CN111054356A - Hydrodeoxygenation Ni/La2O3-SiO2Catalyst and application - Google Patents

Hydrodeoxygenation Ni/La2O3-SiO2Catalyst and application Download PDF

Info

Publication number
CN111054356A
CN111054356A CN201911170457.6A CN201911170457A CN111054356A CN 111054356 A CN111054356 A CN 111054356A CN 201911170457 A CN201911170457 A CN 201911170457A CN 111054356 A CN111054356 A CN 111054356A
Authority
CN
China
Prior art keywords
catalyst
sio
hydrodeoxygenation
reaction
product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911170457.6A
Other languages
Chinese (zh)
Other versions
CN111054356B (en
Inventor
刘跃进
张浩杰
付琳
李勇飞
胡永春
周莉平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangtan University
Original Assignee
Xiangtan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangtan University filed Critical Xiangtan University
Priority to CN201911170457.6A priority Critical patent/CN111054356B/en
Publication of CN111054356A publication Critical patent/CN111054356A/en
Application granted granted Critical
Publication of CN111054356B publication Critical patent/CN111054356B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses hydrodeoxygenation Ni/La2O3‑SiO2Catalyst and application method thereof, and preparation of hydrodeoxygenation Ni/La by adopting one-pot method2O3‑SiO2The catalyst has the advantages of simple preparation method, high activity and stability, strong carbon deposition resistance, good reusability and easy separation from a reaction system. When Ni/La2O3‑SiO2Catalyst and reaction raw material methyl palmitateThe mass ratio of the ester to the reaction solvent n-decane is 0.1:1:10, the reaction temperature is 280 ℃, the reaction hydrogen pressure is 2.6MPa, and the reaction time is 6 hours, the methyl palmitate is catalyzed to carry out hydrodeoxygenation, the molar yield of the n-pentadecane product which is a hydrodeoxygenation product is 98.68%, and the molar yield of the product is still more than 95.40% after the catalyst is repeatedly used for 10 times.

Description

Hydrodeoxygenation Ni/La2O3-SiO2Catalyst and application
Technical Field
The invention belongs to the field of biomass energy catalysis, and relates to hydrodeoxygenation Ni/La2O3-SiO2A catalyst and a method for catalyzing fatty acid methyl ester hydrodeoxygenation by using the same.
Background
With the increasing consumption of fossil energy and the accompanying environmental problems, the demand for green fuels is increasing, wherein biodiesel, in which fatty acid methyl esters prepared by transesterification of triglycerides and methanol are the main components, is continuously developed, but fatty acid methyl esters as important components of biodiesel have the disadvantages of higher freezing point, poorer stability, lower calorific value and the like in the use process, especially as vehicle fuels, compared with the conventional fossil fuels. This is mainly due to the higher oxygen content of fatty acid methyl esters, and therefore further hydrodeoxygenation of fatty acid methyl esters to upgrade to more excellent biofuels is required. In addition, conventional sulfur-free nickel-based catalysts such as Ni/SiO2The high-yield biofuel oil liquid alkane product can be obtained by catalyzing biomass grease such as Ni/SBA-15, Ni/SAPO-11 and the like, but carbon deposition is easy to occur in the hydrodeoxygenation process, so that the catalytic activity is reduced or the catalyst is easy to deactivate. Aiming at the problems, the invention adopts a one-pot method to prepare the hydrodeoxygenation Ni/La2O3-SiO2The catalyst takes methyl palmitate as a fatty acid methyl ester model compound, and the catalytic hydrodeoxygenation is carried out to obtain a biofuel oil product pentadecane with better performance, the product molar yield reaches over 96 percent, the product molar yield still reaches over 95 percent after 10 times of repeated reactions, and the hydrodeoxygenation Ni/La/Ni catalyst is invented2O3-SiO2The catalyst has the advantages of high catalytic activity, good reusability, strong carbon deposition resistance and the like.
Disclosure of Invention
Objects of the invention
The invention aims to provide hydrodeoxygenation Ni/La2O3-SiO2A catalyst and a method for synthesizing biofuel oil by catalyzing fatty acid methyl ester hydrogenation and deoxidation.
Technical scheme of the invention
1. Hydrodeoxygenation catalystAgent Ni/La2O3-SiO2The method is characterized in that:
the hydrodeoxygenation Ni/La2O3-SiO2Catalyst is prepared from Ni and La2O3-SiO2Carrier composition of Ni and La2O3-SiO2The mass ratio of the carrier is 0.1-0.2: 1, La2O3-SiO2The molar ratio of La to Si in the carrier is 0.9-1: 2;
the hydrodeoxygenation Ni/La2O3-SiO2The catalyst is of a blocky porous structure, the aperture is 6-10 nm, the particle size is 18-26 nm, and the pore volume is 0.3-0.6 cm3Per g, the specific surface area is 210-230 m2/g，Ni/La2O3-SiO2The particle size distribution of active site Ni in the catalyst is mainly concentrated at 4-6 nm;
and La2O3Ni/La carrying Ni2O3In contrast, the hydrodeoxygenation Ni/La2O3-SiO2The specific surface area of the catalyst is increased by 5-10 times;
the hydrodeoxygenation Ni/La2O3-SiO2In the catalyst, a part of La is La2O3Form doped in Ni crystal lattice, and the other part of La is carbonate La2O2CO3Form exists of La2O3La after doping Ni crystal lattice3+The strong ionic potential strongly attracts the outer electrons of the metal Ni, so that the Ni band has positive charges, the electron-withdrawing capability of the metal Ni is enhanced, and the catalytic activity of the metal Ni is improved;
the hydrodeoxygenation Ni/La2O3-SiO2The catalyst is prepared by reducing NiO at 300-400 ℃ to precipitate La from Ni crystal lattice2O3Generates embedding effect on the surface or the periphery of the metal Ni, so that the active component Ni crystal grains are reduced and dispersed in the La2O3-SiO2The carrier surface inhibits the agglomeration of an active component Ni;
the hydrodeoxygenation Ni/La2O3-SiO2La in catalyst2O3Is favorable for adsorbing CO by strong alkalinity2Form monoclinic crystalBody La2O2CO3And passing through La at 150-280 deg.C2O2CO3+C→La2O3+2CO reaction to consume carbon deposit on the surface of the catalyst and thus raise Ni/La2O3-SiO2The carbon deposition resistance of the catalyst;
the hydrodeoxygenation Ni/La2O3-SiO2In the catalyst, La2O3The existence of the catalyst weakens the surface acidity of the catalyst, and the catalyst presents medium-strong acid at the temperature of 250-350 ℃, so that the C-C bond of long-chain alkane is prevented from being broken when the catalyst catalyzes the hydrodeoxygenation of fatty acid methyl ester, and the yield of a hydrodeoxygenation product n-pentadecane is ensured;
the hydrodeoxygenation Ni/La2O3-SiO2The catalyst is prepared by the following method: la with certain alkalinity under alkaline condition2O3Doped into metallic Ni lattice because of La3+The strong ionic potential strongly attracts the outer electrons of the metal Ni, so that the Ni band has positive charges, the electron-withdrawing capability of the metal Ni is enhanced, the catalytic activity of the metal Ni is improved, and in addition, tetraethoxysilane is heated and decomposed under the alkaline condition to form SiO with uniform size2Flaky particles for providing good specific surface support for Ni active components, and the hydrodeoxygenation catalyst Ni/La is obtained by hydrothermal synthesis, calcination and reduction2O3-SiO2The method comprises the following specific steps:
mixing Ni (CH)3COO)2、La(NO3)3·6H2Adding deionized water into O and tetraethoxysilane according to the molar ratio of 0.4-0.5: 0.9-1: 2, stirring and dissolving to form a mixed solution with the total molar concentration of 0.15-0.3 mol/L, then slowly adding ammonia water to control the pH value of the mixed solution to be within the range of 9-12 to obtain a blue precipitate, carrying out hydrothermal reflux at the temperature of 80-100 ℃ for 4-6 h, cooling to room temperature, 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 4-6 h, placing the obtained light green powder into a box-type muffle furnace, heating at the temperature rising rate of 2-3 ℃/min to 450-500 ℃ for roasting for 4-6 h, and cooling to obtain the hydrodeoxygenated Ni/La/Si/O2O3-SiO2A catalyst;
hydrodeoxygenation of Ni/La2O3-SiO2Putting the catalyst in a tubular furnace, heating to 450-500 ℃ at a heating rate of 3-5 ℃/min and keeping for 2 hours under the atmosphere of hydrogen flow rate of 45-55 ml/min, and then, adding La2O3-SiO2Reducing NiO phase on the carrier into Ni simple substance catalytic active site, and hydrodeoxygenation Ni/La after activation2O3-SiO2Catalyst in N2The catalytic activity of the catalyst can be effectively maintained for 45-60 days in the atmosphere.
2. Hydrodeoxygenation of Ni/La as described in 12O3-SiO2The method for catalyzing the hydrodeoxygenation of fatty acid methyl ester by using the catalyst is characterized by comprising the following steps: Ni/La2O3-SiO2The mass ratio of the catalyst to the reaction raw material fatty acid methyl ester to the reaction solvent is 0.1-0.15: 1: 10-40, the hydrogen pressure is 2.4-3.0 MPa, the reaction temperature is 270-300 ℃, the reaction time is 4-10 h, after the reaction is finished, the reaction solvent is recovered from the reaction system, the catalyst at the lower layer is centrifugally separated, the hydrodeoxygenation product n-pentadecane is obtained, the product molar yield is more than 96%, and the centrifugally separated Ni/La at the lower layer is2O3-SiO2Precipitating and filtering the catalyst, washing with N-hexane, vacuum drying at 60-80 ℃ for 4-6 h, and storing in N2The atmosphere is used as a catalyst for the next repeated use;
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 0.084-0.085 MPa;
the fatty acid methyl ester raw materials comprise methyl laurate, methyl palmitate, methyl stearate and methyl oleate;
preferably, Ni/La2O3-SiO2The mass ratio of the catalyst to the reaction raw material fatty acid methyl ester to the reaction solvent is 0.1-0.15: 1: 10.
Technical advantages and effects of the invention
1. The invention hydrodeoxidizes Ni/La2O3-SiO2Catalyst preparationThe method is simple, high in catalytic activity and stability, easy to separate from a reaction system, strong in carbon deposition resistance and good in reusability, and can be used for catalyzing the fatty acid methyl ester hydrodeoxygenation reaction to upgrade the biodiesel.
2. When Ni/La2O3-SiO2The catalyst, the reaction raw material methyl palmitate and the reaction solvent have the mass ratio of 0.1:1:10, the reaction temperature is 280 ℃, the reaction hydrogen pressure is 2.6MPa, and the reaction time is 6 hours, so that the methyl palmitate is catalyzed to carry out hydrodeoxygenation, and the molar yield of the hydrodeoxygenation product n-pentadecane product is 98.68%.
3. The invention hydrodeoxidizes Ni/La2O3-SiO2When the catalyst is repeatedly used for 10 times, the catalyst catalyzes the hydrogenation and deoxidation of the methyl palmitate, and the mole yield of the n-pentadecane of the hydrogenation and deoxidation product is still 95.40%.
Drawings
FIG. 1a and B are Ni/La with active component Ni of 10 wt%2O3-SiO2TEM picture of catalyst sample and particle size distribution diagram of catalyst active site Ni show that the carrier La2O3-SiO2Ni is uniformly attached to La in an irregular block structure2O3-SiO2The surface of the carrier has good dispersity without obvious agglomeration, namely Ni/La2O3-SiO2The particle size distribution of active site Ni in the catalyst is mainly concentrated at 4-6 nm;
FIG. 2 shows Ni/La with Ni as the active component accounting for 10% by mass2O3-SiO2SEM images of catalyst samples, which exhibited irregular blocky porous structures;
FIG. 3 shows La with a molar ratio of La to Si of 1:22O3-SiO2Ni/La of carrier loaded with active component Ni with different mass2O3-SiO2XRD pattern of catalyst, wherein a is La2O3-SiO2A carrier, b, c, d and e are Ni/La loaded with Ni of 5%, 10%, 15% and 20% respectively by mass2O3-SiO2A catalyst. In the a curve, 2 theta is a characteristic peak of amorphous silica at 12 DEG to 38 DEG, and La is not observed2O3And La2O2CO3Characteristic peak of (2). This is because of the Ni/La of the present invention2O3-SiO2In the catalyst, when the molar ratio of La to Si is 1:2, SiO is2Existing in an amorphous state, provides a large specific surface area support, and enables La to be2O3、La2O2CO3The dispersion is uniform, so that obvious characteristic peaks are difficult to appear. For the b, c, d, e curves, the characteristic peak of Ni is 44.5 ° at 2 θ. From the comparison of FIGS. 3a, b, c, d, e, it can be seen that: the characteristic peak of Ni decreases as the Ni loading amount decreases, and disappears when the mass percentage of the active component Ni is 10%. This is mainly La precipitated from the Ni lattice2O3The embedding effect is generated on the surface or the periphery of the metal Ni so that the active component Ni is anchored in La2O3-SiO2Carrier for inhibiting the migration of Ni particles on the surface of carrier and reducing the content of Ni in La2O3-SiO2And (5) agglomeration on the surface of the carrier. The active group Ni after NiO reduction is highly dispersed in La2O3-SiO2Surface of the support, evidence of SiO2La of (5)2O3The addition of the catalyst is beneficial to improving the dispersion degree of the active component Ni and inhibiting the sintering and agglomeration of the active component Ni, thereby improving the sintering resistance and the reutilization capability of the catalyst.
FIG. 4a shows Ni/SiO2B is Ni/La2O3-SiO2(molar ratio of La to Si is 1:1) and c is Ni/La2O3-SiO2(molar ratio of La to Si 2:1) and d is Ni/La2O3-SiO2(molar ratio of La to Si 3:1) and e is Ni/La2O3-SiO2(molar ratio of La to Si is 4:1) and f is Ni/La2O3XRD patterns of samples, the mass percentage of active component Ni in the samples is 10%. As can be seen from fig. 4, the characteristic peaks of amorphous silica are observed in the range of 2 θ ═ 12 ° to 38 °, and the characteristic peaks of Ni are observed in the range of 2 θ ═ 44.5 ° to 50.2 °. Further, fig. 4f shows La at 27.9 ° when 2 θ is 27.9 °2O3The characteristic peak of (a) is La at 2 θ ═ 22.2 °, 25.1 °, 27.6 °, 30.3 °, 33.6 °, and 56.8 ° all of which are La2O2CO3Characteristic peak of (2). In a certain timeLa at the temperature of 270-300 ℃ in the chemical reaction2O2CO3Can react with carbon deposit on the surface of the catalyst to achieve the purpose of removing the carbon deposit, and the active component Ni is exposed to La again2O3-SiO2The carrier surface has excellent carbon deposition resistance. In addition, the comparison of a, b, c, d, e and f shows that: the characteristic Ni peak decreases with increasing Si content in the sample, because La decreases with increasing Si content2O3-SiO2The specific surface area of the carrier is increased continuously (see Table 1), and when the molar ratio of La to Si is 1:2, the characteristic peak of Ni is almost completely disappeared, which shows that Ni is in La at the moment2O3-SiO2The support surface is highly dispersed.
FIG. 5a shows Ni/La after 10 times of repeated use2O3-SiO2B is Ni/La before reaction2O3-SiO2XRD patterns of samples, the mass percentage of active component Ni in the samples is 10%. In the a curve, La is 39.5 ° 2 θ2O3The characteristic peak of (2 θ) ═ 44.5 ° is a characteristic peak of Ni. As can be seen from comparison of a and b, after 10 times of repeated use, La was obtained2O3Is significantly increased, whereas in fig. 5b there is no La2O3Due to the characteristic peaks with Ni/La2O3-SiO2The catalyst is recycled for multiple times, and the carbon deposition on the surface of the catalyst is gradually increased and uniformly distributed on SiO2La of the surface2O2CO3Reacting with carbon deposition on the surface of a catalyst at a certain catalytic reaction temperature of 270-300 ℃ to generate La2O3To make La of the surface2O3Gradually increase to generate aggregation, thereby showing more obvious La2O3Characteristic peak of (2). In addition, the characteristic peak of Ni is not obviously changed, and the characteristic peak of carbon or graphite does not appear. This further demonstrates that Ni/La2O3-SiO2La in catalyst carrier2O2CO3Reacting with carbon deposited on the surface of a catalyst at a certain catalytic reaction temperature of 270-300 ℃ to generate La2O3The active component Ni is exposed again and highly dispersed in La2O3-SiO2Surface of the carrier is Ni/La2O3-SiO2The catalyst has excellent sintering resistance and carbon deposition resistance.
FIG. 6a shows Ni/SiO2B is Ni/La2O3-SiO2NH of catalyst3TPD curves, the mass percentage of the active component Ni in these samples being 10%. At NH3In the-TPD diagram, weak acid is below 250 ℃, medium strong acid is 250-350 ℃, and strong acid is above 350 ℃. In FIG. 5, the peak at 150 ℃ to 170 ℃ corresponds to a weak acid, and the peak at 640 ℃ to 700 ℃ corresponds to a strong acid. Through comparison of the positions of two peaks at 158 ℃ and 697 ℃ and the intensities of the peaks in the curves of FIGS. 6a and b, it is found that the addition of La can obviously reduce the peak values of weak acidity and strong acidity and obviously shift the characteristic peak of strong acid site, which shows that the addition of La can make SiO have obvious shift2The acid amount of the surface acid sites is reduced, the strength of the surface acidity is weakened, and the C-C bond fracture of long-chain alkane can be avoided during the catalytic hydrodeoxygenation reaction, so that the yield of the hydrodeoxygenation product long-chain alkane is ensured.
FIG. 7a shows Ni/La2O3B is Ni/La2O3-SiO2(molar ratio of La to Si 2:1) and c is Ni/SiO2H of (A) to (B)2TPR diagram, the mass percentages of the active component Ni in these samples being 10%. In FIG. 7, NiO and support La are shown at 270 ℃ to 280 ℃2O3-SiO2A reduction peak of weak interaction shows NiO and carrier La at 380-400 DEG C2O3-SiO2The reduction peak of the strong interaction shows that part of free NiO and La are generated at 700-780 DEG C2O3The two strongly interact to form LaNiO3Reduced peak of (2). From the comparison of FIGS. 7a, b, and c: when La is added, the reduction peak of NiO moves forward, namely the reduction temperature of NiO is reduced, which shows that the addition of La effectively weakens the active components Ni and La2O2-SiO2SiO in carrier2While favoring Ni/La2O2-SiO2LaNiO in catalyst3And it was also confirmed that the addition of La reduced the interaction of Ni with the carrier to thereby obtain pelletsThe analysis conclusion of the active component Ni with smaller diameter and more uniform dispersion is consistent with the analysis conclusion of the figure 1, the figure 3, the figure 4 and the figure 5.
TABLE 1 physicochemical characteristics of the catalyst samples
Figure BDA0002288571450000051
Note that the mass fractions of the active component Ni in the catalyst samples are 10%, ①② respectively indicate the calcination temperatures of the catalysts at 400 ℃ and 600 ℃, and the numbers 1, 0.5, 0.33 and 0.25 in parentheses after the samples respectively indicate the molar ratio of La to Si in the samples.
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
Mixing Ni (CH)3COO)2、La(NO3)3·6H2Adding deionized water into the O and the tetraethoxysilane according to the molar ratio of 0.4:1:2, stirring and dissolving to form a mixed solution with the total molar concentration of 0.2mol/L, and then slowly adding ammonia water to control the pH value of the mixed solution to be 10 to obtain a blue precipitate; refluxing for 6h at 100 ℃ to form light green precipitate, cooling to room temperature, carrying out suction filtration on the precipitate, washing a filter cake to be neutral by using deionized water, placing the filter cake in a thermostat at 80 ℃ for drying for 6h at constant temperature, placing the light green powder obtained after drying in a muffle furnace, heating to 500 ℃ at a heating rate of 3 ℃/min, roasting for 4h, and cooling to obtain the hydrodeoxygenation Ni/La/Ni composite oxide2O3-SiO2A catalyst.
Hydrodeoxygenation Ni/La is prepared2O3-SiO2The catalyst is placed in a tubular furnace, the temperature is raised to 500 ℃ at the heating rate of 5 ℃/min and kept for 2 hours under the atmosphere of the hydrogen flow rate of 55ml/min, and La is added2O3-SiO2Reducing NiO phase on the carrier into Ni simple substance catalytic active site, and performing hydrogenation deoxidation on the activated sulfur-free nickel base to obtain Ni/La2O3-SiO2The catalyst is black solid powder, wherein the molar ratio of La to Si is 1:2, the mass percent of the active component Ni is 10 percent,in N2The catalytic activity can be effectively maintained for 60 days in the atmosphere.
The prepared hydrodeoxygenation catalyst Ni/La2O3-SiO2Mixing a reaction raw material, namely methyl palmitate and a reaction solvent, namely N-decane in a mass ratio of 0.1:1:20, introducing 2.6MPa of hydrogen, reacting for 6 hours at 280 ℃, vacuumizing to 0.086MPa and recovering the reaction solvent at 125 ℃ after the reaction is finished, cooling to room temperature, centrifugally separating out a lower-layer catalyst to obtain a hydrodeoxygenation product, namely N-pentadecane, wherein the product molar yield is 98.96%, precipitating and filtering the lower-layer catalyst after centrifugal separation, washing with N-hexane, carrying out vacuum drying in a vacuum drying box at 80 ℃ for 4 hours, and storing in an N-containing atmosphere2The catalyst is used as the catalyst in the atmosphere for the next repeated use.
Example 2 the procedure is the same as example 1, but the reaction hydrogen pressure is 3.0MPa, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 98.15%.
Example 3 the procedure is the same as example 1, but the reaction hydrogen pressure is 2.8MPa, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 98.01%.
Example 4 the procedure is the same as example 1, but the reaction hydrogen pressure is 2.4MPa, and the hydrodeoxygenation product pentadecane fuel oil product molar yield is 94.56%.
Example 5 the procedure is the same as example 1, but the reaction hydrogen pressure is 2.2MPa, and the hydrodeoxygenation product pentadecane fuel oil product molar yield is 89.65%.
Example 6 the procedure of example 1 was followed, but the reaction temperature was 300 deg.C, to obtain a hydrodeoxygenation product pentadecane fuel oil product with a molar yield of 96.28%.
Example 7 the procedure of example 1 was followed, but the reaction temperature was 260 c, to give a hydrodeoxygenation product pentadecane fuel product with a molar yield of 79.69%.
Example 8 the procedure of example 1 was followed, but the reaction temperature was 240 c, to give a hydrodeoxygenation product pentadecane fuel oil product molar yield of 48.42%.
Example 9 the procedure of example 1 was followed, but the reaction temperature was 220 deg.C, yielding a hydrodeoxygenation product pentadecane fuel product with a molar yield of 32.26%.
Example 10 the procedure of example 1 was followed, but the reaction time was 10 hours, to obtain a hydrodeoxygenation product pentadecane fuel product with a molar yield of 98.25%.
Example 11 the procedure of example 1 was followed, but the reaction time was 8 hours, to obtain a hydrodeoxygenation product pentadecane fuel oil product with a molar yield of 98.16%.
Example 12 the procedure of example 1 was followed, but the reaction time was 4 hours, to obtain a hydrodeoxygenation product pentadecane fuel oil product with a molar yield of 91.28%.
Example 13 the procedure of example 1 was followed, but the reaction time was 2 hours, to obtain a hydrodeoxygenation product pentadecane fuel product with a molar yield of 71.58%.
EXAMPLE 14 the procedure of example 1 was followed, but using La directly2O3-SiO2The carrier is used as a catalyst to obtain the hydrodeoxygenation product pentadecane fuel oil product with the molar yield of 28.10 percent.
Example 15 the procedure is the same as example 1, but the mass percent of the active component Ni in the catalyst is 5%, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 85.18%.
Example 16 the procedure is the same as example 1, but the mass percent of the active component Ni in the catalyst is 15%, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 94.25%.
Example 17 the procedure is the same as example 1, but the mass percent of the active component Ni in the catalyst is 20%, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 91.36%.
EXAMPLE 18 the procedure of example 1 was followed, except that the catalyst support was La2O3And the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 74.25 percent.
Example 19 the procedure is the same as example 1, but the molar ratio of La to Si in the catalyst is 1:1, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 85.68%.
Example 20 the procedure is the same as example 1, but the molar ratio of La to Si in the catalyst is 1:3, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 96.36%.
Example 21 the procedure is the same as example 1, but the molar ratio of La to Si in the catalyst is 1:4, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 78.97%.
EXAMPLE 22 the procedure of example 1 was followed, except that the catalyst support was SiO2And the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 77.98 percent.
EXAMPLE 23 the procedure of example 1 was followed except that the hydrodeoxygenation catalyst Ni/La was used2O3-SiO2And the mass ratio of the reaction raw material methyl palmitate to the reaction solvent n-decane is 0.1:1:40, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 98.72%.
EXAMPLE 24 the procedure is as in example 1, except that the hydrodeoxygenation catalyst Ni/La is2O3-SiO2And the mass ratio of the reaction raw material methyl palmitate to the reaction solvent is 0.1:1:10, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 98.68%.
EXAMPLE 25 the procedure of example 1 was followed, except that decalin was used as the reaction solvent, to give a hydrodeoxygenated pentadecane fuel product in a molar yield of 88.62%.
EXAMPLE 26 the procedure of example 1 was followed, except that the reaction solvent was cyclohexane, to give a hydrodeoxygenation product pentadecane fuel product in a molar yield of 83.56%.
Example 27 the procedure is the same as example 1, except that the reaction solvent is isopropanol, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 78.59%.
Example 28 the procedure is the same as example 1, but the catalyst is recycled for the 2 nd recovery, and the hydrodeoxygenation product pentadecane fuel oil product molar yield is 98.25%.
Example 29 the procedure is the same as example 1, but the catalyst is recycled for the 4 th recovery, and the molar yield of the hydrodeoxygenation product pentadecane fuel oil product is 97.68%.
Example 30 the procedure is the same as example 1, but the catalyst is recycled for the 6 th recovery, and the hydrodeoxygenation product pentadecane fuel oil product molar yield is 97.06%.
Example 31 the procedure is the same as example 1, but the catalyst is recycled for the 8 th recovery, and the hydrodeoxygenation product pentadecane fuel oil product molar yield is 96.60%.
Example 32 the procedure is the same as example 1, but the catalyst is recycled for the 10 th recovery, and the hydrodeoxygenation product pentadecane fuel oil product molar yield is 95.40%.
TABLE 2 operating conditions and reaction results of examples 1 to 29
Figure BDA0002288571450000081
Figure BDA0002288571450000091
Note: examples 23, 24 are hydrodeoxygenation catalysts Ni/La, respectively2O3-SiO2The mass ratio of the methyl palmitate to the n-decane serving as a reaction raw material to the n-decane serving as a reaction solvent is 0.1:1:40 and 0.1:1: 10;
examples 25, 26, 27 each use decalin, cyclohexane, isopropanol as a solvent;
examples 28, 29, 30, 31, 32 were recycled for the recovered catalysts of 2 nd, 4 th, 6 th, 8 th, and 10 th times, respectively.

Claims (2)

1. Hydrodeoxygenation Ni/La2O3-SiO2The catalyst is characterized in that:
the hydrodeoxygenation Ni/La2O3-SiO2Catalyst is prepared from Ni and La2O3-SiO2Carrier composition of Ni and La2O3-SiO2The mass ratio of the carrier is 0.1-0.2: 1, La2O3-SiO2The molar ratio of La to Si in the carrier is 0.9-1: 2;
the hydrodeoxygenation Ni/La2O3-SiO2The catalyst is of a blocky porous structure, the aperture is 6-10 nm, the particle size is 18-26 nm, and the pore volume is 0.3-0.6 cm3Per g, the specific surface area is 210-230 m2/g，Ni/La2O3-SiO2The particle size distribution of active site Ni in the catalyst is mainly concentrated at 4-6 nm;
and La2O3Ni/La carrying Ni2O3In contrast, the hydrodeoxygenation Ni/La2O3-SiO2The specific surface area of the catalyst is increased by 5-10 times;
the hydrodeoxygenation Ni/La2O3-SiO2In the catalyst, a part of La is La2O3Form doped in Ni crystal lattice, and the other part of La is carbonate La2O2CO3Form exists of La2O3La after doping Ni crystal lattice3+The strong ionic potential strongly attracts the outer electrons of the metal Ni, so that the Ni band has positive charges, the electron-withdrawing capability of the metal Ni is enhanced, and the catalytic activity of the metal Ni is improved;
the hydrodeoxygenation Ni/La2O3-SiO2The catalyst is prepared by reducing NiO at 300-400 ℃ to precipitate La from Ni crystal lattice2O3Generates embedding effect on the surface or the periphery of the metal Ni, so that the active component Ni crystal grains are reduced and dispersed in the La2O3-SiO2The carrier surface inhibits the agglomeration of an active component Ni;
the hydrodeoxygenation Ni/La2O3-SiO2La in catalyst2O3Is favorable for adsorbing CO by strong alkalinity2Formation of monoclinic crystal La2O2CO3And passing through La at 150-280 deg.C2O2CO3+C→La2O3+2CO reaction to consume carbon deposit on the surface of the catalyst and thus raise Ni/La2O3-SiO2The carbon deposition resistance of the catalyst;
the hydrodeoxygenation Ni/La2O3-SiO2In the catalyst, La2O3The existence of the catalyst weakens the surface acidity of the catalyst, and the catalyst presents medium-strong acid at the temperature of 250-350 ℃, so that the C-C bond of long-chain alkane is prevented from being broken when the catalyst catalyzes the hydrodeoxygenation of fatty acid methyl ester, and the yield of a hydrodeoxygenation product n-pentadecane is ensured;
the hydrodeoxygenation Ni/La2O3-SiO2The catalyst is prepared by the following method: la with certain alkalinity under alkaline condition2O3Doped into metallic Ni lattice because of La3+The strong ionic potential strongly attracts the outer electrons of the metal Ni, so that the Ni band has positive charges, the electron-withdrawing capability of the metal Ni is enhanced, the catalytic activity of the metal Ni is improved, and in addition, tetraethoxysilane is heated and decomposed under the alkaline condition to form SiO with uniform size2Flaky particles for providing good specific surface support for Ni active components, and the hydrodeoxygenation catalyst Ni/La is obtained by hydrothermal synthesis, calcination and reduction2O3-SiO2The method comprises the following specific steps:
mixing Ni (CH)3COO)2、La(NO3)3·6H2Adding deionized water into O and tetraethoxysilane according to the molar ratio of 0.4-0.5: 0.9-1: 2, stirring and dissolving to form a mixed solution with the total molar concentration of 0.15-0.3 mol/L, then slowly adding ammonia water to control the pH value of the mixed solution to be within the range of 9-12 to obtain a blue precipitate, carrying out hydrothermal reflux at the temperature of 80-100 ℃ for 4-6 h, cooling to room temperature, 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 4-6 h, placing the obtained light green powder into a box-type muffle furnace, heating at the temperature rising rate of 2-3 ℃/min to 450-500 ℃ for roasting for 4-6 h, and cooling to obtain the hydrodeoxygenated Ni/La/Si/O2O3-SiO2A catalyst;
hydrodeoxygenation of Ni/La2O3-SiO2Putting the catalyst in a tubular furnace, heating to 450-500 ℃ at a heating rate of 3-5 ℃/min and keeping for 2 hours under the atmosphere of hydrogen flow rate of 45-55 ml/min, and then, adding La2O3-SiO2Reducing NiO phase on the carrier into Ni simple substance catalytic active site, and hydrodeoxygenation Ni/La after activation2O3-SiO2Catalyst in N2The catalytic activity of the catalyst can be effectively maintained for 45-60 days in the atmosphere.
2. Hydrodeoxygenation Ni/La as claimed in claim 12O3-SiO2Catalyst and process for preparing sameThe method for catalyzing the hydrodeoxygenation of the fatty acid methyl ester is characterized by comprising the following steps: Ni/La2O3-SiO2The mass ratio of the catalyst to the reaction raw material fatty acid methyl ester to the reaction solvent is 0.1-0.15: 1: 10-40, the hydrogen pressure is 2.4-3.0 MPa, the reaction temperature is 270-300 ℃, the reaction time is 4-10 h, after the reaction is finished, the reaction solvent is recovered from the reaction system, the catalyst at the lower layer is centrifugally separated, the hydrodeoxygenation product n-pentadecane is obtained, the product molar yield is more than 96%, and the centrifugally separated Ni/La at the lower layer is2O3-SiO2Precipitating and filtering the catalyst, washing with N-hexane, vacuum drying in a vacuum drying oven at 60-80 ℃ for 4-6 h, and storing in N2The atmosphere is used as a catalyst for the next repeated use;
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 0.084-0.085 MPa;
the reaction raw material fatty acid methyl ester comprises methyl laurate, methyl palmitate, methyl stearate and methyl oleate.
CN201911170457.6A 2019-11-26 2019-11-26 Hydrodeoxygenation Ni/La 2 O 3 -SiO 2 Catalyst and application Active CN111054356B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911170457.6A CN111054356B (en) 2019-11-26 2019-11-26 Hydrodeoxygenation Ni/La 2 O 3 -SiO 2 Catalyst and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911170457.6A CN111054356B (en) 2019-11-26 2019-11-26 Hydrodeoxygenation Ni/La 2 O 3 -SiO 2 Catalyst and application

Publications (2)

Publication Number Publication Date
CN111054356A true CN111054356A (en) 2020-04-24
CN111054356B CN111054356B (en) 2022-10-18

Family

ID=70298260

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911170457.6A Active CN111054356B (en) 2019-11-26 2019-11-26 Hydrodeoxygenation Ni/La 2 O 3 -SiO 2 Catalyst and application

Country Status (1)

Country Link
CN (1) CN111054356B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114345358A (en) * 2021-12-14 2022-04-15 湘潭大学 Bifunctional catalyst for catalyzing condensation-hydrodeoxygenation of cyclopentanone to prepare high-density aviation fuel
CN114797819A (en) * 2022-03-29 2022-07-29 浙江科技学院 Biomass-based Ni/SiO 2 -La 2 O 3 Catalyst, preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106040255A (en) * 2016-06-12 2016-10-26 山东科技大学 Biomass oil hydrodeoxygenation catalyst and preparation method thereof
WO2017009107A1 (en) * 2015-07-13 2017-01-19 IFP Energies Nouvelles Tantalum-based catalyst deposited on silica for the transformation of ethanol into butadiene
CN109701543A (en) * 2019-01-30 2019-05-03 武汉理工大学 A kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst and preparation method thereof
CN110385133A (en) * 2019-07-22 2019-10-29 四川蜀泰化工科技有限公司 A kind of pre-converting catalyst and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017009107A1 (en) * 2015-07-13 2017-01-19 IFP Energies Nouvelles Tantalum-based catalyst deposited on silica for the transformation of ethanol into butadiene
CN106040255A (en) * 2016-06-12 2016-10-26 山东科技大学 Biomass oil hydrodeoxygenation catalyst and preparation method thereof
CN109701543A (en) * 2019-01-30 2019-05-03 武汉理工大学 A kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst and preparation method thereof
CN110385133A (en) * 2019-07-22 2019-10-29 四川蜀泰化工科技有限公司 A kind of pre-converting catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘迎新等: "溶胶-凝胶法制备Ni-La2O3-SiO2 催化剂及其加氢性能", 《第二届全国化学工程与生物化工年会》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114345358A (en) * 2021-12-14 2022-04-15 湘潭大学 Bifunctional catalyst for catalyzing condensation-hydrodeoxygenation of cyclopentanone to prepare high-density aviation fuel
CN114797819A (en) * 2022-03-29 2022-07-29 浙江科技学院 Biomass-based Ni/SiO 2 -La 2 O 3 Catalyst, preparation method and application thereof
CN114797819B (en) * 2022-03-29 2024-04-26 浙江科技学院 Biomass-based Ni/SiO2-La2O3Catalyst, preparation method and application thereof

Also Published As

Publication number Publication date
CN111054356B (en) 2022-10-18

Similar Documents

Publication Publication Date Title
CN109759064B (en) Co @ C/biomass catalyst and preparation method and application thereof
CN111111679B (en) Sulfur-free nickel-molybdenum bimetallic hydrodeoxygenation catalyst
CN111054356B (en) Hydrodeoxygenation Ni/La 2 O 3 -SiO 2 Catalyst and application
CN112403493A (en) Preparation method and application of PtCu monatomic alloy nano-catalyst
KR102035714B1 (en) Nickel catalysts for reforming hydrocarbons
CN112844476A (en) Biomass-based carbon material loaded nano nickel catalyst and preparation method and application thereof
CN112973759A (en) Preparation method of metal monatomic catalyst, metal monatomic catalyst and application
CN110586112B (en) Hydrodeoxygenation solid acid catalyst Ni/CeO2-Al2O3
CN104001538A (en) Nickel-loaded SBA-15 catalyst modified by cerium dioxide and preparation method and application of nickel-loaded SBA-15 catalyst modified by cerium dioxide
CN112264032B (en) Catalyst for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran
CN110947391B (en) Lanthanum oxide supported nickel-based catalyst and preparation method and application thereof
CN110756194A (en) Sulfur-free nickel-based hydrodeoxygenation catalyst and application thereof
CN110787804A (en) Hydrodeoxygenation sulfur-free nickel-based Ni/Al2O3-ZrO2Catalyst and process for preparing same
CN112427041B (en) Nickel-based catalyst for preparing low-carbon olefin by photo-thermal catalysis of carbon monoxide hydrogenation and preparation method and application thereof
CN116726973A (en) Flower-ball-shaped sulfur indium zinc/carbon nitride heterojunction photocatalyst, and preparation method and application thereof
CN111909737B (en) Method for converting methyl palmitate into biofuel through hydrodeoxygenation
CN114247443A (en) Preparation method of easily-reduced metal-doped cobalt-based catalyst
CN114797857A (en) Nanometer flower-shaped copper-based material and preparation method and application thereof
CN113231090A (en) Cu-Mo2C catalyst and preparation method and application thereof
CN115025774B (en) Ru/C catalyst for hydrocracking lignite model compound, preparation method and application thereof
CN115715987B (en) Bulk transition metal sulfide deoxidization catalyst and preparation method thereof
CN114990570B (en) Preparation method of nickel-germanium serpentine composite material and application of nickel-germanium serpentine composite material in electrocatalysis
CN114917959B (en) Ni-ZIS/MIL-101 catalyst and preparation method thereof
CN116899605B (en) Preparation method of Co@NCNTs catalyst and application of Co@NCNTs catalyst in phenolic hydrogenation
CN111715229A (en) Method for catalyzing methyl laurate hydrodeoxygenation by sulfur-free nickel-based catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant