CN109833897B - Catalyst for producing furfuryl alcohol, preparation method thereof and method for producing furfuryl alcohol - Google Patents
Catalyst for producing furfuryl alcohol, preparation method thereof and method for producing furfuryl alcohol Download PDFInfo
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Abstract
The present invention relates to a catalyst for producing furfuryl alcohol, a preparation method thereof and a method for producing furfuryl alcohol. The catalyst consists of a main active component, an auxiliary agent and a passivated carrier. The main active component is Cu, the auxiliary agent is one or more of alkali metal, alkaline earth metal and rare earth metal oxides, and the passivated carrier is a silicon oxide-containing inorganic carrier. The catalyst of the invention is characterized in that the adopted carrier is passivated, specifically one or more of heat treatment, silanization or etherification. According to the invention, the catalyst is prepared by adopting an ammonia evaporation-induced deposition-precipitation method, the preparation method is simple and convenient, the requirements on equipment required by raw material storage and catalyst preparation are low, and the large-scale application is easy. The catalyst of the invention is used for furfural hydrogenation, shows high conversion per pass of furfural, high furfuryl alcohol selectivity and long catalyst life, and has good industrial application prospect.
Description
Technical Field
The invention relates to a catalyst for producing furfuryl alcohol, a preparation method thereof and a method for producing furfuryl alcohol, and belongs to the technical field of biomass conversion and catalysis.
Background
The growing contradiction between energy supply and demand and the increasingly stringent environmental requirements have promoted the research on the conversion and utilization of renewable biomass resources. Furfural is a chemical raw material mainly derived from wood biomass such as agricultural and forestry waste. China is the biggest furfural producing country in the world, but has very limited high-value utilization of furfural. The furfural can be used for preparing furfuryl alcohol with high added value through selective hydrogenation reaction. The furfuryl alcohol can be used for producing sand core binders, high temperature resistant phenolic resin binders, plasticizers with excellent cold resistance, synthetic fibers, polyurethane foams, tetrahydrofurfuryl alcohol and the like required by the casting industry. In addition, furfuryl alcohol is also a good solvent for varnishes, pigments and the like, and is an intermediate for the production of pesticides, fragrances and medicines. Therefore, the research on the selective hydrogenation of furfural to prepare furfuryl alcohol is receiving extensive attention from both academia and industry.
The furfuryl alcohol preparation by furfural hydrogenation has two processes, namely a liquid phase process and a gas phase process. The liquid phase method using Cu — Cr catalyst was commercialized in 1948. The liquid phase method has the characteristics of high temperature, difficult catalyst separation and regeneration, high equipment requirement and the like. Compared with the prior art, the gas phase method has the advantages of low reaction temperature, low pressure, deep hydrogenation inhibition, simple catalyst recovery and the like. At present, catalysts used in a gas phase method mainly comprise a copper-silicon system and a copper-chromium system, and although the copper-chromium system catalyst has the advantages of high selectivity and high stability, the development of the copper-chromium catalyst is limited because heavy metal Cr can cause pollution to the environment and bring harm to human bodies. Therefore, the development of the chromium-free copper-based catalyst which is pollution-free and harmless to human bodies becomes a research hotspot and development trend of the furfural gas-phase hydrogenation catalyst.
Patent CN 101423505a discloses MgO supported Cu catalyst, which shows high furfural conversion and furfuryl alcohol selectivity, without mentioning the stability of the catalyst. CN 1410161A discloses a Cu-Co bimetallic catalyst loaded by MgO, and the preparation method of the catalyst related to the invention is simple, but the yield of furfuryl alcohol is lower. Patents CN 1149507a and CN 1876233a disclose CuO-ZnO-Al for preparing furfuryl alcohol by furfural gas phase hydrogenation respectively2O3-alkaline earth metal oxide-transition metal oxide and CuO-Ce2O3-Fe2O3-SiO2-TiO2Quinary chromium-free catalysts, although they all exhibit excellent catalytic performance, the complexity of components and the cumbersome preparation process result in increased uncontrollable preparation and increased investment of the catalyst. Patent CN 103007941a discloses a copper oxide-silicon oxide composite oxide catalyst, which has simple composition and higher furfural conversion rate and furfuryl alcohol selectivity, but the use of sodium hydroxide in the catalyst preparation process brings alkaline wastewater treatment problem. Shanxi coal chemical institute (Catal.Sci.Technol.,2017,7, 1880-1891) reports a copper silicate precursor-based copper-silicon furfural hydrogenation catalyst system with silica sol as a silicon source, and finds that the furfural conversion rate and the furfuryl alcohol selectivity are related to the content of metallic copper at a high space velocity, but the stability of the catalyst is not given, and meanwhile, the instability of the silica sol brings certain limits to the storage and the use of the silica sol, so that the large-scale preparation of the catalyst is limited.
In summary, the existing copper-based chromium-free catalysts still need to be improved in one or more aspects of activity, selectivity, stability, catalyst preparation and the like in furfuryl alcohol production by furfural hydrogenation.
Disclosure of Invention
In view of the disadvantages in the prior art, the present invention aims to provide a catalyst for producing furfuryl alcohol and a method for preparing the same, which can realize one or more of the following: (1) the method comprises the following steps of (1) improving the activity of the catalyst, (2) improving the furfural treatment capacity of the catalyst, (3) reducing the furfural loss, (4) simplifying the regeneration condition of the catalyst, (5) realizing the furfuryl alcohol production at a lower reaction temperature, and (6) having simple catalyst composition and low raw material storage requirement and being suitable for large-scale production.
The inventors of the present invention found that: the carrier selection and the reaction performance are closely related, and after passivation treatment, white carbon black and SiO2The number of hydroxyl groups on the surface of the carrier rich in the silicon oxide components, such as SBA-15, MCM-41 and the like, is reduced to a certain extent, the surface acidity of the catalyst is reduced, the polymerization of the raw material furfural and the product furfuryl alcohol on the surface of the catalyst is weakened, the loss of the furfural is reduced, and the inactivation of the catalyst is inhibited. After the main active component and the auxiliary agent are loaded on the passivated carrier, the high activity is shown in the reaction of producing furfuryl alcohol by furfural gas phase hydrogenation, the high furfuryl alcohol selectivity of the catalyst is maintained, the loss of furfural in the reaction process is reduced, and the service cycle of the catalyst is prolonged. Meanwhile, the catalyst prepared by the ammonia evaporation-induced deposition precipitation method ensures strong interaction between metal and the carrier, promotes high dispersion of metal copper and the auxiliary agent on the surface of the carrier, and provides high reaction activity and continuous regeneration possibility. The use of silica solid carriers, especially white carbon black, avoids storage and use limitations caused by instability of silica sol, and makes the catalyst production more suitable for large-scale application. Thereby, one or more of the above objects may be achieved.
Accordingly, in one aspect, the present invention provides a catalyst for the production of furfuryl alcohol, characterized in that: the catalyst consists of a main active component, an auxiliary agent and a passivated carrier, wherein the main active component is Cu, the auxiliary agent is one or more of alkali metal, alkaline earth metal and rare earth metal oxides, and the passivated carrier is a silica-containing inorganic carrier.
In a preferred embodiment, the alkali metal is one or more of Li, Na and K.
In a preferred embodiment, the alkaline earth metal is one or more of Mg, Ca, Sr and Ba.
In a preferred embodiment, the rare earth metal includes, but is not limited to, one or more of La, Ce, Pr, Nd, Sm, and Eu.
In a preferred embodiment, the main active component Cu accounts for 1.0-50.0% of the total weight of the catalyst, and the auxiliary agent accounts for 0.1-30.0% of the total weight of the catalyst.
In a preferred embodiment, the passivated support includes, but is not limited to: white carbon black, MCM-41, SiO2Microspheres, SiO2One or more of nanoparticles and SBA-15.
In a preferred embodiment, the inorganic carrier is passivated by a high-temperature heat treatment, specifically, the carrier is calcined at a temperature of not less than 600 ℃ for not less than 10 min.
In a preferred embodiment, the inorganic carrier is passivated by silanization, specifically, the carrier is contacted with silanization reagent at 80-200 ℃ for 0.5-48 hours.
In a preferred embodiment, the inorganic carrier passivation treatment method is an etherification treatment, and specifically, the carrier is contacted with the etherification agent for 0.5 to 48 hours.
In a preferred embodiment, the silylating agent includes, but is not limited to: one or more of trimethylchlorosilane, dichlorodimethylsilane, trichloromethylsilane, hexamethyldisilazane, aminopropyltriethoxysilane and trimethylbromosilane.
In a preferred embodiment, the etherification reagents include, but are not limited to: one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, butanol, pentanol, propylene glycol, glycerol, butanediol, hexanol and phenol.
The invention also provides a method for preparing the catalyst, which is characterized in that the method is an ammonia-induced deposition precipitation method, and specifically comprises the following steps:
a) silica inorganic carrier (carbon black, MCM-41, SiO)2Microspheres, SiO2Nano particles and SBA-15) are passivated;
b) dissolving metal salt of required metal components in deionized water, and introducing ammonia gas until the metal salt is saturated;
c) adding the carrier obtained by passivation treatment in the step a) into the metal salt solution in the step b), and stirring and mixing uniformly;
d) heat treating the mixture system of c) to remove ammonia from the system;
e) after the pH of the mixture is close to neutral, the mixture is filtered and washed to obtain a filter cake.
f) The filter cake is treated by heat activation to obtain the catalyst.
In a preferred embodiment, the metal salt of step b) is a nitrate, carbonate or oxalate salt.
In a preferred embodiment, the heat treatment temperature in step d) is 50 to 100 ℃.
In a preferred embodiment, the heat treatment method of step f) is: drying at 60-150 ℃ for 2-48 h, and roasting at 350-750 ℃ for 2-48 h.
In another aspect, the present invention also provides a process for producing furfuryl alcohol, characterized in that furfural is subjected to a hydrogenation reaction in a fixed bed reactor in the presence of the above-described catalyst to produce furfuryl alcohol with high selectivity.
In a preferred embodiment, the method is performed under the following conditions: the temperature is 90-300 ℃, the pressure is 0.01-2.0 MPa, the air speed of the furfural is 0.01-10 g/g-catalyst/h, and the molar ratio of hydrogen to furfural is 1-50.
In a preferred embodiment, the catalyst used is activated in an atmosphere containing hydrogen gas at a temperature of 150 to 500 ℃ for 0.5 to 48 hours before use.
Compared with the prior art, the invention has the beneficial effects that: white carbon black in the catalyst of the invention、SiO2The carrier rich in the silica component, such as SBA-15 and MCM-41, is passivated by means of high-temperature heat treatment, silanization treatment or etherification treatment. A large amount of hydroxyl exists on the surface of the carrier rich in the silicon oxide component, especially on the surface of the white carbon black carrier, so that the surface of the catalyst presents a certain acidic environment, the polymerization of furfural and furfuryl alcohol is facilitated to generate carbon deposition, the loss of furfural is increased, and the inactivation of the catalyst is accelerated. The number of hydroxyl groups on the surface of the passivated carrier is reduced to a certain extent, so that the surface acidity of the catalyst is reduced, the polymerization of the raw material furfural and the product furfuryl alcohol on the surface of the catalyst is weakened, the loss of furfural is reduced, and the inactivation of the catalyst is inhibited. After the main active component and the auxiliary agent are loaded on the passivated carrier, the high activity is shown in the reaction of producing furfuryl alcohol by furfural gas phase hydrogenation, the high furfuryl alcohol selectivity of the catalyst is maintained, the loss of furfural in the reaction process is reduced, and the service cycle of the catalyst is prolonged. The use of solid silica carriers such as white carbon black overcomes the barrier of infeasible carrier passivation treatment caused by the use of silica sol type silica precursors, and simultaneously avoids the troubles in the storage and use processes caused by the instability of silica sol. Meanwhile, the catalyst prepared by the ammonia evaporation-induced deposition precipitation method ensures strong interaction between metal and the carrier, promotes high dispersion of metal copper and the auxiliary agent on the surface of the carrier, and provides high reaction activity and continuous regeneration possibility.
Detailed Description
The invention is further illustrated by the following specific examples, wherein the amounts and percentages are by mass.
Example 1
40％Cu-6％CaO-2％CeO2Preparation and application of/SBA-15 catalyst
10g of SBA-15 powder is placed in 200ml of anhydrous toluene, 2g of trimethylchlorosilane is added, reflux treatment is carried out for 12 hours, a solid is obtained by filtration, and the filtrate is washed by using an ethanol water solution until the filtrate is free of chlorine. The solid obtained was dried at 120 ℃ for 12 h. 14.62g of Cu (NO)3)2·3H2O、1.79g Ca(NO3)2·4H2O and 0.49gCe (NO)3)2·6H2Dissolving O in 50ml deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas after the pH value of the system is not increased any more, and stirring the obtained solution system for 20 min. 5g of SBA-15 powder obtained by the above silylation treatment was weighed out and added to the solution, and stirred at room temperature for 4 hours. And transferring the uniformly stirred mixture system into a water bath at 80 ℃, continuously stirring to remove ammonia gas in the mixture, and removing the mixture from the water bath to cool after the pH value of the system is reduced to be close to neutral. And after the system is cooled to room temperature, filtering to obtain a filter cake. Washing the filter cake with deionized water for 5 times, drying the filter cake at 120 ℃ for 12h, then roasting at 450 ℃ for 4h, tabletting and screening to obtain the catalyst A.
Before the catalyst was used, it was reduced in hydrogen at 300 ℃ for 5 hours. After the temperature of the reactor bed layer is reduced to 130 ℃, furfural is injected into the reactor at the speed of 1.4g/H, and H is adjusted2The molar ratio of furfural was 10, and after 48 hours of reaction, a sample was taken for analysis. The reaction results are shown in Table 1.
Example 2
10％Cu-1％MgO-2％CeO2Preparation and application of/MCM-41 catalyst
10g of MCM-41 powder was placed in 200ml of anhydrous toluene, 3g of aminopropyltriethoxysilane was added, reflux treatment was performed at 110 ℃ for 12 hours, a solid was obtained by filtration, and washing was performed with an aqueous ethanol solution until the filtrate was free of chlorine. The solid obtained was dried at 120 ℃ for 12 h. 2.18g of Cu (NO)3)2·3H2O、0.37g Mg(NO3)2·6H2O and 0.29g Ce (NO)3)2·6H2Dissolving O in 50ml deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas after the pH value of the system is not increased any more, and stirring the obtained solution system for 20 min. 5g of passivated MCM-41 powder was weighed into the solution and stirred at room temperature for 4 h. And transferring the uniformly stirred mixture system into a water bath at 80 ℃, continuously stirring to remove ammonia gas in the mixture, and removing the mixture from the water bath to cool after the pH value of the system is reduced to be close to neutral. And after the system is cooled to room temperature, filtering to obtain a filter cake. Washing the filter cake with deionized water for 5 times, and heating the filter cake at 120 deg.COven drying for 12h, then calcining at 400 deg.C for 8h, tabletting and sieving to obtain the catalyst, noted as B. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
Example 3
20％Cu-4％CaO-2％CeO2Preparation and application of white carbon black catalyst
And (3) roasting 10g of white carbon black for 1h at 750 ℃ in an air atmosphere to obtain passivated white carbon black. 5.14g of Cu (NO)3)2·3H2O、0.84g Ca(NO3)2·4H2O and 0.34g Ce (NO)3)2·6H2Dissolving O in 50ml deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas after the pH value of the system is not increased any more, and stirring the obtained solution system for 20 min. 5g of passivated white carbon black is weighed and added into the solution, and stirred for 4h at room temperature. And transferring the uniformly stirred mixture system into a water bath at 80 ℃, continuously stirring to remove ammonia gas in the mixture, and removing the mixture from the water bath to cool after the pH value of the system is reduced to be close to neutral. And after the system is cooled to room temperature, filtering to obtain a filter cake. And washing the filter cake for 5 times by using deionized water, drying the filter cake for 12h at 120 ℃, roasting for 3h at 600 ℃, tabletting and screening to obtain the catalyst C. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
Example 4
Preparation and application of 20% Cu-4% CaO/white carbon black catalyst
And (3) roasting 10g of white carbon black for 1h at 750 ℃ in an air atmosphere to obtain passivated white carbon black. 5.00g of Cu (NO)3)2·3H2O and 0.82g Ca (NO)3)2·4H2Dissolving O in 50ml deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas after the pH value of the system is not increased any more, and stirring the obtained solution system for 20 min. 5g of passivated white carbon black is weighed and added into the solution, and stirred for 4h at room temperature. And transferring the uniformly stirred mixture system into a water bath at 80 ℃, continuously stirring to remove ammonia gas in the mixture, and removing the mixture from the water bath to cool after the pH value of the system is reduced to be close to neutral. Cooling the system to room temperatureAfter that, filtration was carried out to obtain a cake. And washing the filter cake for 5 times by using deionized water, drying the filter cake for 12h at 120 ℃, then roasting for 3h at 500 ℃, tabletting and screening to obtain a catalyst precursor, which is marked as F. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
Example 5
20％Cu-4％CaO-4La2O3Preparation and application of white carbon black catalyst
0.46g of La (NO)3)2·6H2Dissolving O in 10ml deionized water to prepare a solution, impregnating a sample F with the solution, standing overnight at room temperature, drying for 12h at 120 ℃, then roasting for 4h at 450 ℃, tabletting and screening to obtain a catalyst, and marking as G. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
Example 6
20％Cu-4％CaO-1Li2Preparation and application of O/white carbon black catalyst
0.15g of Li (NO)3) Dissolving in 10ml deionized water to prepare a solution, soaking a sample F by using the solution, standing overnight at room temperature, drying for 12H at 160 ℃, then roasting for 4H at 450 ℃, tabletting and screening to obtain a catalyst, and recording as H. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
Example 7
20％Cu-4％CaO-2CeO2Preparation and application of white carbon black catalyst
10g of white carbon black is placed in 200ml of anhydrous toluene, 2g of trimethylchlorosilane is added, reflux treatment is carried out for 12 hours, solid is obtained by filtration, and ethanol water solution is used for washing until filtrate is free of chlorine. The solid obtained was dried at 120 ℃ for 12 h. 5.14g of Cu (NO)3)2·3H2O、0.84g Ca(NO3)2·4H2O and 0.34gCe (NO)3)2·6H2Dissolving O in 50ml deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas after the pH value of the system is not increased any more, and stirring the obtained solution system for 20 min. 5g of passivated white carbon black is weighed and added into the solution, and stirred for 4h at room temperature. Transferring the uniformly stirred mixture system into a water bath at the temperature of 80 ℃,and continuously stirring to remove ammonia gas in the mixture, and removing the mixture out of the water bath to cool after the pH value of the system is reduced to be close to neutral. And after the system is cooled to room temperature, filtering to obtain a filter cake. And washing the filter cake for 5 times by using deionized water, drying the filter cake for 12h at 100 ℃, roasting for 4h at 450 ℃, tabletting and screening to obtain the catalyst I. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
Example 8
Stability test of catalyst, the catalyst prepared according to the catalyst preparation method in example 3 was in a fixed bed reactor, and the reaction conditions were: the temperature is 383-443K, the pressure is 0.1MPa, the liquid space velocity of furfural is 0.4 g/g-catalyst/H, and H2The molar ratio/furfural was 10 and samples were taken every 12 hours for analysis. The reaction result of 1000 hours shows that the conversion rate of the catalyst is maintained above 90 percent, and the selectivity of the furfuryl alcohol is more than 98 percent.
Comparative example 1
Silica pellet loaded 20% Cu/SiO2Catalyst preparation and use
4.75g of Cu (NO)3)2·3H2O was dissolved in 10ml of deionized water to make a solution, 5g of commercial silica beads were added to the solution, allowed to stand overnight at room temperature, oven dried at 120 ℃ for 12h, and then calcined at 450 ℃ for 4h to obtain the catalyst, reported as J. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
Comparative example 2
Preparation of 20% Cu-4% CaO/SiO with silica sol as carrier2Catalyst preparation and use
4.75g of Cu (NO)3)2·3H2O and 0.80g Ca (NO)3)2·4H2Dissolving O in 50ml deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas after the pH value of the system is not increased any more, and stirring the obtained solution system for 20 min. 16.5g of silica sol having a silica content of 30% was weighed into the solution and stirred at room temperature for 4 hours. Transferring the uniformly stirred mixture system into a water bath at 80 ℃, continuously stirring to remove ammonia gas in the mixture, and after the pH value of the system is reduced to be close to neutral, mixing the mixtureAnd (5) moving out of the water bath to cool. And after the system is cooled to room temperature, filtering to obtain a filter cake. And washing the filter cake for 5 times by using deionized water, drying the filter cake for 12h at 120 ℃, roasting for 4h at 450 ℃, tabletting and screening to obtain the catalyst I. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
Comparative example 3
Preparation and application of 20% Cu-4% CaO/white carbon black catalyst with carrier not subjected to passivation treatment
4.75g of Cu (NO)3)2·3H2O and 0.80g Ca (NO)3)2·4H2Dissolving O in 50ml deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas after the pH value of the system is not increased any more, and stirring the obtained solution system for 20 min. 5g of white carbon black without passivation treatment is weighed and added into the solution, and stirred for 4h at room temperature. And transferring the uniformly stirred mixture system into a water bath at 80 ℃, continuously stirring to remove ammonia gas in the mixture, and removing the mixture from the water bath to cool after the pH value of the system is reduced to be close to neutral. And after the system is cooled to room temperature, filtering to obtain a filter cake. And washing the filter cake for 5 times by using deionized water, drying the filter cake for 12h at 120 ℃, roasting for 4h at 450 ℃, tabletting and screening to obtain the catalyst, which is marked as K. See example 1 for catalyst evaluation protocol. The reaction results are shown in Table 1.
The results show that the catalyst can efficiently catalyze selective hydrogenation of furfural to prepare furfuryl alcohol at a high furfural airspeed. The conversion per pass of furfural is more than 90%, the selectivity of furfuryl alcohol is higher than 98%, and the byproduct is only 2-methylfuran. When mild furfural feeding is adopted, the catalyst keeps good stability in the reaction process of 1000 hours, the furfural conversion rate is maintained to be more than 90%, and the selectivity of furfuryl alcohol is higher than 98.5%.
The comparative analysis result can be integrated to determine that the passivated white carbon black solid silicon oxide is selected as a silicon source, the ammonia-induced silence precipitation method is used for preparing the copper-silicon-based catalyst, and the catalyst can be applied to furfural hydrogenation for producing furfuryl alcohol and can realize one or more of the following steps: (1) the method comprises the following steps of (1) improving the activity of the catalyst, (2) improving the furfural treatment capacity of the catalyst, (3) reducing the furfural loss, (4) simplifying the regeneration condition of the catalyst, (5) realizing the furfuryl alcohol production at a lower reaction temperature, and (6) having simple catalyst composition and low raw material storage requirement and being suitable for large-scale production.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
TABLE 1
Claims (8)
1. A method for producing furfuryl alcohol, characterized in that furfural is reacted with hydrogen to produce furfuryl alcohol in a fixed bed reactor packed with a catalyst for producing furfuryl alcohol;
the catalyst is prepared by adopting an ammonia-induced deposition precipitation method, and consists of a main active component copper, an auxiliary agent and a passivated inorganic carrier containing silicon oxide, wherein the auxiliary agent is one or more of Li, Na, K, Mg, Ca, Sr, Ba, La, Ce, Pr, Nd, Sm and Eu,
the ammonia-induced precipitation method comprises the following steps:
a) passivating the silicon oxide inorganic carrier;
b) dissolving metal salt of required metal components in deionized water, and introducing ammonia gas until the metal salt is saturated;
c) adding the carrier obtained by passivation treatment in a) into the metal salt solution, and uniformly stirring and mixing;
d) heating the mixture system in c) to remove ammonia in the system;
e) filtering and washing the mixture after the pH of the mixture is close to neutral to obtain a filter cake;
f) carrying out thermal activation treatment on the filter cake to obtain a catalyst;
the passivated carrier is as follows: white carbon black, MCM-41, SiO2Microspheres, SiO2One or more of nanoparticles and SBA-15;
the passivation treatment method is high-temperature heat treatment or silanization treatment or etherification treatment, wherein the high-temperature heat treatment is to bake the carrier at the temperature of not lower than 600 ℃ for not less than 10 min; the silanization treatment is to contact the carrier and a silanization reagent at 80-200 ℃ for 0.5-48 hours; the etherification treatment is to contact the carrier with an etherification agent for 0.5 to 48 hours.
2. The method for producing furfuryl alcohol according to claim 1, wherein the main active component, Cu, comprises 1.0 to 50.0% by weight of the total weight of the catalyst, and the auxiliary agent comprises 0.1 to 30.0% by weight of the total weight of the catalyst.
3. A process for the production of furfuryl alcohol according to claim 1, wherein the silylating agent is: one or more of trimethylchlorosilane, dichlorodimethylsilane, trichloromethylsilane, hexamethyldisilazane, aminopropyltriethoxysilane and trimethylbromosilane.
4. A process for producing furfuryl alcohol according to claim 1, wherein the etherification agent is: one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, butanol, pentanol, propylene glycol, glycerol, butanediol, hexanol and phenol.
5. A process for producing furfuryl alcohol according to claim 1, wherein the heat treatment temperature in step d) is from 50 to 100 ℃.
6. A process for producing furfuryl alcohol according to claim 1, wherein the heat activation treatment in step f) is: drying at 60-150 ℃ for 2-48 h, and roasting at 350-750 ℃ for 2-48 h.
7. The method for producing furfuryl alcohol according to claim 1, wherein the method is carried out at a temperature of 90 to 300 ℃, a pressure of 0.01 to 2.0MPa, a furfural liquid space velocity of 0.01 to 10 g/g-catalyst/h, and a molar ratio of hydrogen to furfural of 1 to 50.
8. A process for producing furfuryl alcohol according to claim 1, wherein the catalyst is activated prior to use in an atmosphere comprising hydrogen at a temperature of from 150 to 500 ℃ for a time of from 0.5 to 48 hours.
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| CN111632597B (en) * | 2020-04-16 | 2021-06-01 | 天津大学 | Copper-silicon catalyst modified by silanization of silane coupling agent containing tertiary amine, and preparation method and application thereof |
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