CN109603837B - Preparation method of Cu/Ce/Co catalyst for furfural liquid-phase hydrogenation - Google Patents
Preparation method of Cu/Ce/Co catalyst for furfural liquid-phase hydrogenation Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
Abstract
The invention discloses a Cu/Ce/Co catalyst for preparing furfuryl alcohol by furfural liquid-phase hydrogenation, which has the advantages of low Cu loading, high activity and good stability. The Cu/Ce/Co catalyst consists of Cu and CeO2And Co3O4The catalyst comprises the following components in percentage by mass: 5 to 35% of CeO2：5～35％，Co3O4: 30-70%. A preparation method thereof and application thereof in preparing furfuryl alcohol by furfural liquid phase hydrogenation. The Cu/Ce/Co catalyst provided by the invention is only composed of three inorganic substances, is green and nontoxic, has the advantages of simple preparation process, low price, convenience in use, excellent activity, selectivity and stability, and obviously improved furfural conversion rate and furfuryl alcohol selectivity.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a method for preparing furfuryl alcohol by liquid-phase hydrogenation of furfural with Cu and CeO2And Co3O4A method for preparing the catalyst and the application thereof.
Background
Non-renewable fossil resources such as petroleum and coal constitute the cornerstone of the energy and chemical industries today. However, the increasingly exhausted fossil resources, the environmental pollution caused in the using process and the emission of greenhouse gases become bottlenecks which restrict the sustainable development of society and economy. The dual pressure of resources and environment has greatly promoted the research on the utilization of the selective transformation of biomass and derivatives thereof. The furfural is produced by using renewable agricultural and forestry crops such as dry bagasse rich in pentosan, corncobs, rice husks and the like as raw materials, and has the characteristics of inexhaustibility and inexhaustibility. The hydrogenation product furfuryl alcohol is an important organic chemical raw material, and is mainly used for producing furfural resin, furan resin, furfuryl alcohol-urea-formaldehyde resin, phenolic resin and the like. Also used for preparing fruit acid, plasticizer, solvent, rocket fuel, etc. In addition, the rubber composition has wide application in industrial departments such as dye, synthetic fiber, rubber, pesticide, casting and the like. With the rapid development of applied chemistry and fine chemistry, the demand for furfuryl alcohol is also increasing. Therefore, the method finds out the green sustainable development path for producing the furfuryl alcohol by the furfural method, and has profound significance and broad prospect.
The furfural molecule contains active aldehyde group and furan ring has carbon-carbon double bond, so that the hydrogenation reaction is mainly the hydrogenation saturation of the carbon-oxygen double bond in the aldehyde group and the carbon-carbon double bond on the furan ring to generate furfuryl alcohol or tetrahydrofurfuryl alcohol. In addition, the carbon-oxygen bond on the furfuryl alcohol side chain is easily broken due to the influence of the adjacent furan ring, and 2-methylfuran is produced by hydrogenation. Therefore, the method has important significance for realizing the directional conversion of the furfural to the furfuryl alcohol on the metal Cu-based catalyst by constructing different catalysts.
As is well known, the preparation of furfuryl alcohol by furfural hydrogenation can be divided into liquid phase method and gas phase method, and due to factors such as active metal, carrier type, interaction between the auxiliary agent and the carrier, various catalysts show great difference in furfural hydrogenation reaction.
Currently, furfural hydrogenation catalysts mainly comprise:
1) chromium-containing Cu-based catalyst: for example, Zhuyulei et al (petrochemical, 1992, 217, 466-469) disclose a Cu-Cr catalyst prepared by coprecipitation method, which can make the conversion rate of furfural reach 100%, and the selectivity and yield of furfuryl alcohol both reach above 98%. However, the catalyst contains carcinogenic Cr, which causes serious chromium pollution, and the low-chromium or chromium-free catalyst becomes the development trend of furfural production.
2) Chromium-free Cu-based catalyst comprising CuO-SiO2Cu-Zn based catalysts, Cu-Al based catalysts, and the like. For example, Zhou Yaming et al (petrochemical, 1997, 26 (1): 4-7) disclose that activity tests were carried out on Cu-Zn-based catalysts. Liyaan et al (fine petrolizing)Others, 1995, (1):40-) on a support gamma-Al2O3Active carbon, MT-grade white carbon black and SiO2And (5) screening. However, these catalysts have disadvantages in that the reaction temperature is high and copper grains are liable to grow to cause sintering of the catalyst.
3) Framework nickel-based catalyst: liubaijun et al (catalytic bulletin 1997,18(5):176-3/2PM12O40The modified RNi has higher activity for preparing furfuryl alcohol by furfural hydrogenation, and has the disadvantage that the catalyst is easy to deactivate.
4) Skeletal Co-based catalyst: patent CN1066610 discloses a cobalt-based framework catalyst for producing furfuryl alcohol by furfural liquid-phase hydrogenation, but the catalyst contains Cr, which causes chromium pollution.
Therefore, the development of a catalyst which is more environment-friendly and has excellent catalytic performance and is suitable for preparing furfuryl alcohol by furfural liquid-phase hydrogenation is still needed.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide the Cu/Ce/Co catalyst for preparing furfuryl alcohol by furfural liquid-phase hydrogenation, which has the advantages of low Cu loading, high activity and good stability.
The catalyst for selective hydrogenation of furfural consists of Cu and CeO2And Co3O4And (4) forming. Wherein the Cu/Ce/Co catalyst comprises the following components in percentage by mass: 5 to 35% of CeO2：5～35％，Co3O4：30～70％。
Preferably, the mass percent of each component in the Cu/Ce/Co catalyst is Cu: 15 to 20% of CeO2：10～25％，Co3O4：55～75％。
The invention also aims to provide a preparation method of the Cu/Ce/Co catalyst, which comprises the following steps:
preparing inorganic salts of copper, cerium and cobalt into a mixed salt water solution with the concentration of 0.5-3 mol/L according to the stoichiometric ratio of Cu, Ce and Co; and carrying out coprecipitation reaction with 0.1-2 mol/L aqueous alkali, after the reaction is finished, carrying out water bath aging on a mineral salt precursor at 60 ℃ for 2-5 h, carrying out suction filtration, washing to be neutral, and then sequentially carrying out drying, roasting and reduction reaction to obtain the Cu/Ce/Co catalyst.
The preparation method of the copper-based catalyst is characterized by comprising the following steps: the inorganic salts of copper, cerium and cobalt may be nitrates and/or hydrochlorides.
The preparation method of the Cu/Ce/Co catalyst is characterized by comprising the following steps: the concentration of the inorganic salt of copper, cerium and cobalt is preferably 0.5-1 mol/L.
The preparation method of the Cu/Ce/Co catalyst is characterized by comprising the following steps: in the alkali solution, the alkali is at least one selected from sodium hydroxide and sodium carbonate.
The preparation method of the Cu/Ce/Co catalyst is characterized by comprising the following steps: the concentration of the alkali solution is 0.5-2.0 mol/L.
The preparation method of the Cu/Ce/Co catalyst is characterized by comprising the following steps: in the coprecipitation reaction step, the pH value of the reaction is 9-11, preferably 10-11; the reaction temperature is 50-80 ℃.
The preparation method of the copper-based catalyst is characterized by comprising the following steps: in the step of coprecipitation reaction, the aging time is 3-12 h; the drying conditions are as follows: the temperature is 30-150 ℃, and the time is 4-12 h; the roasting conditions are as follows: the temperature is 300-550 ℃, and the time is 2-10 h. In the reduction step, the reduction atmosphere is high-purity hydrogen, the flow of the hydrogen (high-purity hydrogen) is 50-200 mL/min, the temperature is increased from room temperature to the reduction temperature of 300-550 ℃ at the heating rate of 5 ℃/min, and the reduction is carried out for 2-5 h.
The invention also aims to provide the application of the Cu/Ce/Co catalyst in the preparation of furfuryl alcohol by furfural liquid-phase hydrogenation.
It is a further object of the present invention to provide a process for the liquid phase hydrogenation of furfural to produce furfuryl alcohol, which comprises:
adding reaction raw materials of furfural, water and the Cu/Ce/Co catalyst into a closed high-pressure reaction kettle, wherein the initial pressure of hydrogen filled in the reaction kettle at room temperature is 1-8 MPa, the reaction temperature is 60-180 ℃, and the reaction time is 10 min-10 h. The mass ratio of the raw material furfural to water is 1: 50-1: 10, and the mass ratio of the raw material furfural to the catalyst is 1: 1-20: 1.
Preferably, in the method for preparing furfuryl alcohol by furfural liquid-phase hydrogenation, the reaction temperature is 90-140 ℃, the initial pressure of hydrogen in a reaction kettle at room temperature is 3-6 MPa, and the reaction time is 30 min-5 h.
Advantageous effects
The Cu/Ce/Co catalyst provided by the invention is only composed of three inorganic substances, is green and nontoxic, has the advantages of simple preparation process, low price, convenience in use, excellent activity, selectivity and stability, and obviously improved furfural conversion rate and furfuryl alcohol selectivity.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the Cu/Ce/Co catalyst of example 1 prior to reduction.
FIG. 2 is an XRD pattern of the Cu/Ce/Co catalyst after reduction in example 1.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
The Cu/Ce/Co catalyst provided by the invention takes cheap metal copper as a main active component, is low in cost, shows furfural selective hydrogenation performance superior to Cu/Ce and Cu/Co, and has high stability. The catalytic process has high product yield and selectivity, and the yield of the furfuryl alcohol can reach over 90 percent under optimized reaction conditions. Therefore, the method has good application prospect.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
Preparation of Cu/Ce/Co catalyst: preparing Cu (NO) with total metal ion concentration of 2mol/L3)2·3H2O、Ce(NO3)3·6H2O and Co (NO)3)2·6H2O mixed solution, wherein the molar ratio of Cu to Ce to Co is 0.5 to 1 to 4, and mol (NaOH) to mol (Na) is prepared2CO3) 2:1 (total concentration of 3mol/L) mixed alkali solution. And under the condition of strong stirring, simultaneously dropwise adding the salt solution and the alkali solution into a three-neck flask for coprecipitation, controlling the pH of the precipitation solution to be 9-10, and controlling the precipitation temperature to be 50 ℃. Aging for 5h after precipitation is finished, filtering, washing, drying, and roasting for 4h at 400 ℃; and then reducing the catalyst precursor to 300 ℃ at the heating rate of 5 ℃/min in a hydrogen atmosphere for 4h, wherein the flow of hydrogen is 100mL/min, and cooling to room temperature to obtain the Cu/Ce/Co catalyst.
Example 2
Preparation of Cu/Ce/Co catalyst: preparing Cu (NO) with total metal ion concentration of 1.5mol/L3)2·3H2O、Ce(NO3)3·6H2O and Co (NO)3)2·6H2A mixed solution of O, wherein the molar ratio of Cu to Ce to Co is 1:2:5, and a NaOH solution having a concentration of 2.0mol/L was prepared. And under the condition of strong stirring, simultaneously dropwise adding the salt solution and the alkali solution into a three-neck flask for coprecipitation, and controlling the pH of the obtained precipitation solution to be 9-10 and the precipitation temperature to be 60 ℃. And after the precipitation is finished, aging for 10h, filtering, washing, drying, roasting for 5h at 450 ℃, reducing the catalyst precursor to 350 ℃ at the heating rate of 5 ℃/min in a hydrogen atmosphere for 5h, wherein the flow of hydrogen is 120mL/min, and cooling to room temperature to obtain the Cu/Ce/Co catalyst.
Example 3
Preparation of Cu/Ce/Co catalyst: preparation of Total Metal ionsCuCl with concentration of 2.5mol/L2、Ce(NO3)3·6H2O and Co (NO)3)2·6H2A mixed solution of O, wherein the molar ratio of Cu to Ce to Co is 1:0.5:5, and Na is prepared at a concentration of 2.0mol/L2CO3And (3) solution. And under the condition of strong stirring, simultaneously dropwise adding the salt solution and the alkali solution into a three-neck flask for coprecipitation, and controlling the pH of the obtained precipitation solution to be 8-9 and the precipitation temperature to be 70 ℃. And after the precipitation is finished, aging for 6h, filtering, washing, drying, roasting for 3h at 450 ℃, reducing the catalyst precursor to 450 ℃ at the heating rate of 5 ℃/min in a hydrogen atmosphere for 2h, wherein the flow of hydrogen is 110mL/min, and cooling to room temperature to obtain the Cu/Ce/Co catalyst.
Example 4
Preparation of Cu/Ce/Co catalyst: preparing CuCl with total metal ion concentration of 2.0mol/L2、Ce(NH4)2(NO3)6And Co (NO)3)2·6H2A mixed solution of O, wherein the molar ratio of Cu to Ce to Co is 1:1:6, and a NaOH solution having a concentration of 1.5mol/L was prepared. And under the condition of strong stirring, simultaneously dropwise adding the salt solution and the alkali solution into a three-neck flask for coprecipitation, controlling the pH of the precipitation solution to be 10-11, and controlling the precipitation temperature to be 80 ℃. And after the precipitation is finished, aging for 8h, filtering, washing, drying, roasting for 5h at 350 ℃, reducing the catalyst precursor to 300 ℃ at the heating rate of 5 ℃/min in a hydrogen atmosphere for 4h, wherein the flow of hydrogen is 160mL/min, and cooling to room temperature to obtain the Cu/Ce/Co catalyst.
Example 5
Preparation of Cu/Ce/Co catalyst: preparing CuCl with total metal ion concentration of 2.0mol/L2、Ce(NH4)2(NO3)6And CoCl2·6H2A mixed solution of O, wherein the molar ratio of Cu to Ce to Co is 2:1:5, and a NaOH solution having a concentration of 2.0mol/L was prepared. And under the condition of strong stirring, simultaneously dropwise adding the salt solution and the alkali solution into a three-neck flask for coprecipitation, controlling the pH of the solution obtained by precipitation to be 11-12, and controlling the precipitation temperature to be 40 ℃. Aging for 6h after precipitation, filtering, washing, drying, roasting for 3h at 500 ℃, and then putting the catalyst precursor into hydrogenReducing for 3h in the atmosphere at the temperature rising rate of 5 ℃/min to 350 ℃, wherein the flow of hydrogen is 150mL/min, and cooling to room temperature to obtain the Cu/Ce/Co catalyst.
Experimental example 1: catalytic furfural hydrogenation for preparing furfuryl alcohol
And adding pre-weighed furfural, the activated catalyst prepared in the examples 1 to 5 and water into a 50mL stainless steel reaction kettle for hydrogenation reaction, wherein the mass ratio of copper-based catalyst to furfural is 1:12, the reaction temperature is 100 ℃, the reaction pressure is 4MPa, and the reaction time is 5 h. The pressure and temperature changes of the process are recorded and monitored by a computer connected to the reactor. After the reaction was completed, the stirring was stopped, the temperature was lowered to room temperature, the pressure was released, the centrifuged supernatant liquid was filtered through a 0.22 μm filter, and the product was analyzed by gas chromatography, and the results are shown in table 1 below.
TABLE 1
| Catalyst and process for preparing same | Conversion of furfural/% | Furfuryl alcohol selectivity/% |
| Example 1 | 100 | 91 |
| Example 2 | 97 | 92 |
| Example 3 | 96 | 88 |
| Example 4 | 100 | 96 |
| Example 5 | 95 | 96％ |
Therefore, the Cu/Ce/Co catalyst prepared by taking metal salt as a precursor has good activity and furfuryl alcohol selectivity for catalyzing furfural hydrogenation; the catalyst is prepared by a simple coprecipitation method, the raw materials are cheap and easy to obtain, and the cost of the catalyst is low. Therefore, compared with the prior art, the method has economic advantages and industrial application prospects.
Claims (6)
1. A process for the liquid phase hydrogenation of furfural to furfuryl alcohol comprising:
adding reaction raw materials of furfural, water and a Cu/Ce/Co catalyst into a closed high-pressure reaction kettle, wherein the initial pressure of hydrogen filled in the reaction kettle at room temperature is 1-8 MPa, and the reaction temperature is 60-180 DEG CoC, the reaction time is 10 min-10 h; the mass ratio of the raw material furfural to water is 1: 50-1: 10, and the mass ratio of the raw material furfural to the catalyst is 1: 1-20: 1;
the Cu/Ce/Co catalyst consists of Cu and CeO2And Co3O4The catalyst comprises the following components in percentage by mass: 5 to 35% of CeO2：5~35%，Co3O4：30~70%；
The preparation method of the Cu/Ce/Co catalyst comprises the following steps:
preparing inorganic salts of copper, cerium and cobalt into a mixed salt water solution with the concentration of 0.5-3 mol/L according to the stoichiometric ratio of Cu, Ce and Co; carrying out coprecipitation reaction with 0.1-2 mol/L alkali solution, and after the reaction is finished, carrying out 60% reaction on a mineral salt precursoroC, aging in water bath for 2-5 h, performing suction filtration, washing to neutrality, and then sequentially performing drying, roasting and reduction reaction to obtain the Cu/Ce/Co catalystAn oxidizing agent.
2. The method for preparing furfuryl alcohol by furfural liquid-phase hydrogenation according to claim 1, wherein the reaction temperature is 90-140%oAnd C, the initial pressure of hydrogen in the reaction kettle at room temperature is 3-6 MPa, and the reaction time is 30 min-5 h.
3. The method for preparing furfuryl alcohol by furfural liquid-phase hydrogenation according to claim 1, wherein in the preparation method of the Cu/Ce/Co catalyst, the inorganic salts of copper, cerium and cobalt are nitrates and/or hydrochlorides, and the concentration of the inorganic salts of copper, cerium and cobalt is 0.5-1 mol/L.
4. The method for preparing furfuryl alcohol by furfural liquid-phase hydrogenation according to claim 1, wherein the alkali in the alkali solution in the preparation method of the Cu/Ce/Co catalyst is sodium hydroxide, and the concentration of the alkali solution is 0.5-2.0 mol/L.
5. The method for preparing furfuryl alcohol by furfural liquid-phase hydrogenation according to claim 1, wherein in the coprecipitation reaction step in the preparation method of the Cu/Ce/Co catalyst, the reaction pH is 9-11; the reaction temperature is 50-80 deg.CoC; the drying conditions are as follows: the temperature is 30-150 DEG CoC, the time is 4-12 hours; the roasting conditions are as follows: the temperature is 300-550 deg.CoC, the time is 2-10 hours; in the reduction step, the reduction atmosphere is high-purity hydrogen, the hydrogen flow is 50-200 mL/min and is 5oThe temperature rise rate of C/min is increased from room temperature to the reduction temperature of 300-550oAnd C, reducing for 2-5 h.
6. The method for preparing furfuryl alcohol by furfural liquid-phase hydrogenation according to claim 5, wherein in the coprecipitation reaction step, the reaction pH is 10-11.
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