiusAnd W atoms to cause lattice distortion, resulting in an increase in lattice spacing, which is also indirectly indicative of Ni-Mo/SiO 2 And Ni-W/SiO 2 The nano Ni particles are in closer contact with Mo oxide and W oxide than Fe oxide.
STEM-EDX Spectrometry characterization display Ni-Mo/SiO 2 And Ni-W/SiO 2 Wherein Ni, mo and W are uniformly dispersed, and Ni-W/SiO 2 Slight Ni nanoparticle aggregation phenomenon still exists in the local area of the spectrogram; although Ni-Fe/SiO 2 The Fe species in the nano-Ni particles show a high dispersion state in the region, but the nano-Ni particles are obviously aggregated; ni-Mo/SiO 2 And Ni-W/SiO 2 The Ni-Mo and Ni-W are closer in distance, which is more beneficial to the formation of Ni-Mo and Ni-W in the catalyst reduction process to inhibit the agglomeration of nano Ni particles.
H 2 Characterization of the catalyst by TPR at H 2 Three types of characteristic peaks appear on the TPR spectrum: (i) An alpha characteristic peak in the range of 50 to 300 ℃ which is attributed to partial reduction of the surface of the M oxide particles and accompanies the catalyst surface O V Forming species; (ii) Beta characteristic peak in 300-390 deg.C, which is attributed to amorphous NiO and SiO 2 Reduction of the carrier weakly interacting NiO; (iii) Gamma characteristic peak in 390-470 deg.c, which is attributed to Ni 2+ The reduction of NiO, which strongly interacts with the support, of the M oxide, illustrates the strong interaction between Ni and the promoter M oxide; ni/SiO 2 Only beta peak, ni-W/SiO 2 Has alpha, beta and gamma peaks, ni-Fe/SiO 2 Has alpha and beta peaks, ni-Mo/SiO 2 Has an alpha peak and a very broad gamma peak, indicating Ni-Mo/SiO 2 The Ni species in the catalyst mainly comes from the reduction of NiO species of the (iii) th class, ni-Fe/SiO 2 The Ni species in (2) is mainly the reduction of NiO species of the (ii) type, and Ni-W/SiO 2 The Ni species in the method is mainly the reduction of NiO species of the (ii) and (iii) types; although Ni-Fe/SiO 2 No obvious reduction characteristic peak of NiO species belonging to the class (iii) is shown, but Ni-Fe/SiO 2 The position of the middle beta peak is 395 ℃ higher than Ni/SiO 2 348 ℃ of (C.) indicating Ni-Fe/SiO 2 Certain effects of Ni-Fe oxide still exist; in addition, ni-Fe/SiO is combined 2 Reduction characteristics and Ni-W/SiO 2 Positions of gamma peak484 ℃ higher than Ni-Mo/SiO 2 461 ℃, indicating Ni in the three catalysts 2+ Strength of action of M oxide Ni-W/SiO 2 >
Ni-Mo/SiO 2 >Ni-Fe/SiO 2 This is consistent with the affinity of three assistants to Ni, its dissociation energy W-O (653 kJ/mol)>Mo-O(607kJ/mol)>Fe-O(407kJ/mol)>Ni-O(366kJ/mol)；Ni 2+ The change in interaction between the M oxides further demonstrates that the introduction of the oxophilic promoter facilitates the promotion of the thermal stability and dispersibility of the nano Ni particles in the catalyst.
EPR characterization EPR vs. O in catalyst V Content characterization, ni-Mo/SiO 2 、Ni-W/SiO 2 、Ni-Fe>SiO 2 A sharp characteristic peak appears at the g=2.005 position, which is attributed to O V Speciation of the strength Ni-Mo/SiO 2 >Ni-W/SiO 2 >Ni-Fe>SiO 2 Indicating Ni-Mo/SiO 2 Middle O V High content, which is advantageous for adsorption and activation of c=o/C-O in the reactants.
Characterization of magnetic saturation intensity Ni/SiO 2 Saturation magnetization 5.88emu/g Ni The magnetic saturation strength is far lower than 55emu/g of large-particle bulk phase metal Ni (2-3 mu m) Ni This is due to Ni/SiO 2 The reason for the smaller size of the middle nano Ni particles of 6.56 nm;
Ni-Mo/SiO 2 and Ni-W/SiO 2 Has lower saturation magnetization of 0.48 and 1.89emu/g respectively Ni But Ni-Fe/SiO 2 Instead, the saturation magnetization of (C) is 7.12emu/g Ni Saturation magnetization Ni-Fe/SiO of four catalysts 2 >Ni/SiO 2 >Ni-W/SiO 2 >Ni-Mo/SiO 2 This is consistent with the nano-Ni size variation in the four catalysts due to the fact that the stronger the forces between Ni-M oxides in the catalysts, the stronger the sintering resistance of the catalysts during high temperature reduction, and thus the formation of small-sized nano-Ni particles, resulting in lower saturation magnetization.
XPS characterization the surface element valence state and content of the catalyst are characterized by XPS, ni-Mo/SiO 2 Ni 2p appeared at 852.93, 854.71, 856.24 and 861.34eV positions 3/2 Characteristic peaks of orbitals, respectively attributed to Ni 0 、Ni 2+ And its corresponding satellite peak, ni 0 The binding energy of M is Ni-Mo/SiO in turn 2 852.93eV of (V)>Ni-W/SiO 2 852.58eV of (V)>Ni-Fe/SiO 2 852.14eV, ni-Mo/SiO 2 The binding energy of Ni-Mo is larger than that of bulk Ni 0 The binding energy 852.7eV is electron loss, and the charge density on Ni sites is reduced; in addition Ni-Mo/SiO 2 Middle Ni 0 Binding energy 852.93eV higher than bulk Ni 0 852.7eV of (B), indicating Ni-Mo/SiO 2 The electrons at Ni sites are transferred from Ni to Mo oxide, resulting in a decrease in charge density at Ni sites, and in Ni-W/SiO 2 And Ni-Fe/SiO 2 In, their Ni 0 The electron binding energy reduction values were 0.12 and 0.56eV, respectively, and electrons were transferred from the promoter oxide to the Ni sites (WO x →Ni、FeO x Ni) such that the charge density at Ni sites increases, indicating that Ni-Mo/SiO among the three catalysts 2 The charge density of the Ni site is the lowest, so that the adsorption of the electron-rich Ni to the high-activity amorphous carbon generated in the process of catalyzing the hydrodeoxygenation reaction of the biological grease is inhibited, and the Ni site is prevented from being covered by carbon deposit to be inactivated; ni-Mo/SiO 2 Surface nano Ni 0 Particle content 36.05%>Ni-W/SiO 2 Ni of (2) 0 Particle content 31.96%>Ni-Fe/SiO 2 Ni of (2) 0 The particle content is 15.4%, mo reduces the surface energy of Ni nano particles, thereby inhibiting the agglomeration of the Ni nano particles, and the smaller the size of the Ni nano particles, the adsorption and dissociation H of the Ni nano particles 2 The more active the Ni-H species, the higher the catalytic activity.
The O1s spectrogram of the catalyst is subjected to peak separation by a Gaussian peak separation fitting method to obtain O L 、O V And O -OH Three peaks: (1) lattice oxygen (529.78 eV), (2) oxygen vacancies (530.76 eV), (3) chemisorbed oxygen species (531.47 eV), catalyst O V /(O L +O V +O -OH ) The ratio is Ni-Mo/SiO respectively 2 32.72% of>Ni-W/SiO 2 28.87% of>Ni-Fe/SiO 2 21.45% of the total surface O of the catalyst V The higher the species content, the more advantageous is the adsorption and activation of c=o/C-O in the reactants, and also the more advantageous is the formation of Ni-O V -MoO x Interface sites to promote charge on Ni sites from Ni to MoO x Oxygen-up hole transfer, thereby reducing the charge density of Ni sites and the adsorption degree of C atoms to improve the carbon deposition resistance.
Further analysis of Mo 3d, W4 f, fe 2p 3/2 Rail, catalyst removes metal M 0 M is detected in addition to the simple substance δ+ Oxide, ni-Mo/SiO 2 M in (v) δ+ Oxide content 36.09%>Ni-Fe/SiO 2 M in (v) δ+ Oxide content 23.11%>Ni-W/SiO 2 M in (v) δ+ Oxide content 22.82%, ni-W/SiO 2 M in (v) 0 Content 22.5%<Ni-Mo/SiO 2 M in (v) 0 Content 24.84%<Ni-Fe/SiO 2 M in (v) 0 The content is 59.46%; m is M δ+ The oxide is derived from the partial reduction of promoter metal M oxide nanoparticles, which process tends to produce O simultaneously V The stronger the metal-oxygen bond, the more difficult the auxiliary oxide particles are to reduce, and the O is increased V Difficulty in formation, resulting in reduced catalytic activity by reducing the number of adsorption sites for carbonyl oxygen; however, too low a metal-oxygen bond strength will result in further reduction of the M oxide to M 0 The simple substance further forms Ni-M alloy or Ni-M intermetallic compound with Ni site to reduce catalytic activity.
Ni-M/SiO 2 The charge density at Ni sites in the alloy is formed by M oxide and M 0 Determining together; ni-Fe/SiO 2 M in (v) 0 The content is far higher than Ni-W/SiO 2 、Ni-W/SiO 2 And Ni atomic electronegativity 1.88 is greater than Fe atomic electronegativity 1.83, causing its charge to be transferred from Fe to Ni; while Ni-Mo/SiO 2 The strength of the Mo-O bond in the alloy is moderate, O V The species content is the greatest, which is beneficial to accelerating the c=o/C-O bond hydroconversion; ni-W/SiO 2 The W oxide content is slightly higher than W 0 But Ni electronegativity 1.88 is higher than W electronegativity 1.7, ni has a higher charge-extracting ability from W atom than O in W oxide V The site abstracts the charge of Ni atoms, so Ni-W/SiO 2 The medium Ni charge density increases slightly; while Ni-Mo/SiO 2 The content of Mo oxide is higher than Mo 0 Ni and Mo are similar in electronegativity, so that Ni does not abstract charge from Mo atoms, but O in Mo oxide V The sites are numerous, and the charge of abstracting Ni atoms is so much, so Ni-Mo/SiO 2 The Ni charge density is reduced.
CO adsorption in situ FT-IR Spectroscopy in situ FT-IR characterizes the effect of an oxophilic promoter on electron density at Ni sites in a catalyst, and strong absorption peaks represent Ni.C=O adsorption configuration, including linear adsorption of C=O (2125-1975 cm -1 Linear v CO ) And bridge adsorption (1975-1850 cm) -1 Bridge v CO ) The method comprises the steps of carrying out a first treatment on the surface of the At 2070cm -1 And 2014cm -1 The CO molecules belonging to the stretching vibration characteristic peak of the position are linearly adsorbed on Ni in a coordination mode 0 The top position, the oxygen-philic auxiliary agent does not have obvious influence on the vibration frequency corresponding to the adsorption configuration; after introducing the oxygen-philic additive Mo, at 1947cm -1 And 1915cm -1 The new weaker CO molecule stretching vibration characteristic peak (CO bridge adsorption) appears at the position, which is attributed to the CO molecule being adsorbed on the coordination unsaturated site (such as O V A site); CO bridge adsorption characteristic peak intensity Ni-Mo/SiO in three catalysts 2 >Ni-W/SiO 2 >Ni-Fe/SiO 2 This indicates Ni-Mo/SiO 2 Middle O V The number of sites is large; in addition to Ni-Fe/SiO 2 Comparison, ni-Mo/SiO 2 And Ni-W/SiO 2 The characteristic peak of the mid-bridge CO adsorption respectively shows a certain blue shift phenomenon (1921-1930-1947 cm) -1 ,1892→1903→1915cm -1 ) This indicates Ni-MO x There is a certain interaction between them, and Ni-Mo>Ni-W>Ni-Fe, further weakening electron density at Ni sites; and at Ni/SiO 2 No obvious bridge type CO adsorption characteristic peak, which indicates that a certain amount of O can be generated by introducing the oxygen-philic auxiliary agent V Sites, which are consistent with EPR characterization results; ni-Mo/SiO 2 And Ni-W/SiO 2 The blue shift of mid-bridge CO molecules indicates a decrease in electron density at the Ni sites and a charge transfer from Ni-O V -MO x Interface from Ni 0 To its adjacent MO x O on particle surface V Site transfer; ni (Ni) 0 The reduction of charge density at the sites is beneficial to the reduction of Ni 0 For C in c=o functional group in biological oil δ+ Thereby inhibiting cleavage of c=o ortho C-C bond, promoting enhancement of hydrodeoxygenation selectivity; ni reduction 0 The charge density on the sites can weaken the adsorption of Ni0 to high-activity amorphous carbon generated in the process of catalyzing the hydrodeoxygenation reaction of the biological grease, and avoid the Ni sites from being covered and deactivated by carbon deposit.
Claims (1)
1. Ni-Mo/SiO for preparing hydrocarbon fuel by catalytic biological grease hydrodeoxygenation 2 The catalyst is characterized in that:
(1) The biological grease is any one of methyl caprate, methyl laurate, methyl myristate, methyl palmitate and methyl stearate; the biological grease is also from natural oil jatropha curcas oil or waste cooking grease; the Ni-Mo/SiO 2 The catalyst is prepared from Ni, mo and SiO 2 Carrier constitution, ni, mo and SiO 2 The molar ratio of the carrier is 0.1:0.03:1;
Ni-Mo/SiO 2 the catalyst has a mesoporous particle structure with rough surface, the pore diameter is 5.48nm, the particle diameter is 100-200nm, and the pore volume is 0.33cm 3 Per gram, specific surface area 185m 2 /g；
Tables 1 and 2 show several kinds of modified Ni-M/SiO with the oxygen-philic assistant M 2 Comparison of pore structure, composition data and acid strength distribution of the catalyst, it can be seen that Ni-Mo/SiO 2 The pore structure and composition data of the catalyst are relatively good: the particle diameter of the nano Ni particles is smaller than 3.84-4.9 nm, the dispersity of the nano Ni particles is better than 2.35%, and the chemical adsorption Ni-H is 78.3mol/g more, so that the Ni-Mo/SiO is high 2 The catalytic activity is better, and the acidity distribution is moderate;
Ni-M/SiO 2 pore structure and composition data of the catalyst
In table 1: a the specific surface area of the material is equal to the specific surface area, b the volume of the pores is such that, c the diameter of the hole is set to be equal to the diameter of the hole, d the ICP-OES method is used for measuring, E ni particle diameter was calculated according to the half-peak width Edbye-Scherrer (Debye-Scherrer) formula of XRD, f characterizing HRTEM to obtain Ni particle diameter; g dispersion degree of nano Ni particles (dispersion degree means catalystThe ratio of the number of surface active metal atoms of the catalyst to the total number of metal atoms in the catalyst is defined by H 2 Calculated by pulsed chemisorption assay), h h in the temperature range of 50-300 DEG C 2 The Ni-H number of the catalyst surface determined by the TPD curve, wherein the Ni-H number represents the adsorption and dissociation H of the metal active site 2 Generating active H (H) * ) Attack of oxygen-containing functional groups (c= O, C-O, C) Ar -O(C Ar -represent benzene rings), i.e. catalytic bio-grease hydrodeoxygenation activity;
TABLE 1Ni-M/SiO 2 Acidity distribution of catalyst (mmol.g) -1 )
Weak acid @ in Table 2<300 ℃, medium acid (300-500 ℃), strong acid>500 ℃ C. Is according to NH 3 -TPD curve determination;
(2) In Ni-Mo/SiO 2 The mass ratio of the catalyst to the biological oil and fat serving as a reaction raw material is 0.2:1, the hydrogen pressure is 3MPa, the reaction temperature is 300 ℃, the high-pressure closed reaction is carried out for 4 hours, the cooling is carried out, and the product hydrocarbon fuel is obtained after the catalyst is centrifugally separated out: catalytic reaction conversion rate of methyl caprate is 98.7%, and product n-C 10 、n-C 9 Alkane selectivity was 81.4% and 17.3% respectively; catalytic conversion of methyl laurate to product n-C was 97.9% 12 、n-C 11 Alkane selectivity was 79.7% and 18.2% respectively; the reaction conversion rate of catalyzing methyl myristate is 98.5%, and the product n-C 14 、n-C 13 The selectivity was 81.7% and 16.8% respectively; catalytic conversion of methyl palmitate of 99.1%, product n-C 16 、n-C 15 The selectivity was 83.4% and 15.7% respectively; catalytic conversion rate of methyl stearate reaction is 98.3%, and product n-C 18 、n-C 17 Alkane selectivity was 82.5% and 15.8% respectively; catalytic conversion rate of natural oil and fat Jatropha curcas oil reaction and n-C 13-18 The molar yields of alkane were 89.6% of 93.5%, respectively, where n-C N 、n-C N-1 Alkane (N is 14, 16 and 18 respectively) selectivity is 80.3 percent and 15.5 percent respectively; catalytic waste cooking oil hydrogenationDeoxygenation reaction conversion and n-C 13-18 Alkane molar yields were 86.8% and 78.5%, respectively; under the same reaction conditions and processes, several Ni-M/SiO are shown in tables 3 and 4, respectively 2 Comparison results of hydrodeoxygenation of the natural oil, jatropha oil, and waste cooking oil, catalyzed by the catalyst:
TABLE 3Ni-M/SiO 2 Catalytic fatty acid methyl ester hydrodeoxygenation reaction result
TABLE 4Ni-M/SiO 2 Catalytic jatropha oil and waste cooking oil hydrodeoxygenation reaction result
As can be seen from the reaction results in the above tables 3 and 4, the Ni-Mo/SiO catalytic effect is the best;
(3) The content of Ni ions in the reaction liquid after 5 continuous cycles of use of the catalyst is analyzed by ICP-AES, and the result shows that the Ni-M/SiO 2 Ni loss of 0.038%, but Ni/SiO 2 Ni loss of 0.48%;
TEM characterization of the catalyst after 5 continuous cycles of use showed Ni/SiO 2 The agglomeration of nano Ni particles is serious, ni-W/SiO 2 And Ni-Fe/SiO 2 Next, ni-Mo/SiO 2 The nano Ni particles in the catalyst are only slightly agglomerated;
raman spectrum characterization of the catalyst after 5 cycles of use was performed, and all four catalysts were 1261cm in D-band -1 G belt 1593cm -1 There is a broad peak, the former is the defect site of the high activity amorphous carbon species, the latter is the tangential vibration of C-C bond in the graphite carbon structure, i.e. hard carbon species, the intensity ratio of D band to G band I D /I G Is Ni-Mo/SiO 2 3.38 of (2)>Ni-W/SiO 2 3.15 of (3)>Ni-Fe/SiO 2 1.95 of (2)>Ni/SiO 2 1.41 of (C) indicating Ni-Mo/SiO 2 Surface formed carbon depositRenewable amorphous carbon species are the main, and hard carbon is generally removed by calcining at a high temperature above 600 ℃, but the calcination at a high temperature can promote Ni nano particles to agglomerate so as to deactivate the catalyst;
(4)Ni-Mo/SiO 2 the catalyst is prepared by the following method: 0.424 g of Ni (CH) 3 COO) 2 0.085 g (NH) 4 ) 6 Mo 7 O 24 And 2.865 g of tetraethyl orthosilicate (C) 8 H 20 O 4 Si) is dissolved in a 30mL double distilled water eggplant-shaped bottle, continuously stirred for 4 hours at 45 ℃, 20mL of 30 wt% ammonia water solution is added, the pH value is controlled to 13, metal ions are precipitated, tetraethyl orthosilicate is hydrolyzed at the same time, continuously stirred for 2 hours, and then, the mixture is rotationally evaporated for 1 hour at 70 ℃ to remove water, dried for 8 hours at 100 ℃ in a drying oven, and calcined for 6 hours at 500 ℃ at a heating rate of 2 ℃/min in a muffle furnace to obtain Ni-Mo/SiO 2 Oxide of Ni-Mo/SiO 2 Oxide in hydrogen atmosphere in tubular furnace, H 2 The flow rate is 45mL/min, the heating rate is 2 ℃/min, the temperature is increased to 500 ℃ for reduction for 4 hours, and the Ni-Mo/SiO is obtained 2 A bimetallic catalyst;
comparative catalyst Ni/SiO 2 (no auxiliary agent), ni-W/SiO 2 、Ni-Fe/SiO 2 Preparation process and preparation of Ni-Mo/SiO 2 The catalysts are similar, except that no auxiliary agent is added or the added auxiliary agents are respectively corresponding to 0.127 g of ammonium metatungstate and 0.083 g of FeCl 3 ；
(5)Ni-Mo/SiO 2 The characterization characteristics of the catalyst are as follows:
for comparison of Ni-Mo/SiO 2 Characterization of the catalyst the Ni/SiO characteristics are also listed below 2 、Ni-W/SiO 2 、Ni-Fe/SiO 2 And comparing the characterization data of Ni/SiO 2 、Ni-W/SiO 2 、Ni-Fe/SiO 2 、Ni-Mo/SiO 2 Known simply as four catalysts;
XRD characterization of four catalysts each showed an ascribed amorphous SiO at 22.8 deg 2 The characteristic diffraction peaks of metal Ni appear at 44.5 degrees, 51.7 degrees and 76.1 degrees, are respectively attributed to Ni (111), ni (200) and Ni (220 crystal planes), and have no obvious characteristic diffraction peaks of Mo, W and Fe oxide auxiliary agents, which indicates that the auxiliary agents oxide is catalyzedThe inside of the chemical agent is highly dispersed; ni characteristic diffraction peak diffraction intensity Ni-Mo/SiO in catalyst 2 <Ni-W/SiO 2 <Ni/SiO 2 <Ni-Fe/SiO 2 Indicating Ni-Mo/SiO 2 The nano Ni particles are well dispersed, and Mo is introduced to inhibit agglomeration of nano Ni particles in the nano catalyst;
characterization of field emission SEM and HRTEM field emission SEM showed that all four catalysts exhibited nearly spherical particle morphology, except at Ni-Mo/SiO 2 And Ni-W/SiO 2 Uniformly dispersed metal nanoparticles are clearly observed on the surface; high resolution HRTEM characterization showed Ni-Mo/SiO 2 The minimum particle diameter of the nano Ni particles is 3.84nm, which shows that the Mo auxiliary agent is more effective in promoting the dispersion of the nano Ni particles in the catalyst;
STEM-EDX Spectrometry characterization display Ni-Mo/SiO 2 And Ni-W/SiO 2 Ni, mo and W are uniformly dispersed; ni-Mo/SiO 2 And Ni-W/SiO 2 The distance between Ni-Mo and Ni-W is closer, which is more favorable for forming Ni-Mo and Ni-W in the reduction process of the catalyst to inhibit the agglomeration of nano Ni particles;
H 2 characterization of the catalyst by TPR at H 2 Three types of characteristic peaks appear on the TPR spectrum: (i) An alpha characteristic peak in the range of 50 to 300 ℃ which is attributed to partial reduction of the surface of the M oxide particles and accompanies the catalyst surface O V Forming species; (ii) Beta characteristic peak in 300-390 deg.C, which is attributed to amorphous NiO and SiO 2 Reduction of the carrier weakly interacting NiO; (iii) Gamma characteristic peak in 390-470 deg.c, which is attributed to Ni 2+ The reduction of NiO, which strongly interacts with the support, of the M oxide, illustrates the strong interaction between Ni and the promoter M oxide; ni-Mo/SiO 2 Has an alpha peak and a very broad gamma peak, indicating Ni-Mo/SiO 2 Wherein Ni is mainly from NiO reduction of the (iii) class;
EPR characterization EPR vs. O in catalyst V Content characterization, ni-Mo/SiO 2 、Ni-W/SiO 2 、Ni-Fe>SiO 2 A sharp characteristic peak appears at the g=2.005 position, which is attributed to O V Speciation of the strength Ni-Mo/SiO 2 >Ni-W/SiO 2 >Ni-Fe>SiO 2 Indicating Ni-Mo/SiO 2 Middle O V High content, which is advantageous for adsorption and activation of c=o/C-O in the reactants;
characterization of saturation magnetization of four catalysts, ni-Mo/SiO 2 Minimum of 0.48emu/g Ni This is consistent with the nano-Ni size variation in the four catalysts, due to the fact that the different forces act between Ni-M oxides in the catalysts, the stronger the forces act between Ni-M oxides, the stronger the sintering resistance of the catalysts in the high-temperature reduction process, and thus small-size nano-Ni particles are formed, resulting in lower saturation magnetization;
XPS characterization the surface element valence and content of the catalyst were characterized by XPS, and the results are shown in Table 5:
TABLE 5 Ni-M/SiO 2 Surface composition data of catalyst (XPS measurement)
O in Table 5 L 、O V 、O -OH Respectively representing lattice oxygen, oxygen holes and hydroxyl on the surface of the catalyst, wherein M+ oxide is derived from partial reduction of auxiliary metal M oxide nano particles, and OV is often generated simultaneously in the process;
Ni-Mo/SiO 2 ni 2p appeared at 852.93, 854.71, 856.24 and 861.34eV positions 3/2 Characteristic peaks of orbitals, respectively attributed to Ni 0 、Ni 2+ And its corresponding satellite peak, ni 0 Mo binding energy of up to 852.93eV, greater than bulk Ni 0 Binding energy 852.7eV, indicating Ni-Mo/SiO 2 The electrons at the Ni site are transferred from Ni to Mo oxide, so that the charge density at the Ni site is reduced, thereby inhibiting the adsorption of electron-rich Ni on high-activity amorphous carbon generated in the process of catalyzing the hydrodeoxygenation reaction of biological grease, and avoiding the deactivation of the Ni site due to the coverage of carbon deposit; ni-Mo/SiO 2 Surface nano Ni 0 The highest particle content is 36.05%, mo reduces the surface energy of Ni nano particles, so that the agglomeration of the Ni nano particles is inhibited, and the smaller the size of the Ni nano particles, the adsorption and dissociation H of the Ni nano particles 2 The stronger the activity, the more Ni-H species, the higher the catalytic activity;
the O1s spectrogram of the catalyst is subjected to peak separation by a Gaussian peak separation fitting method to obtain O L 、O V And O -OH Three peaks: (1) lattice oxygen (529.78 eV), (2) oxygen vacancies (530.76 eV), (3) chemisorbed oxygen (531.47 eV), ni-Mo/SiO 2 Catalyst O V /(O L +O V +O -OH ) Up to 32.72%, indicating a surface O V The higher the species content, the more advantageous is the adsorption and activation of c=o/C-O in the reactants, and also the more advantageous is the formation of Ni-O V -MoO x Interface sites to promote charge on Ni sites from Ni to MoO x Oxygen-up hole transfer, thereby reducing the charge density of Ni sites and the adsorption degree of the Ni sites on C atoms so as to improve the carbon deposition resistance;
further analysis of Mo 3d, W4 f, fe 2p 3/2 Rail, M oxide content Ni-Mo/SiO 2 Up to 36.09%; m is M δ+ The oxide is derived from the partial reduction of promoter metal M oxide nanoparticles, which process tends to produce O simultaneously V The method is favorable for adsorbing carbonyl oxygen in the reaction raw materials to increase the catalytic activity;
Ni-M/SiO 2 the charge density at Ni sites in the alloy is formed by M oxide and M 0 Co-decisive, ni-Mo/SiO 2 The content of Mo oxide is higher than Mo 0 Ni and Mo are similar in electronegativity, so that Ni does not abstract charge from Mo atoms, but O in Mo oxide V The sites are numerous, and the charge of abstracting Ni atoms is so much, so Ni-Mo/SiO 2 The charge density of the medium Ni is reduced;
CO adsorption in situ FT-IR spectroscopy in situ FT-IR characterizes the effect of the oxophilic promoter M on electron density at Ni sites in the catalyst, strong absorption peaks represent ni·c=o adsorption configuration, including linear adsorption of c=o (2125-1975 cm -1 Linear v CO ) And bridge adsorption (1975-1850 cm) -1 Bridge v CO ) The method comprises the steps of carrying out a first treatment on the surface of the At 2070cm -1 And 2014cm -1 The CO molecules belonging to the stretching vibration characteristic peak of the position are linearly adsorbed on Ni in a coordination mode 0 The top position, the oxygen-philic auxiliary agent M does not have obvious influence on the vibration frequency corresponding to the adsorption configuration; after introducing the oxygen-philic additive Mo, at 1947cm -1 And 1915cm -1 Location occurrenceNovel, weaker CO molecule stretching vibration characteristic peak (CO bridge adsorption) which is attributed to CO molecule adsorption on coordination unsaturated site (such as O V A site); ni-Mo/SiO 2 The characteristic peak of the medium CO bridge adsorption is strongest, indicating O V The number of sites is large; ni-Mo/SiO 2 The characteristic peak of the mid-bridge type CO adsorption respectively shows a certain blue shift (1921-1930-1947 cm) -1 ) Indicating that there is a certain interaction between Ni-Mo oxides, further weakening the electron density at Ni sites and the charge is changed from Ni-O V -MO x Interface from Ni 0 O on the surface of adjacent M oxide particles V Site transfer; ni (Ni) 0 The reduction of charge density at the sites is beneficial to the reduction of Ni 0 For C in c=o functional group in biological oil δ+ Thereby inhibiting cleavage of c=o ortho C-C bond, promoting enhancement of hydrodeoxygenation selectivity; in addition to Ni reduction 0 The charge density at the site can also weaken Ni 0 The adsorption of high-activity amorphous carbon generated in the process of catalyzing the hydrodeoxygenation reaction of the biological grease can avoid the inactivation caused by the coverage of Ni sites by carbon deposit.
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| CN111111679A (en) * | 2020-01-06 | 2020-05-08 | 湘潭大学 | Sulfur-free nickel-molybdenum bimetallic hydrodeoxygenation catalyst |
| CN111298799A (en) * | 2019-12-30 | 2020-06-19 | 广西中医药大学 | Preparation method and application of reduced NiMo bifunctional catalyst |
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| CN1344671A (en) * | 2001-10-17 | 2002-04-17 | 中国科学院兰州化学物理研究所 | Catalyst for reforming mathand and carbon dioxide to synthesize gas |
| CN111298799A (en) * | 2019-12-30 | 2020-06-19 | 广西中医药大学 | Preparation method and application of reduced NiMo bifunctional catalyst |
| CN111111679A (en) * | 2020-01-06 | 2020-05-08 | 湘潭大学 | Sulfur-free nickel-molybdenum bimetallic hydrodeoxygenation catalyst |
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