CN116328775A - Preparation method and application of core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester - Google Patents

Preparation method and application of core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester Download PDF

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CN116328775A
CN116328775A CN202310013775.1A CN202310013775A CN116328775A CN 116328775 A CN116328775 A CN 116328775A CN 202310013775 A CN202310013775 A CN 202310013775A CN 116328775 A CN116328775 A CN 116328775A
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catalyst
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李闯
崔钰函
叶敏
于松印
梁长海
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Dalian University of Technology
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    • 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
    • B01J23/80—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 zinc, cadmium or mercury
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
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Abstract

The invention belongs to the field of catalyst synthesis, and provides a preparation method and application of a core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester. By adopting a hydrothermal in-situ growth method, al is used as 2 O 3 The microsphere is core, in Al 2 O 3 The in-situ grown CuZnAl terrazzo sheet is taken as a shell to prepare a flower-shaped multi-stage micron core-shell structure catalyst, and the existing catalyst applied to the fatty alcohol preparation reaction by fatty acid methyl ester hydrogenation can be simultaneously solved with high production cost, harsh reaction conditions,The catalyst has the advantages of low cost, mild reaction condition, high selectivity and high stability, and has wide application prospect.

Description

Preparation method and application of core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester
Technical Field
The invention belongs to the field of catalyst synthesis, and particularly relates to a preparation method of a core-shell catalyst for preparing fatty alcohol by fatty acid methyl ester selective deoxidation and hydrogenation and application of the core-shell catalyst in fatty acid methyl ester hydrogenation.
Background
Under the age background of the high-speed development of global economy, the degree of dependence of countries around the world on traditional primary energy sources such as coal, petroleum, natural gas and the like is gradually increased, so that the disposable resources in the world are seriously deficient, and the caused environmental problems are increasingly prominent. In order to achieve the long-term emission reduction goal of carbon neutralization, an ideal energy source with economy, environmental protection and sustainability is required to be searched, and biomass is the only substance with renewable carbon sources and is considered to be a promising substitute.
Fatty Acid Methyl Esters (FAMEs), which are the most typical representative of biomass energy sources, are also known as biodiesel in industry, and are an environmentally friendly clean energy source. The fatty alcohol is used as a downstream product of fatty acid methyl ester of a large chemical product, has the characteristic of high added value and has wider application range. In industry, fatty alcohol is called "process monosodium glutamate", which is often used for preparing a series of fine chemical products such as plasticizer, surfactant, detergent, lubricant and the like, and plays an important role in the development of national economy. In recent years, the consumption of fatty alcohols has been increasing in demand in the global fatty alcohol market.
In the prior art, two types of catalysts Cu-Cr catalysts and noble metal catalysts such as Pt and Ru catalysts are mainly used for preparing fatty alcohol by selectively hydrogenating fatty acid methyl ester. However, the CuCr catalyst causes strong environmental pollution due to toxicity of chromium compounds; however, noble metal catalysts are expensive, and the production cost is high, so that it is necessary to provide a hydrogenation catalyst which is environmentally friendly, low in cost and high in stability while having excellent catalytic activity.
Patent CN111701591a discloses a hydrogenation catalyst, a preparation method thereof and a method for preparing fatty alcohol by hydrogenating fatty acid ester, wherein a copper source is added into a dispersed titanium dioxide solution, and when the prepared hydrogenation catalyst is used for preparing fatty alcohol by hydrogenating fatty acid ester, higher fatty alcohol selectivity can be obtained, but the catalyst has single active component and lower catalytic activity.
Patent CN104383921A discloses a preparation and application method of a catalyst for preparing fatty alcohol by reducing higher fatty acid ester, wherein the catalyst takes high-temperature roasting nano alumina as a carrier, copper as an active component and zirconia as an auxiliary agent. The catalyst has high conversion rate and selectivity, but the catalyst preparation process is complex, and the pressure required by the reaction is high.
Patent CN105753653B discloses a process for preparing fatty alcohols. The method uses polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P 123 Or F 127 One of the metal nanoparticles is a metal nanoparticle stabilizer for stabilizing Pd, rh, pt, cr, cu or Ni, and the hydrogenation of fatty acid methyl ester is realized under mild conditions, but the noble metal used in the method is expensive, and Cr may cause environmental pollution.
Patent CN103664514B discloses a method for preparing fatty alcohol by hydrogenating fatty acid ester. The method adopts the copper-zinc-boron catalyst loaded by alumina, can obtain higher fatty acid ester conversion rate and fatty alcohol selectivity under mild reaction conditions, but the catalyst prepared by an impregnation method is easy to cause aggregation and sintering of active components, so that the stability of the catalyst is reduced.
Patent CN106622368B discloses a catalyst for preparing fatty alcohol by hydrogenating fatty acid ester, a preparation method and application thereof. The catalyst has a core-shell structure with a bifunctional catalytic active site, pd or Pt is taken as a core, and a porous organic polymer containing an acidic site is taken as a shell. The catalyst can efficiently catalyze fatty acid ester to prepare fatty alcohol by hydrogenation, and the catalyst can be recycled, but the noble metal used is expensive in nuclear price and high in production cost.
Patent CN 108404919B discloses a copper-carbon catalyst for synthesizing fatty alcohol by liquid phase hydrogenation of esters and a preparation method thereof, wherein a carbon material is used as a carrier, copper is used as an active component, zinc is used as a modification auxiliary agent, and the catalyst has good catalytic performance and stability under mild reaction conditions. But the method is mainly used for synthesizing fatty alcohol by liquid-phase hydrogenation of esters.
Although the existing catalyst for the hydrogenation reaction of fatty acid methyl ester is invented in a large number, the problems of high cost, harsh reaction conditions, poor stability and easy sintering of active components can be solved by using few catalysts. Therefore, the invention adopts an in-situ growth method to control the morphology structure of the catalyst and prepare the flower-shaped multi-stage micron core-shell structure catalyst, which can solve the problems at the same time.
Disclosure of Invention
The invention aims to solve the problems that the existing catalyst for preparing fatty alcohol by hydrogenating fatty acid methyl ester is less in quantity and can simultaneously solve the problems of high cost, harsh reaction conditions, poor stability and easy sintering of active components.
The technical scheme of the invention is as follows:
preparation method of core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester, wherein the core-shell catalyst uses Al 2 O 3 As a nucleus, in Al 2 O 3 The CuZnAl hydrotalcite sheets grown in situ are staggered to form flower-like multi-stage micron shell layers, and the flower-like multi-stage micron shell layers are used for preparing fatty alcohol with high selectivity by deoxidizing and hydrogenating fatty acid methyl ester, and the conversion rate of 40% -98% and the selectivity of 90% -100% are achieved under mild conditions; the preparation method comprises the following steps:
(1) And (3) preparing a carrier: al is added with 2 (SO 4 ) 3 Dissolving and mixing urea and potassium sodium tartrate in a molar ratio of 10:40:1, stirring for 30 minutes, transferring into a hydrothermal kettle liner, carrying out hydrothermal treatment for 2 hours at 165 ℃, transferring into air, and cooling to room temperature; alternately washing with deionized water and ethanol, and suction filtering; drying at 80deg.C for 12 hr, taking out solid powder, grinding, and calcining at 550deg.C for 6 hr to obtain Al with diameter of 3-5 μm 2 O 3 Microspheres, which are used as carriers for standby;
(2) Preparation of a catalyst precursor: mixing copper nitrate and zinc nitrate solution with total concentration of 0.03M, adding 0.134M ammonium nitrate and 0.018M ammonium fluoride, stirring thoroughly for 30min, pouring urea and Al with mass ratio of 2.5:1 2 O 3 Controlling the molar ratio of the total amount of Cu and Zn metal ions to the amount of Al metal in the hydrothermal kettle lining of the microsphere to be 2:1, carrying out hydrothermal treatment for 12 hours at the temperature of 100 ℃, and then cooling to room temperature in air; repeatedly washing the obtained slurry with deionized water and ethanol, suction filtering, drying at 80deg.C for 12 hr, and grinding to obtain Al 2 O 3 A @ CuZnAl-LDH catalyst precursor;
(3) And (3) preparing a catalyst: roasting the catalyst precursor obtained in the step (2) in air at 400 ℃ for 4 hours to obtain Al 2 O 3 @CuZnAl-LDO catalyst.
The concentration ratio of the copper nitrate to the zinc nitrate is 3:1-1:2.
The core-shell catalyst obtained by the preparation method is used for activating reduction treatment before catalytic hydrogenation reaction, and the treatment method is as follows: in-situ reduction in a fixed bed reactor under the condition of H 2 The pressure is 0.1-10MPa, H 2 The volume flow rate is 40mL/min, the reduction temperature is 300 ℃, and the reduction time is 2h.
The core-shell catalyst is used for hydrodeoxygenation reaction of fatty acid methyl ester, and the reaction is carried out in a fixed bed reactor; the reaction temperature in a fixed bed reactor is 200-300 ℃, the hydrogen pressure is 0.1-10MPa, the hydrogen-oil ratio is 400, and the airspeed WHSV is 0.19-1.40h -1 。
The prepared core-shell catalyst is used for C 8 -C 20 The fatty acid methyl ester hydrogenation selectivity of (2) is used for preparing fatty alcohol.
The invention has the beneficial effects that: the invention adopts a hydrotalcite-like intercalation assembly method to prepare a flower-shaped multi-stage micron core-shell catalyst, wherein the core is amorphous alumina, the shell is CuZnAl-LDH intercalation, and Al is obtained after roasting 2 O 3 The @ CuZnAl-LDO is used for the reaction of preparing fatty alcohol by hydrodeoxygenation of fatty acid methyl ester. The catalyst prepared by the method realizes the uniform introduction of the catalyst auxiliary agent by utilizing the adjustable property of the LDH laminate element on the basis of taking Cu as an active center. Compared with the traditional catalyst, the catalyst has larger specific surface area and developed pore canal structure, can maximally realize the dispersion and exposure of active centers, is beneficial to the adsorption and diffusion of reactant molecules and product molecules, and thus improvesReaction efficiency. The alumina is used as a carrier and simultaneously provides an aluminum source, so that the core-shell structure formed by the alumina can further improve the structural stability of the catalyst, and meanwhile, the catalyst adopts green pollution-free non-noble metal, is low in price and environment-friendly, and has a wide application value.
Drawings
FIG. 1 is an SEM photograph of a carrier, (a) at 4 ten thousand magnification; (b) magnification of 2 ten thousand times.
FIG. 2 is a SEM photograph of a core-shell catalyst, (a) at 7 tens of thousands of magnifications; (b) 4-fold magnification; (c) the magnification is 2 ten thousand times.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1
Carrier for preparing the catalyst of the invention
0.1M Al 2 (SO 4 ) 3 Mixing the solution, 0.4M urea solution and 0.025M potassium sodium tartrate solution, stirring for 30min, transferring into a 100ml hydrothermal kettle liner, hydrothermal for 2h at 165 ℃, transferring into air, and cooling to room temperature; alternately washing with deionized water and ethanol, and suction filtering; drying in an oven at 80 ℃ for 12 hours; taking out the solid powder, grinding, transferring to a muffle furnace, and roasting at 550 ℃ for 6 hours to obtain amorphous Al 2 O 3 Microspheres, about 3-5 μm in diameter.
Example 2
Preparation of Al 2 O 3 @Cu 3 Zn 1 Al-LDO core-shell catalyst
Mixing copper nitrate with total concentration of 0.0225M and zinc nitrate solution of 0.0075M, adding ammonium nitrate and ammonium fluoride, stirring thoroughly for 30min, pouring into a container containing 0.2552g urea and 0.1g Al 2 O 3 The microsphere is arranged in the inner lining of the hydrothermal kettle; hydrothermal treatment is carried out for 12h at 100 ℃, and then cooling is carried out to room temperature in air; repeatedly washing the obtained slurry with deionized water and ethanol, suction filtering, drying in an oven at 80 ℃ for 12 hours, and grinding to obtain Al 2 O 3 @Cu 3 Zn 1 Al-LDH catalyst precursor. The catalyst precursor is put into a tube furnace for emptyingRoasting for 4 hours at 400 ℃ to obtain Al 2 O 3 @Cu 3 Zn 1 Al-LDO core-shell catalyst.
Example 3
Preparation of Al 2 O 3 @Cu 2 Zn 1 Al-LDO core-shell catalyst
Mixing copper nitrate with total concentration of 0.02M and zinc nitrate solution of 0.01M, adding ammonium nitrate and ammonium fluoride, stirring thoroughly for 30min, pouring into a container containing 0.2552g urea and 0.1g Al 2 O 3 The microsphere is arranged in the inner lining of the hydrothermal kettle; hydrothermal treatment is carried out for 12h at 100 ℃, and then cooling is carried out to room temperature in air; repeatedly washing the obtained slurry with deionized water and ethanol, suction filtering, drying in an oven at 80 ℃ for 12 hours, and grinding to obtain Al 2 O 3 @Cu 2 Zn 1 Al-LDH catalyst precursor. Placing the catalyst precursor into a tube furnace, and roasting for 4 hours at the temperature of 400 ℃ by using air to obtain Al 2 O 3 @Cu 2 Zn 1 Al-LDO core-shell catalyst.
Example 4
Preparation of Al 2 O 3 @Cu 1 Zn 1 Al-LDO core-shell catalyst
Mixing copper nitrate with total concentration of 0.015M and zinc nitrate solution of 0.015M, adding ammonium nitrate and ammonium fluoride, stirring thoroughly for 30min, pouring into a container containing 0.2552g urea and 0.1g Al 2 O 3 The microsphere is arranged in the inner lining of the hydrothermal kettle; hydrothermal treatment is carried out for 12h at 100 ℃, and then cooling is carried out to room temperature in air; repeatedly washing the obtained slurry with deionized water and ethanol, suction filtering, drying in an oven at 80 ℃ for 12 hours, and grinding to obtain Al 2 O 3 @Cu 1 Zn 1 Al-LDH catalyst precursor. Placing the catalyst precursor into a tube furnace, and roasting for 4 hours at the temperature of 400 ℃ by using air to obtain Al 2 O 3 @Cu 1 Zn 1 Al-LDO core-shell catalyst.
Example 5
Preparation of Al 2 O 3 @Cu 1 Zn 2 Al-LDO core-shell catalyst
Mixing copper nitrate with total concentration of 0.01M and zinc nitrate solution of 0.02M, adding ammonium nitrate and ammonium fluoride, stirring thoroughly for 30min, pouring into a container containing 0.2552g urea and 0.1g Al 2 O 3 The microsphere is arranged in the inner lining of the hydrothermal kettle; hydrothermal treatment is carried out for 12h at 100 ℃, and then cooling is carried out to room temperature in air; repeatedly washing the obtained slurry with deionized water and ethanol, suction filtering, drying in an oven at 80 ℃ for 12 hours, and grinding to obtain Al 2 O 3 @Cu 1 Zn 2 Al-LDH catalyst precursor. Placing the catalyst precursor into a tube furnace, and roasting for 4 hours at the temperature of 400 ℃ by using air to obtain Al 2 O 3 @Cu 1 Zn 2 Al-LDO core-shell catalyst.
Example 6
Preparation of impregnation Supported CuZn/Al 2 O 3 Catalyst
The Al prepared in example 1 was used as a reference to the catalyst loading described in example 3 2 O 3 Microspheres as a carrier, 3.17g of copper nitrate and 1.59g of zinc nitrate were dissolved in 30ml of deionized water, stirred for 30 minutes, and poured with 1g of Al 2 O 3 Stirring the microspheres in a round-bottom flask for 12 hours, steaming and drying the microspheres overnight, grinding the microspheres, then placing the catalyst precursor into a tube furnace, and roasting the catalyst precursor for 4 hours at the temperature of 400 ℃ by using air to obtain the impregnated supported CuZn/Al 2 O 3 A catalyst.
Example 7
Preparation of uniform CuZnAl-LDO catalyst
Taking the catalyst loading as described in example 3 as a reference, 1.21g of copper nitrate, 0.61g of zinc nitrate and 2.82g of aluminum nitrate are dissolved in 70ml of deionized water, stirred for 30min, poured into a hydrothermal kettle liner, hydrothermal-treated at 100 ℃ for 12h, and then cooled to room temperature in air; repeatedly washing the obtained slurry with deionized water and ethanol, carrying out suction filtration, drying in an oven at 80 ℃ for 12 hours, and grinding to obtain the CuZnAl-LDH catalyst precursor. And (3) placing the catalyst precursor into a tube furnace, and roasting for 4 hours at the temperature of 400 ℃ by using air to obtain the uniform CuZnAl-LDO catalyst.
Example 8
Hydrogenation performance tests were performed using the catalysts of examples 2-5 to examine the effect of different metal ratios on the catalytic performance of the catalysts. The results were as follows:
catalyst Conversion (%) Selectivity (%)
Example 2 94.62 86.79
Example 3 97.79 92.88
Example 4 94.54 88.86
Example 5 88.46 87.72
Example 9
Hydrogenation performance tests were performed using the catalyst of example 3 to examine the effect of temperature on the catalytic performance of the catalyst.
0.1g of the oxidation state catalyst of example 3 was weighed and placed in the middle of the tube of the fixed bed reactor, and plugged with 20-40 mesh quartz sand support on both sides. The catalyst was hydrogen activated, the reactor furnace temperature was set at 300℃and the pressure was adjusted to 4MPa, the hydrogen flow was set at 40mL/min and the reduction time was 2h. After the activation, the pressure of the reactor is regulated to 4Mpa, and the airspeed is regulated to 0.42h -1 The initial furnace temperature is 200 ℃, and the mass fraction is conveyed to the reactor after the system temperature, pressure and gas flow are stableThe reaction was carried out at intervals of 2h with 1% methyl laurate in cyclohexane, and the liquid sample was analyzed by an internal chromatographic standard. The results were as follows:
reaction temperature (. Degree. C.) Conversion (%) Selectivity (%)
200 90.68 98.71
220 92.60 98.88
240 96.39 98.34
260 97.79 92.88
280 99.43 88.82
Example 10
Hydrogenation performance tests were performed using the catalyst of example 3 to investigate the effect of space velocity on the catalyst's catalytic performance.
0.1g of the oxidation state catalyst of example 3 was weighed and placed in the middle of the tube of the fixed bed reactor, and plugged with 20-40 mesh quartz sand support on both sides. The catalyst was hydrogen activated, the reactor furnace temperature was set at 300℃and the pressure was adjusted to 4MPa, the hydrogen flow was set at 40mL/min and the reduction time was 2h. After the activation, the pressure of the reactor is regulated to 4Mpa, the furnace temperature is 240 ℃ and the airspeed is 0.19h -1 After the system temperature, pressure and gas flow are stable, a cyclohexane solution of methyl laurate with the mass fraction of 1% is conveyed to a reactor, the feeding rate is adjusted every 2 hours in the reaction, and a liquid sample is taken for analysis and test by using a chromatographic internal standard method. The reaction results were as follows:
Figure BDA0004038603740000081
Figure BDA0004038603740000091
example 11
Hydrogenation performance tests were performed using the catalysts of example 3 and examples 6-7 to examine the effect of catalysts of different structures on the catalytic performance.
The reaction pressure is 4Mpa, the temperature is 240 ℃ and the space velocity is 0.42h -1 After the system temperature, pressure and gas flow are stable, a cyclohexane solution of methyl laurate with the mass fraction of 1% is conveyed to a reactor, and a liquid sample is taken for analysis and test by using a chromatographic internal standard method. The reaction results were as follows:
catalyst Conversion (%) Selectivity (%)
Example 3 97.79 92.88
Example 6 34.71 86.65
Example 7 85.72 79.29
Example 3 and example 7 have higher catalytic activity than example 6 due to the hydrotalcite structure formed. Example 3 shows the highest catalytic activity, due to its special core-shell structure, can greatly improve the utilization of active centers, and is beneficial to adsorption and diffusion of reactant molecules and product molecules.
Example 12
Stability testing was performed using example 3. The reaction results were as follows:
reaction time (h) Conversion (%) Selectivity (%)
10 94.02％ 93.87％
30 94.71％ 92.18％
50 93.96％ 94.75％
100 94.88％ 95.82％
300 94.41％ 93.59％
500 93.18％ 92.02％
600 92.66％ 91.07％
700 90.08％ 91.47％
。

Claims (5)

1. Preparation method of core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester, wherein the core-shell catalyst uses Al 2 O 3 As a nucleus, in Al 2 O 3 The CuZnAl hydrotalcite sheets grown in situ are staggered to form flower-like multi-stage micron shell layers, and the flower-like multi-stage micron shell layers are used for preparing fatty alcohol with high selectivity by deoxidizing and hydrogenating fatty acid methyl ester, and reach 40-98% of conversion rate and conversion rate under mild conditionsSelectivity of 90% -100%; the preparation method is characterized by comprising the following preparation steps:
(1) And (3) preparing a carrier: al is added with 2 (SO 4 ) 3 Dissolving and mixing urea and potassium sodium tartrate in a molar ratio of 10:40:1, stirring for 30 minutes, transferring into a hydrothermal kettle liner, carrying out hydrothermal treatment for 2 hours at 165 ℃, transferring into air, and cooling to room temperature; alternately washing with deionized water and ethanol, and suction filtering; drying at 80deg.C for 12 hr, taking out solid powder, grinding, and calcining at 550deg.C for 6 hr to obtain Al with diameter of 3-5 μm 2 O 3 Microspheres, which are used as carriers for standby;
(2) Preparation of a catalyst precursor: mixing copper nitrate and zinc nitrate solution with total concentration of 0.03M, adding 0.134M ammonium nitrate and 0.018M ammonium fluoride, stirring thoroughly for 30min, pouring urea and Al with mass ratio of 2.5:1 2 O 3 Controlling the molar ratio of the total amount of Cu and Zn metal ions to the amount of Al metal in the hydrothermal kettle lining of the microsphere to be 2:1, carrying out hydrothermal treatment for 12 hours at the temperature of 100 ℃, and then cooling to room temperature in air; repeatedly washing the obtained slurry with deionized water and ethanol, suction filtering, drying at 80deg.C for 12 hr, and grinding to obtain Al 2 O 3 A @ CuZnAl-LDH catalyst precursor;
(3) And (3) preparing a catalyst: roasting the catalyst precursor obtained in the step (2) in air at 400 ℃ for 4 hours to obtain Al 2 O 3 @CuZnAl-LDO catalyst.
2. The method for preparing a core-shell catalyst according to claim 1, wherein the concentration ratio of copper nitrate to zinc nitrate is 3:1-1:2.
3. The method for preparing a core-shell catalyst according to claim 1 or 2, wherein the core-shell catalyst is subjected to an activation reduction treatment before being used for catalytic hydrogenation reaction, and the treatment method is as follows: in-situ reduction in a fixed bed reactor under the condition of H 2 The pressure is 0.1-10MPa, H 2 The volume flow rate is 40mL/min, the reduction temperature is 300 ℃, and the reduction time is 2h.
4. The core-shell catalyst obtained by the process for preparing a core-shell catalyst according to claim 1 or 2, which is used for hydrodeoxygenation of fatty acid methyl esters, characterized in that the reaction is carried out in a fixed bed reactor; the reaction temperature in a fixed bed reactor is 200-300 ℃, the hydrogen pressure is 0.1-10MPa, the hydrogen-oil ratio is 400, and the airspeed WHSV is 0.19-1.40h -1 。
5. The use of the core-shell catalyst according to claim 4 for hydrodeoxygenation of fatty acid methyl esters, wherein the core-shell catalyst is used for C 8 -C 20 The fatty acid methyl ester hydrogenation selectivity of (2) is used for preparing fatty alcohol.
CN202310013775.1A 2023-01-05 2023-01-05 Preparation method and application of core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester Pending CN116328775A (en)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007289855A (en) * 2006-04-25 2007-11-08 Sakai Chem Ind Co Ltd Hydrogenation catalyst, its use and its manufacturing method
CN101298052A (en) * 2008-06-20 2008-11-05 华东理工大学 Copper zinc catalyst and precursor, preparation and use thereof
US20130143731A1 (en) * 2010-05-27 2013-06-06 Beijing University Of Chemical Technology Supported noble metal catalyst and process for preparing the same in situ
CN105536802A (en) * 2015-12-17 2016-05-04 中国科学院上海高等研究院 Micro-nano structure copper-based catalyst and preparation method and application thereof
WO2016078261A1 (en) * 2014-11-20 2016-05-26 北京化工大学 Supported high dispersion nickel-based alloy catalyst preparation method and catalytic application thereof
CN106076346A (en) * 2016-05-20 2016-11-09 辽宁石油化工大学 Catalyst, preparation method and application for methanol steam catalytically reforming hydrogen producing
CN113649017A (en) * 2021-08-17 2021-11-16 大连理工大学 Preparation method and application of vegetable oil hydrodeoxygenation water-resistant core-shell type catalyst
CN114308087A (en) * 2022-01-13 2022-04-12 福州大学 Supported nickel phosphide catalyst for petroleum resin hydrogenation and preparation method thereof
CN114653372A (en) * 2022-03-07 2022-06-24 国网综合能源服务集团有限公司 Preparation method of high-dispersion nickel-based catalyst and application of high-dispersion nickel-based catalyst in catalyzing high-temperature water gas shift reaction
CN115090292A (en) * 2022-05-06 2022-09-23 北京化工大学 Preparation method of cobalt-zinc bimetallic alloy catalyst and application of cobalt-zinc bimetallic alloy catalyst in catalyzing fatty acid methyl ester and fatty acid hydrodeoxygenation reaction
CN115301235A (en) * 2022-08-17 2022-11-08 福州大学 Catalyst for preparing high-carbon alcohol by hydrogenation of fatty acid methyl ester and preparation method and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007289855A (en) * 2006-04-25 2007-11-08 Sakai Chem Ind Co Ltd Hydrogenation catalyst, its use and its manufacturing method
CN101298052A (en) * 2008-06-20 2008-11-05 华东理工大学 Copper zinc catalyst and precursor, preparation and use thereof
US20130143731A1 (en) * 2010-05-27 2013-06-06 Beijing University Of Chemical Technology Supported noble metal catalyst and process for preparing the same in situ
WO2016078261A1 (en) * 2014-11-20 2016-05-26 北京化工大学 Supported high dispersion nickel-based alloy catalyst preparation method and catalytic application thereof
CN105536802A (en) * 2015-12-17 2016-05-04 中国科学院上海高等研究院 Micro-nano structure copper-based catalyst and preparation method and application thereof
CN106076346A (en) * 2016-05-20 2016-11-09 辽宁石油化工大学 Catalyst, preparation method and application for methanol steam catalytically reforming hydrogen producing
CN113649017A (en) * 2021-08-17 2021-11-16 大连理工大学 Preparation method and application of vegetable oil hydrodeoxygenation water-resistant core-shell type catalyst
CN114308087A (en) * 2022-01-13 2022-04-12 福州大学 Supported nickel phosphide catalyst for petroleum resin hydrogenation and preparation method thereof
CN114653372A (en) * 2022-03-07 2022-06-24 国网综合能源服务集团有限公司 Preparation method of high-dispersion nickel-based catalyst and application of high-dispersion nickel-based catalyst in catalyzing high-temperature water gas shift reaction
CN115090292A (en) * 2022-05-06 2022-09-23 北京化工大学 Preparation method of cobalt-zinc bimetallic alloy catalyst and application of cobalt-zinc bimetallic alloy catalyst in catalyzing fatty acid methyl ester and fatty acid hydrodeoxygenation reaction
CN115301235A (en) * 2022-08-17 2022-11-08 福州大学 Catalyst for preparing high-carbon alcohol by hydrogenation of fatty acid methyl ester and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUAN PENG ET AL.: "Cu-Zn/Al2O3 Catalyst for the Hydrogenation of Esters to Alcohols", 《CHINESE JOURNAL OF CATALYSIS》, vol. 31, no. 7, 31 July 2010 (2010-07-31), pages 1 *

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