CN114130399A - Ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst and application thereof - Google Patents

Ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst and application thereof Download PDF

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CN114130399A
CN114130399A CN202111209238.1A CN202111209238A CN114130399A CN 114130399 A CN114130399 A CN 114130399A CN 202111209238 A CN202111209238 A CN 202111209238A CN 114130399 A CN114130399 A CN 114130399A
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rare earth
earth metal
copper
aluminum
soluble salt
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江大好
赵豪健
胡晓利
张继生
侯圣国
孟华
胡皓森
许孝良
张群峰
李小年
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Feicheng Pyramid Alcohol Chemical Equipment Co ltd
Zhejiang University of Technology ZJUT
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Feicheng Pyramid Alcohol Chemical Equipment Co ltd
Zhejiang University of Technology ZJUT
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    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/615—100-500 m2/g
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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
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst has a highly ordered mesoporous structure and a higher specific surface area, and copper, rare earth metal oxide and alumina are tightly interacted and highly uniformly dispersed. The highly dispersed Cu active component provides a large amount of ethanol dehydrogenation activity or crotonaldehyde hydrogenation centers, and the highly dispersed rare earth metal oxide and the alumina carrier provide a large amount of acid-base active centers for promoting acetaldehyde aldol condensation, so that the efficient conversion of ethanol to higher alcohols is finally realized. Meanwhile, the mutual doping and strong interaction among the oxides of copper, rare earth metal and aluminum limit the sintering and growth of the oxides of Cu and rare earth metal, so that the catalyst shows excellent stability in long-term evaluation for 500 hours.

Description

Ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst and application thereof
(I) technical field
The invention relates to an ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst (CuO-MO)x-Al2O3) The catalyst shows excellent catalytic activity, selectivity and stability in the reaction of preparing higher alcohol from ethanol, thereby having good industrial application prospect.
(II) background of the invention
Due to the increasing exhaustion of fossil resources and the problem of greenhouse effect brought by the use of fossil resources, the development and utilization of renewable biomass fuels are more and more paid attention by people. As a renewable biomass fuel, bioethanol is widely used as a gasoline blending component in the united states, brazil, china, etc. However, ethanol has problems of high hygroscopicity, low energy density, corrosion of engine cylinders, and the like, and thus is not an ideal gasoline blending component. Compared with ethanol, the n-butanol is insoluble in water, has high energy density and low corrosivity to automobile engines, can be mixed with gasoline in a higher proportion, and does not cause the problem that the automobile is difficult to start due to fuel oil layering, so that the n-butanol is an ideal substitute for the current ethanol gasoline blending component. The n-butyl alcohol is also an important chemical raw material and product, can be used for preparing a plurality of chemicals by taking the n-butyl alcohol as a platform molecule, and is widely applied to the fields of petrochemical industry, food, medicine and the like. The industry mainly uses petroleum-based propylene as a raw material to synthesize the n-butanol through carbonylation and hydrogenation reactions. Although the n-butanol can also be prepared by fermenting biomass raw materials, the efficiency of the biological fermentation method for preparing the n-butanol is very low, and the production of the n-butanol needs facilities such as large evaporation, heating, cooling and the like, so that the investment cost is high. On the other hand, the process for industrially preparing the biomass ethanol by adopting the biological fermentation method is quite mature and has a certain scale, and a solid support is provided for the development of downstream products of the ethanol. Therefore, the production of high value-added chemicals by catalytic conversion of ethanol has become one of the hot spots of current academic and industrial concerns.
The preparation of the n-butanol by starting from the bioethanol relates to a plurality of catalytic processes such as ethanol dehydrogenation, acetaldehyde aldol condensation, crotonaldehyde hydrogenation and the like, and mutual restriction is caused, so that the yield of the n-butanol is generally low. The design and regulation of the catalyst structure realize the synergistic effect of efficient dehydrogenation of ethanol, acetaldehyde aldol condensation and crotonaldehyde hydrogenation, and are the key for effectively communicating the series of series reactions. In published documents, iridium and ruthenium complex catalysts are used in the reaction of preparing n-butanol by dehydrogenating and condensing ethanol, and higher butanol selectivity and yield are obtained, but the preparation is complicated, soluble strong bases such as sodium hydroxide and sodium ethoxide are used as catalysts in the acetaldehyde aldol condensation step, and particularly, a kettle-type reactor is adopted, so that the separation of the catalysts is difficult, and the reaction cannot be continuously carried out, thereby being unfavorable for the future mass production of butanol fuel [ Angew.chem.int.Ed.,2013,52, 9005-; J.am.chem.Soc.2015,137,14264-14267]. The metal-loaded multifunctional catalyst is widely used for the reaction of preparing n-butanol by dehydrogenating and condensing ethanol, and shows excellent catalytic performance. Such as CeO with a high specific surface2The supported copper-based catalyst achieved 67% ethanol conversion and up to 30 wt% butanol yield at a reaction temperature of 250 ℃, but it was required to be in supercritical CO2The reaction pressure of more than 10MPa in the medium has high requirements on the material of reaction equipment, the reaction process is complex, the production capacity of butanol in a unit volume reactor is low, and the industrial application of the method is limited to a certain degree [ Green chem.]. Activated carbon loaded Cu-CeO2the/AC catalyst is used for preparing alcohol by dehydrogenation and condensationReaction of N-butanol at 250 ℃ under 2MPa (N)2)、LHSV＝2h-1Shows an ethanol conversion of 46% and a butanol yield of nearly 20 wt% under the reaction conditions of (1), and no small molecule gas product is produced, but the catalytic activity is slightly decreased in the long-term reaction evaluation [ chem.commun.,2016,52, 13749-13752; patent CN106076344]。
Copper-based catalysts, although low in cost and high in activity, have poor thermal stability and durability [ prog.solid State chem.,1975,9,21-25 ] due to the weak interaction between the metal and the carrier, which makes the copper nanoparticles easy to sinter.]. One of the ways to improve the stability of copper-based catalysts is to form a copper spinel oxide structure. For example, Cu-based spinel oxide CuM2O4(M ═ Fe, Al, etc.) than CuO-ZnO-Al2O3The catalyst shows higher catalytic activity and stability [ appl.Catal.A,2008,341,139-145 ].]. At present, partial embedding of copper nanoparticles in thermally stable mesoporous alumina is an attractive method to inhibit sintering of copper nanoparticles. Meanwhile, Ordered Mesoporous Alumina (OMA) has the characteristics of large specific surface, larger pore diameter, ordered pore structure, good thermal stability and the like, and is considered as an ideal catalyst carrier for various catalytic reactions [ J Catal, 2015,326, 127-138; catal Sci Technol, 2014,4,3169-3202.]。
The invention adopts a one-pot evaporation induction self-assembly method to prepare the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst, realizes the high dispersion and stable existence of active components of copper and rare earth metal oxides in the catalyst, simultaneously the specific surface of the catalyst is large, the aperture is in the mesoporous range, and the catalyst is beneficial to the reaction and diffusion of reactants, intermediates and product molecules. The catalyst is applied to the reaction of synthesizing higher alcohol by continuous catalytic conversion of an ethanol fixed bed, and the reaction is carried out at the temperature of 150-300 ℃, the normal pressure of 4.0MPa and the LHSV of 0.5-5 mL/(h.g)cat) The reaction conditions of 100: 1-600: 1 (volume ratio) of nitrogen/ethanol show that the conversion rate of ethanol is up to 52.2% and the yield of higher alcohol is 37.7%; meanwhile, due to the strong limiting action among the three oxides, the aggregation and sintering of active centers are effectively prevented, so that the high-stability oxide material has excellent stability in long-time evaluation of 500h and is goodGood industrial application prospect.
Disclosure of the invention
The invention provides an ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst (CuO-MO)x-Al2O3) The preparation method and the application thereof are that the catalyst with large specific surface, ordered pore canal and mesoporous, highly dispersed active components and good stability is directly synthesized by a one-pot evaporation induction self-assembly method and is applied to the reaction of synthesizing the higher alcohol by continuous and high-efficiency catalytic conversion of an ethanol fixed bed.
The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst synthesized in situ by a one-pot method realizes high dispersion and stable existence of active components of copper and rare earth metal oxides on the catalyst, and meanwhile, the catalyst has a large specific surface and a pore diameter in a mesoporous range, and is beneficial to reaction and diffusion of reactants, intermediates and product molecules. The method is applied to the reaction of synthesizing n-butanol by continuous catalytic conversion of an ethanol fixed bed, and the reaction is carried out at the temperature of 150-300 ℃ and the normal pressure of 4.0MPa, and the LHSV is 0.5-5 mL/(h.g)cat) And the yield of higher alcohol is as high as 15-38% under the reaction condition of 100: 1-600: 1 (volume ratio), and the product has excellent stability in long-term evaluation for 500 h.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst (CuO-MO)x-Al2O3) The catalyst is prepared by the following method:
dissolving a template agent in absolute ethyl alcohol, adding inorganic strong acid, salicylic acid and citric acid, and uniformly mixing; adding soluble salt of copper, soluble salt of rare earth metal and soluble salt of aluminum, and mixing uniformly; evaporating the solvent at 25-80 ℃ for 1-72 h (preferably evaporating the solvent at 60 ℃ for 24h), and then drying at 60-120 ℃ for 2-96 h (preferably drying at 65 ℃ for 48 h); heating the obtained mixture to 350-550 ℃ at the speed of 1-10 ℃/min (preferably 1 ℃/min) in a muffle furnace, roasting for 2-10 h (preferably 400 ℃ for 4h), then continuously heating to 600-800 ℃ at the speed of 10-30 ℃/min (preferably 10 ℃/min), and roasting for 0.5-6 h (preferably 700 ℃ for 1h) to obtain the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst; the template agent is a triblock polymer surfactant;
the amount of aluminum in the soluble salt of aluminum is calculated according to the theoretical mass of the soluble salt of aluminum completely generating aluminum oxide, and the ratio of the amount of the template agent, hydrogen ions in inorganic strong acid, salicylic acid, citric acid and the amount of the aluminum in the soluble salt of aluminum is 0.015-0.02: 1-5: 0.05-0.1: 0.03-0.08: 1;
the mass of the soluble salt of copper, the mass of the soluble salt of rare earth metal and the mass of the soluble salt of aluminum are respectively calculated according to the theoretical mass that the soluble salt of copper completely generates copper oxide, the soluble salt of rare earth metal completely generates rare earth metal oxide and the soluble salt of aluminum completely generates aluminum oxide, and the mass of the copper oxide is 2.5-8.5% of the mass of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst; the mass of the rare earth metal oxide is 3-15% of that of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst; the mass of the alumina is 76.5-94.5% of that of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst.
The catalyst can be used after being naturally cooled.
The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst can be subjected to reduction activation in a reaction bed by any means known in the art before use, and then can be subjected to catalytic reaction. The reduction activation operation of the present invention is as follows: the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst is loaded into a fixed bed reactor and treated with N at the temperature of 100-325 DEG C2Preheating the ethanol carried by carrier gas, and introducing into a fixed bed reactor for in-situ reduction, wherein the liquid airspeed of the ethanol is 2 mL/(h.g)cat) The volume ratio of nitrogen to ethanol was 250: 1.
Further, the volume of the absolute ethyl alcohol is 2-20mL/g (preferably 10mL/g) based on the mass of the soluble salt of the aluminum.
Further, the soluble salt of copper is one or a mixture of more of soluble copper salts such as copper acetate, copper nitrate, copper chloride and the like.
The rare earth metal in the soluble salt of the rare earth metal can be one or a mixture of more than two of the rare earth metals; specifically, the rare earth metal in the soluble salt of the rare earth metal is one or a mixture of more than two of La, Ce, Sm, Pr and the like. The soluble salt of the rare earth metal is one or a mixture of more of acetate, nitrate, chloride and other soluble rare earth metal salts of the rare earth metal.
Further, the soluble salt of aluminum is one or a mixture of more of soluble aluminum salts such as aluminum nitrate, aluminum isopropoxide, aluminum chloride and the like.
In the above preparation method, the template is preferably P123 (EO)20PO70EO20)、F127((C3H6O·C2H4O)x) One or more of the three-block polymer surfactants, the inorganic strong acid is preferably one or a mixture of two of hydrogen chloride and nitric acid, and can be added in the form of aqueous solution, and particularly preferably one or a mixture of two of inorganic acids such as 35 wt% hydrochloric acid and 68 wt% nitric acid.
The specific surface area of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst is 190-400 m2(iv)/g, average pore diameter is 6-15 nm, and pore volume is 0.7-1.5 mL/g.
The invention also provides an application of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst in the reaction of preparing higher alcohol by dehydrogenating and condensing ethanol.
The reaction is carried out continuously in a fixed bed reactor. The catalyst of the invention has ethanol conversion rate and higher alcohol yield respectively up to 52.2 percent and 37.7 percent in the reaction, and no micromolecule cracking product is generated; meanwhile, due to the strong limiting effect among the three oxides, the catalyst is excellent in stability test of 500h, so that a good industrial application prospect is shown.
Specifically, the application is as follows: introducing nitrogen and ethanol into a fixed bed reactor at the temperature of 150-300 ℃ and the reaction pressure of normal pressure to 4.0MPa, wherein the liquid airspeed is 0.5-5 mL/(h.g)cat) Of said nitrogen with ethanolAnd (3) carrying out the reaction for preparing the higher alcohol by dehydrogenating and condensing the ethanol under the condition that the volume ratio is 100-600: 1.
The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst has the advantages of highest higher alcohol selectivity and yield, and excellent stability. The main by-products of the reaction include acetaldehyde, diethyl ether, butyraldehyde, ethyl acetate, etc., and the unreacted ethanol can be recycled.
Compared with the prior art, the invention has the beneficial effects that:
the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst prepared by the method has a highly ordered mesoporous structure and a high specific surface area (190-400 m)2/g), copper and rare earth metal oxides interact tightly with the alumina carrier and are highly uniformly dispersed. The highly dispersed Cu active component provides a large amount of ethanol dehydrogenation activity or crotonaldehyde hydrogenation centers, and the highly dispersed rare earth metal oxide and the alumina carrier provide a large amount of acid-base active centers for promoting acetaldehyde aldol condensation, so that the efficient conversion of ethanol to higher alcohols is finally realized. Meanwhile, the mutual doping and strong interaction among the oxides of the copper, the rare earth metal M and the aluminum limit the sintering and the growth of the oxides of the Cu and the rare earth metal, so that the catalyst shows excellent stability in long-term evaluation for 500 hours.
In conclusion, the catalyst preparation method is simple, convenient, effective and low in cost, a fixed bed continuous reaction process is adopted when the catalyst is applied to the reaction of preparing higher alcohol by ethanol dehydrogenation and condensation, the flow is simple, the reaction conditions are relatively mild, the yield of the higher alcohol in the product can reach 37.7 wt%, and particularly the catalyst is good in stability and suitable for industrial application.
(IV) description of the drawings
FIG. 1 is a schematic diagram of a fixed bed reaction device for synthesizing higher alcohol by continuous catalytic conversion of ethanol: 1-hydrogen cylinder, 2-nitrogen cylinder, 3-raw material cylinder, 4-high pressure constant flow pump, 5-three-way valve, 6-pressure reducing valve, 7-stop valve, 8-mass flow meter, 9-one-way valve, 10-reaction tube, 11-reaction furnace, 12-catalyst, 13-condenser, 14-condensed water, 15-back pressure valve and 16-collecting tank.
FIG. 2 is a high resolution projection electron microscopy (HRTEM) image (A), a high angle annular dark field scanning transmission (HAADF-STEM) image and a corresponding element distribution image (B) of the catalyst B prepared in example 2 after reaction
FIG. 3 is an X-ray diffraction (XRD) pattern before and after the reaction of catalyst B prepared in example 2: (a) before reaction; (b) after the reaction.
FIG. 4 shows the results of stability tests of catalyst B prepared according to example 2 in the fixed bed reaction for the continuous catalytic conversion of ethanol to higher alcohols; the reaction conditions are as follows: the temperature is 260 ℃, the pressure is 3.0MPa, and the liquid space velocity is 2 mL/(h.g)cat) Nitrogen/ethanol ratio 250:1 (volume ratio).
FIG. 5 is a graph comparing the results of stability tests of catalyst B prepared according to example 2 and catalyst O prepared according to comparative example 3 in the reaction of synthesizing higher alcohols by continuous catalytic conversion of fixed bed ethanol; the reaction conditions are as follows: the temperature is 260 ℃, the pressure is 3.0MPa, and the liquid space velocity is 2 mL/(h.g)cat) Nitrogen/ethanol ratio 250:1 (volume ratio).
(V) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
Example 1
At room temperature, 2.0g P123 (EO)20PO70EO20) (0.00035mol) was dissolved in 40mL of anhydrous ethanol, then 3.2mL of 35 wt% hydrochloric acid (0.036mol), 0.286g of salicylic acid (0.0016mol) and 0.2g of citric acid (0.0010mol) were added and vigorously stirred uniformly, then 4.08g of aluminum isopropoxide (0.02mol), 0.0857g of copper acetate (0.00047mol) and 0.1616g of lanthanum acetate (0.00051mol) were added and vigorously stirred for 6 hours to obtain a uniform mixed solution. The solvent was evaporated at 60 ℃ for 24h under an air atmosphere and then dried at 65 ℃ for 48 h. And finally, putting the obtained dried sample into a muffle furnace, heating to 400 ℃ at the speed of 1 ℃/min, roasting for 4h, continuing heating to 700 ℃ at the speed of 10 ℃/min, roasting for 1h, and naturally cooling to obtain the catalyst A.
Loading the catalyst into a fixed bed reactor, closing the passage of hydrogen cylinder 1 connected with reaction tube 10, and filling N2Until the system pressure reaches 3MPa and then 10 ℃Heating the reactor at min to the reaction temperature (260 deg.C or 300 deg.C) for preparing higher alcohol from ethanol, and adding N2Preheating the ethanol carried by carrier gas in the raw material bottle 3, and then entering the reaction tube 10 to carry out in-situ reduction on the catalyst, wherein the liquid airspeed of the ethanol is 2 mL/(h.g)cat) The volume ratio of nitrogen to ethanol is 250: 1. The material after passing through the catalyst bed was collected by cooling in a condenser 13 and analyzed, and when its composition was constant, it indicated that the catalyst reduction was complete. After the reduction is finished, continuing to use N2Preheating the carrier gas carrying ethanol raw material, and then entering the reaction tube to start reaction, wherein the liquid airspeed of the ethanol is 2 mL/(h.g)cat) The volume ratio of nitrogen to ethanol is 250: 1. The reaction product after passing through the catalyst bed and unreacted ethanol are cooled and collected by a condenser 13 and analyzed
Example 2
Catalyst B was prepared as in example 1, except that 0.1429g (0.00079mol) of cupric acetate was added.
The reduction of catalyst B and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
The ordered mesoporous structure of catalyst B after the reaction [ Chem Eng j.,2017,303, 1583-. In the elemental distribution map like FIG. 2(B), the bright stripes correspond to the Al and O signals and clearly form an ordered framework, while the Cu-K and La-L signals are uniformly distributed over the ordered framework material. The above results indicate that the copper and rare earth metal oxide active components are highly dispersed in the catalyst and are stably present due to strong interactions between the three oxides of copper, lanthanum and aluminum.
Fig. 3 is an XRD pattern of catalyst B before and after the reaction. The XRD spectrum of the catalyst before reaction hardly has any obvious diffraction peak, and the XRD spectrum of the catalyst B after reaction has no gamma-Al2O3In addition to the diffraction peaks, no diffraction peaks of copper and lanthanum species occurred. Combining the results of HRTEM and HAADF-STEM analysis, it can be concluded that there is close interaction between three oxides in the one-pot evaporation-induced self-assembly synthesis method, so as to realize high dispersion of active components in the catalyst and effectiveAggregation and sintering of the active component are prevented.
In industrial applications, the catalyst is required to have not only good catalytic activity and selectivity to the target product, but also good stability. As shown in FIG. 4, the catalyst B shows excellent stability in 500h continuous reaction evaluation, and shows good industrial application prospects.
Example 3
Catalyst C was prepared as in example 1, except that 0.1858g (0.00102mol) of cupric acetate was added.
The reduction of catalyst C and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Example 4
Catalyst D was prepared as in example 1, except that 0.2286g (0.00126mol) of cupric acetate was added.
The reduction of catalyst D and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Example 5
Catalyst E was prepared as in example 1, except that the amount of lanthanum acetate added was 0.1347g (0.00043 mol).
The reduction of catalyst E and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Example 6
Catalyst F was prepared as in example 1, except that lanthanum acetate was added in an amount of 0.2155g (0.00068 mol).
The reduction of the catalyst F and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Example 7
Catalyst G was prepared as in example 2, except that lanthanum acetate was added in an amount of 0.2155G (0.00068 mol).
The reduction of catalyst G and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Example 8
At room temperature, 2.0g P123 (EO)20PO70EO20) (0.00035mol) was dissolved in 40mL of anhydrous ethanol, then 3.2mL of 35 wt% hydrochloric acid (0.036mol), 0.286g of salicylic acid (0.0016mol) and 0.2g of citric acid (0.0010mol) were added and vigorously stirred, and 4.08g of isopropyl alcohol was addedAluminum alkoxide (0.02mol), 0.1429g copper acetate (0.00079mol) and 0.1623g cerium acetate (0.00051mol) were vigorously stirred for 6 hours to obtain a uniform mixed solution. The solvent was evaporated at 60 ℃ for 24h under an air atmosphere and then dried at 65 ℃ for 48 h. And finally, putting the obtained dried sample into a muffle furnace, heating to 400 ℃ at the speed of 1 ℃/min, roasting for 4H, continuing heating to 700 ℃ at the speed of 10 ℃/min, roasting for 1H, and naturally cooling to obtain the catalyst H.
The reduction of catalyst H and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Example 9
At room temperature, 2.0g P123 (EO)20PO70EO20) (0.00035mol) was dissolved in 40mL of anhydrous ethanol, and then 3.2mL of 35 wt% hydrochloric acid (0.036mol), 0.286g of salicylic acid (0.0016mol) and 0.2g of citric acid (0.0010mol) were added thereto and vigorously stirred, and then 4.08g of aluminum isopropoxide (0.02mol), 0.1429g of copper acetate (0.00079mol) and 0.1866g of samarium chloride (0.00051mol) were added thereto and vigorously stirred for 6 hours to obtain a uniform mixed solution. The solvent was evaporated at 60 ℃ for 24h under an air atmosphere and then dried at 65 ℃ for 48 h. And finally, putting the obtained dried sample into a muffle furnace, heating to 400 ℃ at the speed of 1 ℃/min, roasting for 4h, then continuously heating to 700 ℃ at the speed of 10 ℃/min, roasting for 1h, and naturally cooling to obtain the catalyst I.
The reduction of catalyst I and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Example 10
At room temperature, 2.0g P123 (EO)20PO70EO20) (0.00035mol) was dissolved in 40mL of anhydrous ethanol, then 3.2mL of 35 wt% hydrochloric acid (0.036mol), 0.286g of salicylic acid (0.0016mol) and 0.2g of citric acid (0.0010mol) were added and vigorously stirred uniformly, and then 4.08g of aluminum isopropoxide (0.02mol), 0.1429g of copper acetate (0.00079mol) and 0.1959g of yttrium nitrate (0.00051mol) were added and vigorously stirred for 6 hours to obtain a uniform mixed solution. The solvent was evaporated at 60 ℃ for 24h under an air atmosphere and then dried at 65 ℃ for 48 h. And finally, putting the obtained dried sample into a muffle furnace, heating to 400 ℃ at the speed of 1 ℃/min, roasting for 4h, then continuously heating to 700 ℃ at the speed of 10 ℃/min, roasting for 1h, and naturally cooling to obtain the catalyst J.
The reduction of catalyst J and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Example 11
At room temperature, 2.0g P123 (EO)20PO70EO20) (0.00035mol) was dissolved in 40mL of anhydrous ethanol, then 3.2mL of 35 wt% hydrochloric acid (0.036mol), 0.286g of salicylic acid (0.0016mol) and 0.2g of citric acid (0.0010mol) were added and vigorously stirred uniformly, and then 4.08g of aluminum isopropoxide (0.02mol), 0.1429g of copper acetate (0.00079mol) and 0.2225g of praseodymium nitrate (0.00051mol) were added and vigorously stirred for 6 hours to obtain a uniform mixed solution. The solvent was evaporated at 60 ℃ for 24h under an air atmosphere and then dried at 65 ℃ for 48 h. And finally, putting the obtained dried sample into a muffle furnace, heating to 400 ℃ at the speed of 1 ℃/min, roasting for 4h, continuing heating to 700 ℃ at the speed of 10 ℃/min, roasting for 1h, and naturally cooling to obtain the catalyst K.
The reduction of catalyst K and the reaction of ethanol to higher alcohol were carried out in the same manner as in example 1.
Example 12
At room temperature, 2.0g P123 (EO)20PO70EO20) (0.00035mol) was dissolved in 40mL of anhydrous ethanol, then 3.2mL of 68 wt% nitric acid (0.049mol), 0.286g of salicylic acid (0.0016mol) and 0.2g of citric acid (0.0010mol) were added and vigorously stirred uniformly, and then 4.08g of aluminum isopropoxide (0.02mol), 0.1901g of copper nitrate (0.00079mol) and 0.1703g of lanthanum nitrate (0.00051mol) were added and vigorously stirred for 6 hours to obtain a uniform mixed solution. The solvent was evaporated at 60 ℃ for 24h under an air atmosphere and then dried at 65 ℃ for 48 h. And finally, putting the obtained dried sample into a muffle furnace, heating to 400 ℃ at the speed of 1 ℃/min, roasting for 4h, then continuously heating to 700 ℃ at the speed of 10 ℃/min, roasting for 1h, and naturally cooling to obtain the catalyst L.
The reduction of the catalyst L and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
Comparative example 1
Catalyst M was prepared as in example 1, except that 0.0286g (0.00016mol) of cupric acetate was added.
The reduction of the catalyst M and the reaction method for producing higher alcohols from ethanol were the same as in example 1.
Comparative example 2
Catalyst N was prepared as in example 1, except that 0.2858g (0.00157mol) of cupric acetate was added.
The reduction of catalyst N and the reaction of ethanol to higher alcohol were carried out in the same manner as in example 1.
Comparative example 3
At room temperature, 2.0g P123 (EO)20PO70EO20) (0.00035mol) was dissolved in 40mL of anhydrous ethanol, then 3.2mL of 35 wt% hydrochloric acid (0.036mol), 0.286g of salicylic acid (0.0016mol) and 0.2g of citric acid (0.0010mol) were added and vigorously stirred uniformly, and then 4.08g of aluminum isopropoxide (0.02mol) was added and vigorously stirred for 6 hours to obtain a uniform mixed solution. The solvent was evaporated at 60 ℃ for 24h under an air atmosphere and then dried at 65 ℃ for 48 h. And finally, putting the obtained dried sample into a muffle furnace, heating to 400 ℃ at the speed of 1 ℃/min, roasting for 4h, then continuously heating to 700 ℃ at the speed of 10 ℃/min, roasting for 1h, and naturally cooling to obtain the ordered mesoporous alumina carrier.
0.1901g of copper nitrate (0.00079mol) and 0.2214g of lanthanum nitrate (0.00051mol) are dissolved in 5ml of absolute ethyl alcohol to obtain a precursor solution, the ordered mesoporous alumina carrier is poured into the precursor solution, dried in the shade at room temperature and then dried in an oven at 110 ℃ for 4 hours. And (3) continuously heating the dried solid in a muffle furnace at the speed of 10 ℃/min to 450 ℃ for roasting for 3h, and naturally cooling to obtain the catalyst O.
The reduction of the catalyst O and the reaction of ethanol to higher alcohols were carried out in the same manner as in example 1.
As can be seen from fig. 5, the catalytic activity of catalyst O showed a significant decline, and the yield of higher alcohols at 200h decreased to 36.1%, which was already lower than 37.3% of catalyst B; and the catalyst B has no obvious activity reduction in the reaction process of 500h, and the excellent stability of the catalyst B is further proved.
The reaction conditions and results are shown in table 1.
TABLE 1 reaction results of different catalysts in fixed bed ethanol continuous dehydrogenation condensation to produce higher alcohols
Figure BDA0003308222250000101
Figure BDA0003308222250000111

Claims (10)

1. An ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst, which is characterized by being prepared by the following method:
dissolving a template agent in absolute ethyl alcohol, adding inorganic strong acid, salicylic acid and citric acid, and uniformly mixing; adding soluble salt of copper, soluble salt of rare earth metal and soluble salt of aluminum, and mixing uniformly; evaporating the solvent at 25-80 ℃ for 1-72 h, and then drying at 60-120 ℃ for 2-96 h; heating the obtained mixture to 350-550 ℃ at the speed of 1-10 ℃/min in a muffle furnace, roasting for 2-10 h, then continuously heating to 600-800 ℃ at the speed of 10-30 ℃/min, and roasting for 0.5-6 h to obtain the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst; the template agent is a triblock polymer surfactant;
the amount of aluminum in the soluble salt of aluminum is calculated according to the theoretical mass of the soluble salt of aluminum completely generating aluminum oxide, and the ratio of the amount of the template agent, hydrogen ions in inorganic strong acid, salicylic acid, citric acid and the amount of the aluminum in the soluble salt of aluminum is 0.015-0.02: 1-5: 0.05-0.1: 0.03-0.08: 1;
the mass of the soluble salt of copper, the mass of the soluble salt of rare earth metal and the mass of the soluble salt of aluminum are respectively calculated according to the theoretical mass that the soluble salt of copper completely generates copper oxide, the soluble salt of rare earth metal completely generates rare earth metal oxide and the soluble salt of aluminum completely generates aluminum oxide, and the mass of the copper oxide is 2.5-8.5% of the mass of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst; the mass of the rare earth metal oxide is 3-15% of that of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst; the mass of the alumina is 76.5-94.5% of that of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst.
2. The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst according to claim 1, wherein: the volume of the absolute ethyl alcohol is 2-20mL/g calculated by the mass of the soluble salt of the aluminum.
3. The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst according to claim 1, wherein: the soluble salt of copper is one or a mixture of more of copper acetate, copper nitrate and copper chloride.
4. The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst according to claim 1, wherein: the rare earth metal in the soluble salt of the rare earth metal is one or a mixture of more than two of the rare earth metals.
5. The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst according to claim 1, wherein: the soluble salt of the rare earth metal is one or a mixture of more of acetate, nitrate and chloride of the rare earth metal.
6. The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst according to claim 1, wherein: the soluble salt of aluminum is one or a mixture of more of aluminum nitrate, aluminum isopropoxide and aluminum chloride.
7. The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst according to claim 1, wherein: the template agent is one or a mixture of P123 and F127.
8. The ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst according to claim 1, wherein: the inorganic strong acid is one or a mixture of two of hydrogen chloride and nitric acid.
9. Use of the ordered mesoporous copper-rare earth metal-aluminum composite oxide catalyst of claim 1 in the reaction of dehydrogenation condensation of ethanol to produce higher alcohols.
10. The use according to claim 9, characterized in that the use is: introducing nitrogen and ethanol into a fixed bed reactor at the temperature of 150-300 ℃ and the reaction pressure of normal pressure to 4.0MPa, wherein the liquid airspeed is 0.5-5 mL/(h.g)cat) And carrying out the reaction of preparing higher alcohol by dehydrogenating and condensing the ethanol under the condition that the volume ratio of the nitrogen to the ethanol is 100-600: 1.
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