CN112264032A - Catalyst for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran - Google Patents
Catalyst for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran Download PDFInfo
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- CN112264032A CN112264032A CN202011160159.1A CN202011160159A CN112264032A CN 112264032 A CN112264032 A CN 112264032A CN 202011160159 A CN202011160159 A CN 202011160159A CN 112264032 A CN112264032 A CN 112264032A
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- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910003294 NiMo Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000002349 favourable effect Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 description 6
- 229910015338 MoNi Inorganic materials 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QGXJTDHPWUQRFT-UHFFFAOYSA-N 2-methyl-3H-furan-2-carboxylic acid Chemical compound CC1(OC=CC1)C(=O)O QGXJTDHPWUQRFT-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910006227 ZrO4 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- 229940033495 antimalarials Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/40—
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- B01J35/613—
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- B01J35/633—
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- B01J35/647—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
Abstract
The invention discloses a catalyst NiMo/ZrO for catalyzing furfural to prepare 2-methylfuran through hydrodeoxygenation2The catalyst has high catalytic activity and stability at low temperature, strong carbon deposition resistance, good reusability and easy separation from a reaction system. When NiMo/ZrO2The mass ratio of the catalyst to the furfural serving as a reaction raw material is 0.1:1, the reaction temperature is 180 ℃, the reaction hydrogen pressure is 3MPa, the furfural is catalyzed for hydrogenation and deoxidation reaction for 6 hours, the molar yield of the 2-methylfuran crude product which is a hydrogenation and deoxidation product is obtained after the furfural is cooled to the room temperature and is 94%, and the molar yield of the 2-methylfuran crude product is still more than 86% after the catalyst is repeatedly used for 4 times.
Description
Technical Field
The invention belongs to the field of biomass energy catalysis, and relates to a catalyst NiMo/ZrO for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran2。
Background
2-methylfuran is an important organic chemical raw material, is widely used for pesticides, spices and antimalarials, and can also be used as a gasoline additive and the like due to higher octane number and calorific value. Furfural is a platform compound that can be derived directly from biomass. Thus, furfural production is utilizedThe production of the 2-methylfuran has green sustainable development significance. Nandan S (Green Chemistry,2018,20(9):2027-2The furfural is catalyzed for hydrogenation and deoxidation for 5 hours to obtain 95 percent of 2-methylfuran molar yield, but the use of noble metal is limited by resources and price. Geng (Fuel,2020,259) used 15% CuCu2O/N-RGO (N-RGO is N-doped graphene oxide carrier) at 240 deg.C and 1.5MPa H2The furfural is catalyzed for hydrogenation and deoxidation for 4 hours, and the molar yield of the 2-methylfuran is 95.5%, but the reaction temperature is higher. Niu (Industrial)&Engineering Chemistry Research,2019,58(16):6298-2-Al2O3At 180 ℃ and 0.1MPa H2The furfural is catalyzed for hydrogenation and deoxidation for 4 hours, and the molar yield of the 2-methylfuran is only 72 percent. Therefore, aiming at the problems, the invention provides a catalyst NiMo/ZrO for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran2At 180 ℃ and 3MPa H2The furfural is catalyzed for hydrogenation and deoxidation for 6 hours, and the molar yield of the obtained product 2-methylfuran is 93.9%, so that the method has a good application prospect.
Disclosure of Invention
The invention aims to provide a low-temperature high-efficiency hydrodeoxygenation catalyst NiMo/ZrO for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran2。
Technical scheme of the invention
1. A catalyst for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran is characterized in that:
(1) the catalyst for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran is NiMo/ZrO2Is made of Ni, Mo and ZrO2Carrier composition of Ni, Mo and ZrO2The carrier molar ratio is 0.1-0.4: 1;
the NiMo/ZrO2The catalyst is a porous blocky structure with a rough surface, the aperture is 6-10 nm, the particle size is 7-9 nm, and the pore volume is 0.05-0.15 cm3A specific surface area of 35-45 m/g2/g；
The NiMo/ZrO2In the catalyst, a part of Mo is MoO2And MoO3Form exists by being in 4NiO and MoO at 50-500 DEG C3Co-reduction of (3) so that Mo6+And Mo4+Reducing the Mo into simple substance Mo with catalytic oxygen removal activity, wherein a part of Mo and Ni form MoNi4Alloy of NiMo/ZrO2The catalyst has the catalytic oxygen removal capacity of Mo and the high catalytic hydrogenation activity of Ni;
the NiMo/ZrO2Is a strong acid catalyst, and the strong acid catalytic site is favorable for catalyzing the hydrogenation deoxidation of the furfural to generate the 2-methylfuran.
(2) The NiMo/ZrO2The catalyst is used for catalyzing furfural to prepare 2-methylfuran through hydrodeoxygenation, and is characterized in that: NiMo/ZrO2The mass ratio of the catalyst to the reaction raw material furfural is 0.1-0.15: 1, the added hydrogen pressure is 2.4-3.0 MPa, the reaction temperature is 180 ℃, the reaction is carried out for 6 hours under high pressure and closed conditions, after the reaction is finished, the reaction product is cooled to room temperature, the lower layer catalyst is centrifugally separated to obtain a crude 2-methylfuran product, the centrifugally separated lower layer catalyst is precipitated and filtered, washed by isopropanol, dried in vacuum at 60-80 ℃ for 4-6 hours, and stored in N2The atmosphere is used as a catalyst for the next repeated use.
(3) The NiMo/ZrO2The catalyst is prepared by the following method:
weighing a certain amount of Zr (NO)3)4·5H2Stirring and dissolving O in deionized water to form Zr (NO) of 0.4-0.5 mol/L3)4Slowly adding ammonia water into an aqueous solution while stirring, controlling the pH value of the solution to be 9-12, standing for layering, removing a supernatant to obtain a white precipitate, washing and filtering the white precipitate, drying the white precipitate at the temperature of 60-80 ℃ for 10-12 hours, cooling and grinding the white precipitate, sieving the ground white precipitate with a 100-120-mesh sieve, placing the obtained white solid powder into a muffle furnace, heating the white solid powder to the temperature of 450-500 ℃ at the heating rate of 2-3 ℃/min, calcining the white solid powder for 4-6 hours, cooling and grinding the cooled white solid powder, and sieving the ground solid powder with a 100-2A carrier;
mixing Ni (CH)3COO)2、(NH4)6Mo7O24Dissolving the mixture in methanol according to the molar ratio of Mo to Ni of 0.1-1: 1 to obtain a light green solution with the total ion concentration of 0.2-0.4 mol/L, and then dissolving the solution in Ni and ZrO according to the molar ratio of Ni to ZrO2ZrO is added according to the mass ratio of 0.1-0.4: 12Carrier at 30 ℃Stirring and dipping for 10-12 h at 50 ℃, performing suspension evaporation on turbid liquid to recover methanol to obtain light green solid, drying for 10-12 h at 60-80 ℃, cooling, grinding, sieving with a 100-120 mesh sieve, placing the obtained light green solid powder in a muffle furnace, heating to 450-500 ℃ at a heating rate of 2-3 ℃/min, calcining for 4-6 h, cooling to obtain gray yellow solid powder, namely NiMo/ZrO2A catalyst.
Mixing NiMo/ZrO2Putting the catalyst in a tubular furnace, raising the temperature to 450-500 ℃ at a heating rate of 3-5 ℃/min in a hydrogen atmosphere, keeping the temperature for 2-4 h, reducing and activating the catalyst, and reacting the catalyst in N2The catalytic activity of the catalyst can be effectively maintained for 45-60 days in the atmosphere.
Technical advantages and effects of the invention
The invention relates to a hydrodeoxygenation catalyst NiMo/ZrO for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran2High low-temperature catalytic activity, strong carbon deposition resistance and good reusability, and is used for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran when NiMo/ZrO2The mass ratio of the catalyst to the reaction raw material furfural is 0.1:1, furfural is catalyzed to carry out hydrodeoxygenation reaction for 6 hours at 180 ℃ under the hydrogen pressure of 3MPa, the molar yield of the 2-methylfuran crude product is 94%, and the catalyst is repeatedly used for 4 times and still obtains the molar yield of the 2-methylfuran of 86%.
Drawings
FIG. 1 shows 10 wt% NiMo with Ni content of 10 wt% and Ni/Mo molar ratio of 1:0.60.6/ZrO2TEM photograph of a catalyst sample, FIG. 2 is 10 wt% NiMo0.6/ZrO2Medium active component MoNi4Particle size distribution plot of the alloy, FIG. 3 is 10 wt% NiMo0.6/ZrO2A pattern of lattice fringes. As can be seen from FIG. 1, the active component in the catalyst has uniform surface distribution, and as can be seen from FIG. 2, the active component MoNi in the catalyst4The particle diameter distribution of the alloy is mainly concentrated in 7-10 nm, and lattice stripes d-0.208 nm and d-0.181 nm in fig. 3 respectively correspond to MoNi 4121 and 310 planes, demonstrate the MoNi in the catalyst4The presence of an alloy.
FIG. 4 is 10 wt% NiMo0.6/ZrO2SEM image of catalyst sample, sample presenting surface roughnessIrregular block-like porous structures.
FIG. 5 is ZrO2Support, 10 wt% Mo/ZrO2And 10 wt% NiMo of different Ni/Mo molar ratiosx/ZrO2XRD pattern (10 wt% is Ni 10% of the total mass of the catalyst and the subscript x represents the Mo/Ni molar ratio) of (A) is ZrO2Carrier, b, c, d, e are 10 wt% NiMo with Mo/Ni molar ratio of 0:1, 0.2:1, 0.4:1, 0.6:1 respectivelyx/ZrO2And f is 10 wt% Mo/ZrO2。
ZrO2Diffraction peaks at 24.05 °, 28.17 °, 31.47 °, 34.16 °, 40.72 °, 49.27 °, 50.56 °, 55.4 °, and 60.05 ° of the carrier 2 θ correspond to ZrO in a monoclinic phase2(PDF Standard card No. 37-1484), ZrO2The carrier 2 theta is 30.22 degrees, 34.57 degrees, 35.27 degrees, 50.22 degrees and 60.20 degrees, and diffraction peaks correspond to tetragonal-phase ZrO2(PDF Standard card No. 79-1764) to explain ZrO2The carrier is a mixture of monoclinic phase and tetragonal phase.
10wt％Ni/ZrO2Diffraction peaks at 44.48 degrees, 51.83 degrees and 76.35 degrees respectively correspond to crystal faces (111), (200) and (220) of Ni (PDF standard card number 70-2849), which indicates that Ni simple substance is successfully loaded on ZrO2On a carrier.
10wt％Mo/ZrO2The disappearance of the diffraction peak at 30.22 ° or 2 θ in the catalyst indicates the tetragonal phase of ZrO in the catalyst2The content is reduced because of MoO3So that ZrO2Towards a more stable monoclinic phase.
In the curve of region (b) to (e) in fig. 5, as the Mo content increases, the Ni (111) diffraction peak at 44.48 ° 2 θ in these samples is 10 wt% Ni/ZrO2、10wt％NiMo0.2/ZrO2、10wt％NiMo0.4/ZrO2、10wt％NiMo0.6/ZrO2The offset is to the left in sequence, i.e. their 2 theta angles are moved to 44.46 deg., 43.96 deg., 43.70 deg., 43.51 deg., respectively.
In FIG. 5, 10 wt% NiMo is shown in the regions III and IV0.6/ZrO2The characteristic peak of Ni at 2 theta of 51.83 DEG and 76.35 DEG disappears to form MoNi4Diffraction peaks at 50.41 ° and 74.72 ° for the alloy, 10 wt% NiMo0.6/ZrO22 θ of 43.51 ° and 50.Three diffraction peaks of 41 degrees and 74.72 degrees respectively correspond to MoNi4The (121), (310) and (312) crystal planes of the alloy (PDF standard card number 65-5480).
In the region (i) of fig. 5, as the Mo loading amount increases, the diffraction peak intensity in the range of 42 ° to 45 ° 2 θ significantly decreases in the b-e curve, indicating that Mo and Ni form uniformly dispersed MoNi4And (3) alloying.
The above reveals MoNi4The alloy forming process comprises the following steps: that is, when Mo is loaded at a Mo/Ni molar ratio of 0.1-0.5: 1, Mo is not enough to form MoNi together with all Ni4Alloys, samples of which therefore contain elemental Ni and MoNi4And (3) alloying. The peak position of the sample shifted from Ni/ZrO with varying Mo/Ni molar ratio2In which Ni (2 θ ═ 44.48 °, 51.83 °, 76.35 °) is offset to NiMo0.6MoNi of ZrO4(2 theta. 43.51 deg., 50.41 deg. and 74.72 deg.) when Mo loading was increased to a Mo/Ni molar ratio of 0.6:1, the elemental Ni in the sample was all forming mori4And (3) alloying.
FIG. 6 is NH of sample3TPD curves, in which a, b and c are each ZrO2、10wt％Ni/ZrO2、10wt％NiMo0.6/ZrO2. NH in the range of 0-250 ℃, 250-3The desorption peaks correspond to weak acid, medium acid and strong acid sites, respectively. Visible ZrO2The carrier itself has weak and medium acid sites. When ZrO2After the carrier is loaded with Ni, the strong acid peak of the sample is obviously increased, which indicates that Ni increases the medium strong acid site of the catalyst. After further Mo incorporation, the strong acid peak in the sample decreased, but the strong acid sites increased significantly. Thus, NiMo/ZrO prepared2The catalyst is a strong acid catalyst, and the strong acid sites are favorable for catalyzing the hydrogenation deoxidation of the furfural to generate the 2-methylfuran.
FIG. 7 is H2TPR curves, where a, b and c are each 10 wt% Ni/ZrO2、10wt％Mo/ZrO2And 10 wt% NiMo0.6/ZrO2。Ni/ZrO2H appears at 330 ℃ and 480 ℃ respectively2Consumption peak, in which H appears at 330 ℃2Consumption peak represents ZrO2Partial Ni without carrier interaction2+Reduction of oxides to Ni monoMass, and H at 480 ℃2The consumption peak is represented by the relation of ZrO2Part of Ni with weak interaction of carriers2+The oxide is reduced to Ni simple substance. 10 wt% Mo/ZrO2Three H of the catalyst appear at 400 ℃, 470 ℃ and 735 ℃ respectively2Consumption peaks respectively represent Mo6+Reduction of oxides to Mo5+Oxide, Mo5+Reduction of oxides to Mo4+Oxide, Mo4+The oxide is reduced into Mo simple substance. And 10 wt% NiMo0.6/ZrO2H of catalyst at 330 ℃2The consumption peak intensity is greatly reduced, and the H at 480 ℃ is2The consumption peak intensity is greatly increased, and the H at 730 ℃ is simultaneously increased2The consumption peak intensity is greatly reduced because the elemental Ni enhances the catalyst surface H after the NiO is reduced into the elemental Ni2Thereby promoting the reduction of Mo oxide, so that part of Mo4+The oxide is reduced into a Mo simple substance at the temperature of 450-500 ℃, and in the process, the Ni simple substance and the reduced Mo simple substance are doped together to form MoNi4And (3) alloying.
TABLE 1 physicochemical characteristics of the catalyst samples
The samples in Table 1 were all loaded with Ni at 10 mass percent and the Mo subscripts represent the Mo/Ni molar ratio, as can be seen in the data of Table 1.
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 weighing of Zr (NO)3)4·5H2The O is stirred by deionized water and completely dissolved to form 0.5mol/L Zr (NO)3)4Slowly adding ammonia water into the aqueous solution under stirring, controlling pH value of the solution to 10 to obtain a white precipitate, standing, layering, removing supernatant, adding distilled water, stirring and washing the white precipitate, filtering the white precipitate, drying at 60 deg.C for 12 hr, cooling, grinding, sieving with 100 mesh sieve, placing the obtained white solid powder in a muffle furnace, heating at 2 deg.C/minThe rate is increased to 500 ℃, calcined for 6h, cooled, ground and sieved by a 100-mesh sieve to obtain the ZrO2A carrier;
mixing Ni (CH)3COO)2、(NH4)6Mo7O24Dissolving in methanol at a molar ratio of Mo/Ni of 0.6:1 to obtain a light green solution with a total ion concentration of 0.37mol/L, and adding ZrO at a molar ratio of Ni/Zr of 0.27:12Stirring and soaking a carrier at 50 ℃ for 12h, rotationally evaporating turbid liquid to recover methanol to obtain light green solid, drying the light green solid at 60 ℃ for 12h, cooling, grinding, sieving with a 100-mesh sieve, putting the obtained light green solid powder into a muffle furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining for 6h, and cooling to obtain gray yellow solid powder, namely NiMo/ZrO2A catalyst;
mixing NiMo/ZrO2The catalyst is placed in a tubular furnace, the temperature is raised to 500 ℃ at the temperature raising rate of 5 ℃/min and kept for 4h under the atmosphere of the hydrogen flow rate of 50mL/min, and ZrO is treated2MoNiO on a supportxPhase reduction to MoNi4Catalytically active sites of the alloy, activated NiMo/ZrO2Catalyst in N2The catalytic activity can be effectively maintained for 60 days in the atmosphere.
The prepared NiMo/ZrO2Mixing a catalyst and a reaction raw material furfural according to a mass ratio of 0.1:1, introducing 3MPa hydrogen, reacting at 180 ℃ for 6 hours, cooling to room temperature after the reaction is finished, and centrifugally separating out a lower-layer catalyst to obtain a crude product of 2-methylfuran, wherein the molar yield of the crude product is 93.9%. Filtering the lower layer catalyst precipitate after centrifugal separation, washing with isopropanol, vacuum drying in a vacuum drying oven at 60 deg.C for 4 hr, and storing in N2The catalyst is used as the catalyst in the atmosphere for the next repeated use.
EXAMPLE 2 the procedure of example 1 was followed, except that the hydrogen pressure was 4.0MPa, to obtain a crude 2-methylfuran in 88.4% molar yield.
EXAMPLE 3 the procedure of example 1 was followed, except that the hydrogen pressure was 2.0MPa, to obtain a crude 2-methylfuran in a molar yield of 86.2%.
EXAMPLE 4 the procedure of example 1 was followed, except that the hydrogen pressure was 1.0MPa, to obtain a crude 2-methylfuran product in a molar yield of 50.2%.
Example 5 the procedure of example 1 was followed, except that the hydrogen pressure was 0MPa, to obtain a crude 2-methylfuran product in a molar yield of 0%.
EXAMPLE 6 the procedure of example 1 was followed, but the reaction temperature was 190 ℃ to give 89.6% of crude 2-methylfuran in molar yield.
EXAMPLE 7 the procedure of example 1 was followed, but the reaction temperature was 170 ℃ to give a crude 2-methylfuran in 78.2% molar yield.
EXAMPLE 8 the procedure of example 1 was followed, but the reaction temperature was 160 ℃ and the molar yield of the hydrodeoxygenation product, 2-methylfuran, was 67.8%.
EXAMPLE 9 the procedure of example 1 was followed, except that the reaction temperature was 150 deg.C, to obtain a hydrodeoxygenation product, 2-methylfuran, in a molar yield of 58.2%.
EXAMPLE 10 the procedure of example 1 was followed, except that the reaction time was 8 hours, to obtain a molar yield of 81.8% of crude 2-methylfuran.
EXAMPLE 11 the procedure of example 1 was followed, except that the reaction time was 7 hours, to obtain a crude 2-methylfuran product in a molar yield of 86.2%.
EXAMPLE 12 the procedure of example 1 was followed, except that the reaction time was 5 hours, to obtain a crude 2-methylfuran product in a molar yield of 86.6%.
EXAMPLE 13 the procedure of example 1 was followed, except that the reaction time was 4 hours, to obtain a crude 2-methylfuran in a molar yield of 80.6%.
EXAMPLE 14 the procedure of example 1 was followed, except that the reaction time was 3 hours, to obtain a crude 2-methylfuran in a molar yield of 65.1%.
EXAMPLE 15 the procedure of example 1 was followed, except that the reaction time was 2 hours, to obtain a crude 2-methylfuran in a molar yield of 35.5%.
EXAMPLE 16 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:1.0, to give a crude 2-methylfuran product in a molar yield of 85.0%.
EXAMPLE 17 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:0.9, to give a crude 2-methylfuran product in 85.3% molar yield.
EXAMPLE 18 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:0.8, to give a crude 2-methylfuran product in 89.2% molar yield.
EXAMPLE 19 the procedure of example 1 was followed except that the molar ratio of Ni to Mo in the catalyst was 1:0.7, giving a crude 2-methylfuran product in a molar yield of 91.0%
EXAMPLE 20 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:0.5, to give a crude 2-methylfuran product in 79.3% molar yield.
EXAMPLE 21 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:0.4, to give a crude 2-methylfuran product in a molar yield of 72.2%.
EXAMPLE 22 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:0.3, to give a hydrodeoxygenation product, 2-methylfuran, in a molar yield of 60.4%.
EXAMPLE 23 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:0.2, to give a crude 2-methylfuran product in a molar yield of 51.8%.
EXAMPLE 24 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:0.1, to give a crude 2-methylfuran product in a molar yield of 35.8%.
EXAMPLE 25 the procedure of example 1 was followed, except that the molar ratio of Ni to Mo in the catalyst was 1:0, to give a crude 2-methylfuran product in 13.9% molar yield.
EXAMPLE 26 the procedure of example 1 was followed, except that the catalyst was recovered for the 2 nd cycle, and the molar yield of the crude 2-methylfuran product was 91.2%.
EXAMPLE 27 the procedure of example 1 was followed, except that the catalyst was recovered for the 3 rd cycle, giving 89.5% molar yield of crude 2-methylfuran.
EXAMPLE 28 the procedure of example 1 was followed, except that the catalyst was recovered for the 4 th cycle, to give crude 2-methylfuran in 86.1% molar yield.
EXAMPLE 29 the procedure of example 1 was followed, except that the catalyst was recovered for the 5 th cycle, to give a crude 2-methylfuran in 81.2% molar yield.
TABLE 2 operating conditions and reaction results of examples 1 to 31
Examples 26, 27, 28, 29 are for the 2 nd, 3 rd, 4 th, 5 th recovered catalyst cycle use respectively.
Claims (1)
1. A catalyst for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran is characterized in that:
(1) the catalyst for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran is NiMo/ZrO2Is made of Ni, Mo and ZrO2Carrier composition of Ni, Mo and ZrO2The carrier molar ratio is 0.1-0.4: 1;
the NiMo/ZrO2The catalyst is a porous blocky structure with a rough surface, the aperture is 6-10 nm, the particle size is 7-9 nm, and the pore volume is 0.05-0.15 cm3A specific surface area of 35-45 m/g2/g；
The NiMo/ZrO2In the catalyst, a part of Mo is MoO2And MoO3The form exists through NiO and MoO at 450-500 DEG C3Co-reduction of (3) so that Mo6+And Mo4+Reducing the Mo into simple substance Mo with catalytic oxygen removal activity, wherein a part of Mo and Ni form MoNi4Alloy of NiMo/ZrO2The catalyst has the catalytic oxygen removal capacity of Mo and the high catalytic hydrogenation activity of Ni;
the NiMo/ZrO2The catalyst is a strong acid catalyst, and the strong acid catalytic site is favorable for catalyzing the hydrogenation deoxidation of furfural to generate 2-methylfuran;
(2) the NiMo/ZrO2The catalyst is used for catalyzing furfural to prepare 2-methylfuran through hydrodeoxygenation, and is characterized in that: NiMo/ZrO2The mass ratio of the catalyst to the reaction raw material furfural is 0.1-0.15: 1, the added hydrogen pressure is 2.4-3.0 MPa, the reaction temperature is 180 ℃, the high pressure closed reaction is carried out for 6h, after the reaction is finished, the temperature is cooled to room temperature, the lower layer catalyst is centrifugally separated, the crude product of 2-methylfuran is obtained, and the crude product of 2-methylfuran is obtainedPrecipitating and filtering the catalyst at the lower layer after centrifugal separation, washing the catalyst by isopropanol, drying the catalyst for 4 to 6 hours in vacuum at the temperature of between 60 and 80 ℃, and storing the catalyst in N2The atmosphere is used as a catalyst for the next repeated use;
(3) the NiMo/ZrO2The catalyst is prepared by the following method:
weighing a certain amount of Zr (NO)3)4·5H2Stirring and dissolving O in deionized water to form Zr (NO) of 0.4-0.5 mol/L3)4Slowly adding ammonia water into an aqueous solution while stirring, controlling the pH value of the solution to be 9-12, standing for layering, removing a supernatant to obtain a white precipitate, washing and filtering the white precipitate, drying the white precipitate at the temperature of 60-80 ℃ for 10-12 hours, cooling and grinding the white precipitate, sieving the ground white precipitate with a 100-120-mesh sieve, placing the obtained white solid powder into a muffle furnace, heating the white solid powder to the temperature of 450-500 ℃ at the heating rate of 2-3 ℃/min, calcining the white solid powder for 4-6 hours, cooling and grinding the cooled white solid powder, and sieving the ground solid powder with a 100-2A carrier;
mixing Ni (CH)3COO)2、(NH4)6Mo7O24Dissolving the mixture in methanol according to the molar ratio of Mo to Ni of 0.1-1: 1 to obtain a light green solution with the total ion concentration of 0.2-0.4 mol/L, and then dissolving the solution in Ni and ZrO according to the molar ratio of Ni to ZrO2ZrO is added according to the mass ratio of 0.1-0.4: 12Stirring and dipping a carrier at 30-50 ℃ for 10-12 h, performing suspension evaporation on turbid liquid to recover methanol to obtain light green solid, drying at 60-80 ℃ for 10-12 h, cooling, grinding, sieving with a 100-120 mesh sieve, placing the obtained light green solid powder in a muffle furnace, heating to 450-500 ℃ at a heating rate of 2-3 ℃/min, calcining for 4-6 h, cooling to obtain gray yellow solid powder, namely NiMo/ZrO powder2A catalyst;
mixing NiMo/ZrO2Putting the catalyst in a tubular furnace, raising the temperature to 450-500 ℃ at a heating rate of 3-5 ℃/min in a hydrogen atmosphere, keeping the temperature for 2-4 h, reducing and activating the catalyst, and reacting the catalyst in N2The catalytic activity of the catalyst can be effectively maintained for 45-60 days in the atmosphere.
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| CN113304756A (en) * | 2021-06-15 | 2021-08-27 | 湘潭大学 | Ni-Mo bimetal alloy catalyst and preparation method and application thereof |
| WO2023113725A1 (en) * | 2021-12-14 | 2023-06-22 | T.C. Ankara Universitesi Rektorlugu | Ni-fe dopped tungsten-zirconium oxide-based catalyst for obtaining 2-methyl furan from furfural |
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| JPH05277374A (en) * | 1991-12-06 | 1993-10-26 | Tanaka Kikinzoku Kogyo Kk | Ni-base alloy substrate for catalyst and catalyst support |
| CN106496165A (en) * | 2016-10-31 | 2017-03-15 | 中国科学院过程工程研究所 | A kind of method of catalyzed conversion furfural |
| CN107376927A (en) * | 2017-07-03 | 2017-11-24 | 大连理工大学 | Method for preparing catalyst and the application of a kind of step change catalyzer active sites and carrier structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05277374A (en) * | 1991-12-06 | 1993-10-26 | Tanaka Kikinzoku Kogyo Kk | Ni-base alloy substrate for catalyst and catalyst support |
| CN106496165A (en) * | 2016-10-31 | 2017-03-15 | 中国科学院过程工程研究所 | A kind of method of catalyzed conversion furfural |
| CN107376927A (en) * | 2017-07-03 | 2017-11-24 | 大连理工大学 | Method for preparing catalyst and the application of a kind of step change catalyzer active sites and carrier structure |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113304756A (en) * | 2021-06-15 | 2021-08-27 | 湘潭大学 | Ni-Mo bimetal alloy catalyst and preparation method and application thereof |
| CN113304756B (en) * | 2021-06-15 | 2022-06-17 | 湘潭大学 | Ni-Mo bimetal alloy catalyst and preparation method and application thereof |
| WO2023113725A1 (en) * | 2021-12-14 | 2023-06-22 | T.C. Ankara Universitesi Rektorlugu | Ni-fe dopped tungsten-zirconium oxide-based catalyst for obtaining 2-methyl furan from furfural |
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