CN110756194A - Sulfur-free nickel-based hydrodeoxygenation catalyst and application thereof - Google Patents
Sulfur-free nickel-based hydrodeoxygenation catalyst and application thereof Download PDFInfo
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- CN110756194A CN110756194A CN201910822317.6A CN201910822317A CN110756194A CN 110756194 A CN110756194 A CN 110756194A CN 201910822317 A CN201910822317 A CN 201910822317A CN 110756194 A CN110756194 A CN 110756194A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 45
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 66
- 239000000047 product Substances 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 41
- 239000010955 niobium Substances 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 claims description 12
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical group CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 6
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 6
- 229940073769 methyl oleate Drugs 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000009286 beneficial effect Effects 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 238000006392 deoxygenation reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910019792 NbO4 Inorganic materials 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- -1 Compound methyl laurate Chemical class 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N trans-decahydronaphthalene Natural products C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a catalytic hydrodeoxygenation sulfur-free nickel-based Ni/CeO2‑Nb2O5The catalyst has high catalytic activity and is easy to be usedThe catalyst is separated from a reaction system, the reusability is good, the catalyst can be used for catalyzing the hydrodeoxygenation reaction of fatty acid methyl ester, when the mass ratio of the catalyst to the reaction raw material methyl laurate to the reaction solvent is 0.1-0.3: 1: 20-30, the added hydrogen pressure is 2.5-3.0 MPa, the reaction temperature is 280-300 ℃, and the reaction time is 8-10 h, the mass yield of the obtained hydrodeoxygenation product reaches 90%.
Description
Technical Field
The invention belongs to the field of biomass energy catalysis, and relates to a sulfur-free nickel-based catalyst Ni/CeO2-Nb2O5A method for catalyzing hydrodeoxygenation of methyl laurate.
Background
With the increasing requirement for environmental protection of energy, renewable biomass clean energy has been developed in recent years. Biomass with triglyceride as a main component is used for producing biodiesel, and fatty acid methyl ester obtained by transesterification of triglyceride and methanol is an important component of biodiesel. However, since the fatty acid methyl ester has high oxygen content and has the disadvantages of high viscosity, low cloud point, low calorific value and the like (a.e. coumans, appl.catal.b 201 (2017)) 290-.
The invention adopts a sulfur-free nickel-based catalyst Ni/CeO2-Nb2O5Methyl laurate is used as a fatty acid methyl ester model compound to catalyze the hydrodeoxygenation of the fatty acid methyl ester model compound to obtain a biofuel oil product undecane with better performance, the product quality yield reaches 90 percent, and the sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO is invented2-Nb2O5The catalyst has the advantages of high catalytic activity, good reusability, difficult loss of active components and the like.
Disclosure of Invention
Objects of the invention
The invention aims to provide a sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-Nb2O5And a method for synthesizing the biofuel oil by carrying out hydrodeoxygenation on the fatty acid methyl ester compound.
Technical scheme of the invention
1. A non-sulfur Ni-base hydrodeoxygenation catalyst is prepared from Ni and CeO2-Nb2O5Carrier constituent, Ni and CeO2-Nb2O5The mass ratio of the carriers is 0.1-0.2: 1;
the CeO2-Nb2O5Cerium in the carrier provides oxygen holes, niobium is an acid site, and the molar ratio of Ce to Nb is 0.1-1: 1;
in the sulfur-free nickel-based hydrodeoxygenation catalyst, the crystal lattices of cerium oxide are distorted and deformed due to the existence of Nb, so that oxygen in the crystal lattices of cerium oxide is easier to migrate, more oxygen vacancies are generated, and the hydrodeoxygenation performance of the catalyst is further improved;
in the sulfur-free nickel-based hydrodeoxygenation catalyst, the existence of Nb cation aerobic sites generates stronger interaction with carbonyl oxygen in the fatty acid methyl ester raw material, so that the energy required by C ═ O double bond fracture in the fatty acid methyl ester raw material is reduced, and the hydrodeoxygenation performance of the catalyst is further enhanced;
the CeO2-Nb2O5In the carrier, CeO on the surface of the carrier2An oxygen cavity is generated in the process of reduction by hydrogen, which is beneficial to the adsorption of carbonyl oxygen in the fatty acid methyl ester raw material and promotes the hydrogenation deoxidation reaction of the fatty acid methyl ester raw material;
the sulfur-free nickel-based hydrodeoxygenation catalyst is in a granular porous structure, the pore diameter is 5-10 nm, and the pore volume is 0.05-0.4 cm3A specific surface area of 55 to 65 m/g2/g；
The fatty acid methyl ester raw materials comprise methyl laurate, methyl palmitate, methyl stearate and methyl oleate.
2. The method for preparing the sulfur-free nickel-based hydrodeoxygenation catalyst 1 is to use Nb with strong acidity2O5Doping CeO capable of being reduced by hydrogen at 400-440 ℃ to generate oxygen cavity2By precipitation and calcination, sulfur-free CeO with stable granular porous structure is formed2-Nb2O5Bimetallic oxide support, impregnated with Ni (NO)3)2·6H2Roasting the O to obtain the Ni/CeO serving as the sulfur-free nickel-based hydrodeoxygenation catalyst2-Nb2O5The method comprises the following specific steps:
adding Ce (NH)4)2(NO3)6And Nb (HC)2O4)5Adding deionized water according to the molar ratio of 0.1-1: 1, stirring and dissolving to form a mixed solution with the total molar concentration of 0.1-0.25 mol/L, then slowly adding ammonia water to control the pH value of the mixed solution within the range of 11-14 to obtain a tawny precipitate, standing at room temperature for 2-4 h, carrying out suction filtration on the precipitate, washing a filter cake to be neutral by using deionized water, drying at the constant temperature of 80-110 ℃ for 8-12 h, raising the temperature to 500-600 ℃ at the heating rate of 2-3 ℃/min in a box-type muffle furnace, roasting for 2-4 h, and cooling to obtain the CeO2-Nb2O5A carrier;
mixing Ni (NO)3)2·6H2O, CeO prepared above2-Nb2O5Adding a carrier and an impregnant into a reactor according to a mass ratio of 0.1-0.2: 1: 5-7, impregnating and stirring for 2-6 h at 40-60 ℃, evaporating and recovering the impregnant at 40-60 ℃, drying the obtained yellow-green powder for 4-6 h at a constant temperature of 60-80 ℃, placing the dried yellow-green powder into a box-type muffle furnace, raising the temperature to 350-450 ℃ at a rate of 2-3 ℃/min, roasting for 4-6 h, and cooling to obtain the sulfur-free nickel-based hydrodeoxygenation catalyst;
the impregnant is absolute methanol or absolute ethanol;
reducing the prepared sulfur-free nickel-based hydrodeoxygenation catalyst for 1-2 hours at the temperature of 450-500 ℃ in a hydrogen atmosphere, and carrying out reaction in the presence of N2The catalytic activity of the catalyst can be effectively maintained for 45-60 days in the atmosphere;
the reduction is to place the sulfur-free nickel-based hydrodeoxygenation catalyst in a tubular furnace, increase the temperature to 450-500 ℃ at the heating rate of 3-5 ℃/min under the atmosphere of hydrogen flow rate of 45-55 ml/min, and load the catalyst on CeO2-Nb2O5NiO on a support2Reducing to Ni simple substance catalytic active site at CeO2-Nb2O5CeO in a carrier2Reduction to Ce3+Oxygen cavities are generated, which is beneficial to the adsorption of the fatty acid methyl ester raw material and the promotion of the hydrodeoxygenation reaction of the fatty acid methyl ester raw material, and bulk CeO2The hydrogen reduction temperature is 690-740 ℃, and Nb is2O5The hydrogen reduction temperature is 800-875 ℃, and the reduction temperature is 450-500 DEG CContinuously maintaining CeO in the original temperature range2-Nb2O5The bulk structure and physicochemical properties of the carrier are characterized;
the fatty acid methyl ester raw materials comprise methyl laurate, methyl palmitate, methyl stearate and methyl oleate.
3. The method for catalyzing the fatty acid methyl ester raw material methyl laurate for hydrodeoxygenation by the sulfur-free nickel-based hydrodeoxygenation catalyst 1 comprises the following steps: the mass ratio of the sulfur-free nickel-based hydrodeoxygenation catalyst to the reaction raw material methyl laurate to the reaction solvent is 0.1-0.3: 1: 20-30, the pressure of added hydrogen is 2.5-3.0 MPa, the reaction temperature is 280-300 ℃, the reaction time is 8-10 hours, after the reaction is finished, the reaction solvent is recovered from a reaction system, the lower-layer catalyst is centrifugally separated, and the hydrodeoxygenation product undecane is obtained, wherein the mass yield of the product reaches 90%, the centrifugally separated lower-layer catalyst is precipitated and filtered, washed by ethyl acetate, dried at the constant temperature of 60-80 ℃ for 4-6 hours, then placed in a box-type muffle furnace, heated to 350-450 ℃ at the heating rate of 2-3 ℃/min, roasted for 4-6 hours, and reduced by hydrogen at the temperature of 450-500 ℃ for 1-2 hours to be used as the catalyst for the next time for reuse;
the reaction solvent is n-decane;
the reaction solvent is recovered by evaporating n-decadecane at 120-130 ℃ under the condition of vacuum pumping of 0.084-0.0848 MPa;
evaporating at 120-130 ℃ to recover n-decane serving as a reaction solvent;
the fatty acid methyl ester raw materials comprise methyl laurate, methyl palmitate, methyl stearate and methyl oleate.
Technical advantages and effects of the invention
1. The invention relates to a sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-Nb2O5The catalyst has high catalytic activity, is easy to separate from a reaction system, has good reusability, and can be used for catalyzing the hydrodeoxygenation reaction of fatty acid methyl ester to realize the upgrading of biodiesel.
2. The mass ratio of the catalyst, the reaction raw material methyl laurate and the reaction solvent in the catalytic reaction process of the sulfur-free nickel-based hydrodeoxygenation catalyst is 0.1-0.3: 1: 20-30, the reaction hydrogen pressure is 2.5-3.5 MPa, the reaction temperature is 280-300 ℃, the reaction time is 8-10 hours, and the catalyst is cooled to room temperature after the reaction is finished to obtain a hydrodeoxygenation product, wherein the mass yield of the product is 90%.
3. When the sulfur-free nickel-based hydrodeoxygenation catalyst is repeatedly used for 5 times, the mass yield of the hydrodeoxygenation product undecane is 78%.
Drawings
FIG. 1(a) is CeO2-Nb2O5SEM photograph of carrier, FIG. 1(b) is Ni catalyst 10% Ni/CeO with 10% of load mass percent2-Nb2O5SEM photograph of (a). FIG. 1(a) shows CeO2-Nb2O5The carrier has an irregular lamellar and granular structure, and FIG. 1(b) shows that in CeO2-Nb2O5When Ni is supported on the carrier, a granular porous structure is formed, and the surface is rough and uneven.
FIG. 2 shows CeO2-Nb2O5XRD (X-ray diffraction) spectrums of Ni with different masses loaded on a carrier, wherein a, b, c, d and e are Ni/CeO (nickel/CeO) with Ni loading mass percentages of 20%, 15%, 10% and 5% respectively2-Nb2O5Catalyst, e is CeO2-Nb2O5And (3) a carrier. In the e-curve, the peaks at 28.6 °, 33.1 °, 47.5 °, and 56.3 ° were ascribed to CeO2Corresponding to the (111), (200), (220) and (311) crystal planes, respectively. The raman spectrum results, taken in fig. 3 below, show the presence of Nb in the catalyst, but no Nb peak is observed in fig. 2, which can be concluded because of its low content and uniform distribution in the support. For the curves a, b, c and d of the supported nickel, the peaks at 44.5 degrees and 51.9 degrees correspond to the (111) and (200) crystal planes of the simple substance nickel respectively.
FIG. 3 shows a carrier CeO2-Nb2O5In which a is Nb2O5B is Ce0.3Nb0.7O2(CeO2-Nb2O5The mol ratio of Ce, Nb and O in the carrier is 0.3:0.7:2), and c is Ce0.8Nb0.2O2(CeO2-Nb2O5The mol ratio of Ce, Nb and O in the carrier is 0.8:0.2:2), d is CeO2. For a, b, at 690cm-1The peak appeared in the process is attributed to NbO6The existence of an octahedral structure of the species is 200-400 cm-1The broad peak appearing there is attributed to the bending vibration of Nb-O-Nb. CeO in c is observed on Raman spectrum for b and c2Peak much higher than CeO in b2Peak, and Nb in b2O5Peak much higher than Nb in a2O5Peak, indicating Nb2O5CeO as the main component of catalyst b2Is the main component of catalyst c. Because of CeO2-Nb2O5CeO in a carrier2Oxygen cavities can be generated in the catalytic reaction process, which is beneficial to the adsorption of the fatty acid methyl ester raw material and the promotion of the hydrodeoxygenation reaction of the fatty acid methyl ester raw material, and Nb2O5Only CeO can be promoted in the process of catalytic reaction2More oxygen vacancies are generated, and the deoxidation performance of the catalyst is enhanced. For c, d, at 464cm-1The peak of (a) is attributed to the symmetric stretching of the Ce-O bond of the metal oxide having a cubic fluoride structure. The results of the raman spectroscopy further demonstrate that the peak made in the discussion of XRD results where no Nb was observed is due to the discussion that it was less abundant and uniformly distributed in the support.
FIG. 4 shows a Ni catalyst 10% Ni/CeO with a loading mass percent of 10%2-Nb2O5NH of (2)3-TPD. The peaks appearing at 100 ℃ and 250 ℃ are attributed to NbO6Species and NbO4Presence of species, NbO6Provision of Nb-O bonds forming a strong bond with O
Acid, NbO4The tetrahedral structure of the species provides Lewis acid, the peak at 380 ℃ is due to the coexistence of Nb and Ce, and the broad peak at 600-800 ℃ is due to NH3Is caused by desorption. The appearance of the Ce peak at 380 ℃ indicates that CeO2-Nb2O5The Ce oxide in the carrier can dissociate hydrogen under mild conditions to generate oxygen vacancy, which is beneficial to the adsorption of carbonyl oxygen in fatty acid methyl ester raw materials and enhances the deoxidation performance of the added catalyst. Into Ce oxideDoping Nb can distort the ceria lattice, allowing oxygen in the ceria lattice to migrate more readily, creating more oxygen vacancies. Further, the CeO2-Nb2O5With Nb in the carrier4+And Nb5+The presence of cationic oxophilic sites, which can interact strongly with the carbonyl oxygen in the starting methyl laurate, reduces the energy required for C ═ O double bond cleavage, and facilitates catalytic hydrodeoxygenation.
The technical solution and the embodiments of the present invention will be described below by way of examples, but the present invention is not limited to the following examples.
Example 1
1. Preparation of the catalyst
Ce(NH4)2(NO3)6And Nb (HC)2O4)5Adding deionized water according to the molar ratio of 0.8:0.2, fully stirring and dissolving, then slowly adding ammonia water to control the pH value of the mixed solution to be 14 to obtain a tawny precipitate, standing for 2 hours at room temperature, carrying out suction filtration on the precipitate, washing a filter cake to be neutral by using deionized water, placing the obtained filter cake in a constant-temperature drying box at 80 ℃ for drying for 12 hours, placing the dried filter cake in a box-type muffle furnace, raising the temperature to 600 ℃ at the heating rate of 2 ℃/min, roasting for 2 hours, and cooling to obtain the sulfur-free nickel-based hydrodeoxygenation catalyst carrier CeO2-Nb2O5And the carrier, wherein the molar ratio of Ce, Nb and O is 0.8:0.2: 2.
Mixing Ni (NO)3)2·6H2O, CeO prepared as above2-Nb2O5Adding a carrier and an impregnant into a reactor according to the mass ratio of 0.1:1:5, impregnating and stirring for 6 hours at 40 ℃, evaporating and recovering the impregnant at 30 ℃, drying the obtained yellow green powdery solid in a constant-temperature drying box at 80 ℃ for 4 hours, putting the dried yellow green powdery solid in a box-type muffle furnace, heating to 350 ℃ at the heating rate of 2 ℃/min, roasting for 6 hours, and cooling to obtain the sulfur-free nickel-based hydrodeoxygenation catalyst loaded with 10 mass percent of Ni, namely 10 percent of Ni/CeO2-Nb2O5(ii) a The impregnant is absolute methanol.
The prepared sulfur-free nickel-based hydrodeoxygenation catalyst is reduced for 2 hours at 500 ℃ by hydrogen and is subjected to N reaction2The atmosphere can be effectively maintained for 60 days.
The hydrogen reduction is to place the catalyst in a tubular furnace, raise the temperature to 500 ℃ at the heating rate of 5 ℃/min under the atmosphere of hydrogen flow rate of 50ml/min, and load the catalyst on CeO2-Nb2O5NiO on bimetallic oxide support2Reducing the Ni into Ni simple substance as a catalytic active site.
2. Hydrodeoxygenation of a model Compound methyl laurate
The sulfur-free nickel-based hydrodeoxygenation catalyst Ni/CeO2-Nb2O5The method for catalyzing the hydrodeoxygenation of the fatty acid methyl ester raw material methyl laurate is characterized by comprising the following steps: prepared 10% Ni/CeO2-Nb2O5The mass ratio of the sulfur-free nickel-based hydrodeoxygenation catalyst to the reaction raw material methyl laurate to the reaction solvent n-decane is 0.2:1:20, the reaction hydrogen pressure is 2.5MPa, the reaction temperature is 280 ℃, the reaction time is 8 hours, after the reaction is finished, the reaction solvent is evaporated and recovered under the conditions of vacuum pumping 0.086MPa and 125 ℃, the reaction solvent is cooled to room temperature, the lower-layer catalyst is centrifugally separated out, and the hydrodeoxygenation product undecane is obtained, the product mass yield reaches 90%, the centrifugally separated lower-layer catalyst is precipitated and filtered, washed by ethyl acetate, dried at the constant temperature of 80 ℃ for 6 hours, then placed in a box-type muffle furnace, heated to 350 ℃ at the heating rate of 2 ℃/min and roasted for 6 hours, and reduced by hydrogen at the temperature of 500 ℃ for 2 hours to be used as the catalyst for the next time for repeated use;
example 2 the procedure is the same as example 1, but the reaction hydrogen pressure is 3.5MPa, and the quality yield of the hydrodeoxygenation product undecane product is 76%.
Example 3 the procedure is the same as example 1, but the reaction hydrogen pressure is 3.0MPa, and the quality yield of the hydrodeoxygenation product undecane product is 85%.
Example 4 the procedure of example 1 was followed, but the reaction hydrogen pressure was 2.0MPa, which gave a hydrodeoxygenation product, undecane, product mass yield of 77%.
Example 5 the procedure is the same as in example 1, but the reaction hydrogen pressure is 1.5MPa, and the quality yield of the hydrodeoxygenation product undecane product is 2.5%.
Example 6 the procedure of example 1 was followed, but the reaction temperature was 320 ℃ to give 77% mass yield of the hydrodeoxygenated undecane product.
Example 7 the procedure of example 1 was followed, but the reaction temperature was 300 deg.C, to give a hydrodeoxygenation product undecane product with a mass yield of 84%.
Example 8 the procedure of example 1 was followed, but the reaction temperature was 260 ℃ to give a hydrodeoxygenation product undecane product with a mass yield of 42%.
Example 9 the procedure of example 1 was followed, but the reaction temperature was 240 ℃ to give a hydrodeoxygenation product undecane product with a mass yield of 32%.
Example 10 the procedure is the same as example 1, but the reaction time is 12h, and the quality yield of the hydrodeoxygenation product undecane product is 85%.
Example 11 the procedure is the same as example 1, but the reaction time is 10h, and the quality yield of the hydrodeoxygenation product undecane product is 85%.
Example 12 the procedure is the same as example 1, but the reaction time is 6h, and the quality yield of the hydrodeoxygenation product undecane product is 63%.
Example 13 the procedure of example 1 was followed, but the reaction time was 4 hours, resulting in a hydrodeoxygenation product undecane product mass yield of 35%.
Example 14 the procedure of example 1 was followed, but the calcination temperature was 450 ℃ to give a hydrodeoxygenated undecane product with a yield of 86% by mass.
Example 15 the procedure of example 1 was followed, but the calcination temperature was 550 ℃ to give a hydrodeoxygenated undecane product with a yield of 86% by mass.
Example 16 the procedure of example 1 was followed, except that the calcination temperature was 650 deg.C, to give a hydrodeoxygenated undecane product having a yield of 80% by mass.
Example 17 the procedure of example 1 was followed, except that the calcination temperature was 750 deg.C, to give a hydrodeoxygenated undecane product having a mass yield of 80%.
EXAMPLE 18 the procedure of example 1 was followed, but CeO was used as it is2-Nb2O5The carrier is used as a catalyst, and the quality yield of the hydrodeoxygenation product undecane product is 34 percent.
EXAMPLE 19 the procedure of example 1 was followed, except that Ni and CeO were present in the catalyst2-Nb2O5The mass ratio of the carrier is 0.05:1, and the mass yield of the hydrodeoxygenation product undecane product is 67%.
EXAMPLE 20 the procedure of example 1 was followed, except that Ni and CeO were present in the catalyst2-Nb2O5The mass ratio of the carrier is 0.15:1, and the mass yield of the hydrodeoxygenation product undecane product is 89%.
EXAMPLE 21 the procedure of example 1 was followed, except that Ni and CeO were present in the catalyst2-Nb2O5The mass ratio of the carrier is 0.2:1, and the mass yield of the hydrodeoxygenation product undecane product is 86%.
EXAMPLE 22 the procedure of example 1 was followed, but the catalyst raw material Ce (NH) was prepared4)2(NO3)6And Nb (HC)2O4)5The molar ratio is 0.3:0.7, and the mass yield of the hydrodeoxygenation product undecane product is 64 percent.
EXAMPLE 23 the procedure of example 1 was followed to prepare Ce (NH) as the catalyst starting material4)2(NO3)6And Nb (HC)2O4)5The molar ratio is 0:1, and the mass yield of the hydrodeoxygenation product undecane product is 58%.
EXAMPLE 24 procedure as in example 1, but preparation of catalyst raw material Ce (NH)4)2(NO3)6And Nb (HC)2O4)5The molar ratio is 1:0, and the mass yield of the hydrodeoxygenation product undecane product is 73%.
Example 25 the procedure is the same as example 1, but the catalyst is recycled for the 2 nd time, and the mass yield of the hydrodeoxygenation product, undecane product, is 87%.
Example 26 the procedure is the same as example 1, but the catalyst is recycled for the 3 rd time, and the quality yield of the hydrodeoxygenation product undecane product is 86%.
Example 28 the procedure is the same as example 1, but the catalyst is recycled for the 4 th time, and the quality yield of the hydrodeoxygenation product undecane product is 80%.
Example 29 the procedure is the same as example 1, but the catalyst is recycled for the 5 th time, and the hydrodeoxygenation product undecane product quality yield is 78%.
Example 30 the procedure is the same as in example 1, except that the reaction solvent is decalin, to obtain the hydrodeoxygenation product undecane with a mass yield of 89%.
Claims (3)
1. A sulfur-free nickel-based hydrodeoxygenation catalyst is characterized in that:
the sulfur-free nickel-based hydrodeoxygenation catalyst consists of Ni and CeO2-Nb2O5Carrier constituent, Ni and CeO2-Nb2O5The mass ratio of the carriers is 0.10-0.15: 1;
the CeO2-Nb2O5Cerium in the carrier provides oxygen holes, niobium is an acid site, and the molar ratio of Ce to Nb is 0.1-1: 1;
in the sulfur-free nickel-based hydrodeoxygenation catalyst, the existence of Nb enables cerium oxide lattices to be distorted and deformed, so that oxygen in cerium oxide lattices is easier to migrate, more oxygen vacancies are generated, the adsorption of carbonyl oxygen in fatty acid methyl ester raw materials is facilitated, and the deoxygenation performance of the hydrodeoxygenation catalyst is enhanced;
in the sulfur-free nickel-based hydrodeoxygenation catalyst, the existence of Nb cation aerobic sites generates strong interaction with carbonyl oxygen in the fatty acid methyl ester raw material, so that the energy required by C ═ O double bond fracture in the fatty acid methyl ester raw material is reduced, the deoxidation reaction is facilitated, and the deoxidation performance of the hydrodeoxygenation catalyst is enhanced;
the CeO2-Nb2O5In the carrier, CeO is on the surface of the carrier2Oxygen vacancy is generated in the process of reduction by hydrogen, so that oxygen adsorption of carbonyl in the fatty acid methyl ester raw material is facilitated, and the deoxidation performance of the hydrodeoxygenation catalyst is enhanced;
the sulfur-free nickel-based hydrodeoxygenation catalyst is in a granular porous structure, the pore diameter is 5-10 nm, and the pore volume is 0.05-0.4 cm3A specific surface area of 55 to 65 m/g2/g；
The fatty acid methyl ester raw materials comprise methyl laurate, methyl palmitate, methyl stearate and methyl oleate.
2. A process for preparing a sulfur-free nickel-based hydrodeoxygenation catalyst as claimed in claim 1, characterized in that: firstly, Nb with strong acidity is used2O5Doping CeO capable of being reduced by hydrogen at 400-440 ℃ to generate oxygen cavity2CeO with stable granular porous structure formed by precipitation and roasting2-Nb2O5Carrier, further impregnated with Ni (NO)3)2·6H2Roasting the mixture after O to obtain the sulfur-free nickel-based hydrodeoxygenation catalyst, which comprises the following specific steps:
adding Ce (NH)4)2(NO3)6And Nb (HC)2O4)5Adding deionized water according to the molar ratio of 0.1-1: 1, stirring and dissolving to form a mixed solution with the total molar concentration of 0.1-0.25 mol/L, then slowly adding ammonia water to control the pH value of the mixed solution within the range of 11-14 to obtain a tawny precipitate, standing at room temperature for 2-4 h, carrying out suction filtration on the precipitate, washing a filter cake to be neutral by using deionized water, drying at the constant temperature of 80-110 ℃ for 8-12 h, raising the temperature to 500-600 ℃ at the heating rate of 2-3 ℃/min in a box-type muffle furnace, roasting for 2-4 h, and cooling to obtain the CeO2-Nb2O5A carrier;
mixing Ni (NO)3)2·6H2O, CeO prepared above2-Nb2O5Adding a carrier and an impregnant into a reactor according to a mass ratio of 0.1-0.2: 1: 5-7, impregnating and stirring for 2-6 h at 40-60 ℃, evaporating and recovering the impregnant at 40-60 ℃, drying the obtained yellow-green powder for 4-6 h at a constant temperature of 60-80 ℃, placing the dried yellow-green powder into a box-type muffle furnace, raising the temperature to 350-450 ℃ at a rate of 2-3 ℃/min, roasting for 4-6 h, and cooling to obtain the sulfur-free nickel-based hydrodeoxygenation catalyst;
the impregnant is absolute methanol or absolute ethanol;
the prepared sulfur-free nickel-based hydrodeoxygenation catalyst is placed in a hydrogen atmosphere of 450-500 DEG CReducing at the temperature of N for 1-2 h2The catalytic activity of the catalyst can be effectively maintained for 45-60 days in the atmosphere;
the reduction is to place the sulfur-free nickel-based hydrodeoxygenation catalyst in a tubular furnace, increase the temperature to 450-500 ℃ at the heating rate of 3-5 ℃/min under the atmosphere of hydrogen flow rate of 45-55 ml/min, and load the catalyst on CeO2-Nb2O5NiO on a support2Reducing to Ni simple substance catalytic active site at CeO2-Nb2O5CeO in a carrier2Reduction to Ce3+Oxygen cavities are generated, which is beneficial to the adsorption of the fatty acid methyl ester raw material and the promotion of the hydrodeoxygenation reaction of the fatty acid methyl ester raw material, and bulk CeO2The hydrogen reduction temperature is 690-740 ℃, and Nb is2O5The reduction temperature of the hydrogen is 800-875 ℃, and the CeO is continuously kept within the reduction temperature range of 450-500 DEG C2-Nb2O5The bulk structure and physicochemical properties of the carrier are characterized;
the fatty acid methyl ester raw materials comprise methyl laurate, methyl palmitate, methyl stearate and methyl oleate.
3. The method for catalyzing the hydrodeoxygenation of the fatty acid methyl ester raw material methyl laurate by the sulfur-free nickel-based hydrodeoxygenation catalyst as claimed in claim 1, is characterized in that: the mass ratio of the sulfur-free nickel-based hydrodeoxygenation catalyst to the reaction raw material methyl laurate to the reaction solvent is 0.1-0.3: 1: 20-30, the pressure of added hydrogen is 2.5-3.0 MPa, the reaction temperature is 280-300 ℃, the reaction time is 8-10 hours, after the reaction is finished, the reaction solvent is recovered from a reaction system, the lower-layer catalyst is centrifugally separated, and the hydrodeoxygenation product undecane is obtained, wherein the mass yield of the product reaches 90%, the centrifugally separated lower-layer catalyst is precipitated and filtered, washed by ethyl acetate, dried at the constant temperature of 60-80 ℃ for 4-6 hours, then placed in a box-type muffle furnace, heated to 350-450 ℃ at the heating rate of 2-3 ℃/min, roasted for 4-6 hours, and reduced by hydrogen at the temperature of 450-500 ℃ for 1-2 hours to be used as the catalyst for the next time for reuse;
the reaction solvent is n-decane;
the reaction solvent is recovered by evaporating n-decadecane at 120-130 ℃ under the condition of vacuum pumping of 0.084-0.0848 MPa;
the fatty acid methyl ester raw materials comprise methyl laurate, methyl palmitate, methyl stearate and methyl oleate.
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