CN109999880B - Nitrogen-doped porous carbon loaded bimetallic catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped porous carbon loaded bimetallic catalyst and preparation method and application thereof Download PDFInfo
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- CN109999880B CN109999880B CN201910317149.5A CN201910317149A CN109999880B CN 109999880 B CN109999880 B CN 109999880B CN 201910317149 A CN201910317149 A CN 201910317149A CN 109999880 B CN109999880 B CN 109999880B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 48
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
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- 150000002009 diols Chemical class 0.000 abstract description 2
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a bimetal-nitrogen-doped carbon-based bifunctional catalyst synthesized by a one-pot method by taking nitrogen-doped bio-based porous carbon as a carrier, and a preparation method and application thereof. The catalyst can be used for catalyzing biomass such as bio-based sorbitol, xylitol, cellulose, lignocellulose and the like to prepare low-polyhydric alcohols such as diol through efficient selective hydrogenation. According to the catalyst disclosed by the invention, cheap and renewable biomass is used as a raw material to prepare the porous nitrogen-doped carbon material, nitrogen-containing organic matters are not required to be added as nitrogen sources to dope nitrogen elements, and the catalyst is green, environment-friendly and low in price. The prepared metal-loaded catalyst has excellent catalytic activity, stability and selectivity when being used for catalyzing biomass selective hydrogenation in a water phase system. And the product and the catalyst are separated simply, the yield of the ethylene glycol and the propylene glycol in the product can reach more than 85%, the reaction steps are few, the condition is mild, the operation is simple, and the application prospect is wide.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a double-metal-nitrogen-doped carbon-based bifunctional catalyst synthesized by a one-pot method by taking nitrogen-doped bio-based porous carbon as a carrier, which is used for catalyzing biomass such as bio-based sorbitol, xylitol, cellulose, lignocellulose and the like to efficiently and selectively hydrogenate to prepare low-polyhydric alcohols such as diol and the like, and a preparation method and application of the catalyst.
Background
Ethylene glycol and propylene glycol, as a high value-added chemical, are widely used in the fields of artificially synthesized polyester resins, cosmetics, medical industry, pharmaceutical industry and the like. At present, the downstream products of petroleum cracking and coal are mainly used as raw materials in industry, and ethylene glycol and propylene glycol are produced through the traditional catalytic hydrogenolysis and other harsh conditions. The traditional industrial synthesis route has the problems that the raw materials are highly dependent on petroleum and coal, the reaction route is complex, a large amount of pollutants are generated, and the like. With the increasing shortage of global fossil resources, the renewable agriculture and forestry waste resources are utilized to prepare the ethylene glycol and the propylene glycol, so that the problem of dependence on the fossil resources can be solved, the resource utilization rate of the agriculture and forestry waste can be improved, and the ethylene glycol and the propylene glycol are expected to become an alternative route of the traditional petroleum and coal chemical industry route.
At present, in a low-alcohol catalytic system for preparing ethylene glycol, propylene glycol and the like by taking biomass as a raw material, commonly adopted catalysts comprise metals such as Ni, Cu, Ru, Pt, Au, Pd, Rh and the like, and carriers comprise silicon dioxide, activated carbon, carbon nano tubes, zeolite molecular sieves and the like. The carbon nanotube and graphene composite carrier developed by the professor group in the world realizes the highest sorbitol conversion rate of less than 70 percent (Chinese.J.Catal., 35(2014)692) under the conditions of 220 ℃ and 8MPa by using the catalyst synthesized by processes such as equal-volume impregnation loading ruthenium, post-treatment and the like. Ruthenium and tungsten are loaded on a silicon dioxide carrier developed by Zhang Yi professor team, and the reaction is carried out for 50 hours at the temperature of 200 ℃ and under the pressure of 4MPa, so that the 100 percent conversion rate of glucose is realized, and the selectivity of ethylene glycol and propylene glycol is not more than 70 percent (App.Catal.B, 242 (2019)) 100. The silicon dioxide carrier developed by the professor group of the Liuhai super professor loads copper through a coprecipitation method to catalyze xylitol, and the selectivity of ethylene glycol and propylene glycol is not more than 65 percent under the conditions of 200 ℃ and 6MPa (App.Catal.B,147(2014) 377). In the reported literature, the heterogeneous catalyst is mainly synthesized by multiple steps such as a coprecipitation method, an isovolumetric impregnation method and the like, and the steps are complicated, the efficiency is low, and the synthesis of the catalyst required by industrial amplification in the future is not facilitated.
The invention develops a one-pot catalyst synthesis method, which takes biomass rich in protein as a raw material to prepare a nitrogen-doped porous carbon loaded bimetallic catalyst by a one-step hydrothermal method. The synthetic method is simple, and bimetallic is loaded by selecting nitrogen-doped porous carbon as a carrier. The loaded transition metal selectively breaks C-C bonds of the biomass polyol by adjusting acid-base sites on the surface of the catalyst carrier, the noble metal provides a hydrogenation active site, and the selectivity of a target product is improved. The prepared bifunctional catalyst not only greatly improves the conversion rate of reactants and the selectivity of products, but also reduces the temperature (<200 ℃) and the pressure (<4MPa) of catalytic reaction, and has the advantages of green and environment-friendly process, simple and safe operation. Therefore, the development of a heterogeneous catalyst which is simple to synthesize, high in activity and selectivity on a water system is of great significance to the production of ethylene glycol, propylene glycol and other low-polyhydric alcohol products.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a nitrogen-doped bio-based material, and a bio-based nitrogen-doped porous carbon supported bimetallic catalyst is synthesized by a one-pot hydrothermal method, so that high-activity and high-selectivity catalysis on selective hydrogenolysis of biomass polyol and polysaccharide is realized.
The supported catalyst is composed of 0.5-20 wt% of noble metal particles, 1-30 wt% of transition metal elements and 50-98.5 wt% of bio-based nitrogen-doped porous carbon material carriers.
Wherein the specific surface area of the bio-based nitrogen-doped porous carbon material carrier is 150-1500m2Per g, nitrogen content is 1-10 wt.%.
The noble metal particles are one or more noble metal particles selected from palladium, gold, platinum, ruthenium, rhodium and iridium, and are preferably palladium, platinum or ruthenium; the transition metal element is one or more transition metal elements selected from iron, copper, tungsten, chromium, manganese, cobalt and nickel, and is preferably tungsten, manganese or cobalt.
Another object of the present invention is to provide a preparation method for synthesizing a bio-based nitrogen-doped porous carbon-supported bimetallic catalyst by a one-pot method, wherein the preparation method comprises the following steps:
1) drying the biomass material, and grinding into fine powder;
2) dispersing the fine powder obtained in the step 1), the noble metal and the transition metal precursor solution into water;
3) transferring the mixture obtained in the step 2) into a reaction kettle, heating to 300 ℃ under the hydrothermal reaction condition, preferably 150 ℃ under the hydrothermal reaction condition, preserving the heat for 1-56 hours, cooling, and washing to obtain a brown solid;
4) drying and grinding the brown solid obtained in the step 3), and then roasting in a tubular furnace under the protection of an inert atmosphere, wherein the roasting temperature is 200-1500 ℃, and the heat preservation time is 1-100 hours; and after the temperature of the tubular furnace is reduced to the room temperature, taking out the sample to obtain the nitrogen-doped porous carbon supported bimetallic catalyst prepared by the one-pot method.
Wherein, the biomass material in the step 1) is a plant rich in protein, and comprises at least one of elm, dandelion leaves, jute leaves, burdock leaves, asparagus, bamboo shoots, white cauliflower, spinach and broccoli, preferably at least one of spinach and bamboo shoots, which are simultaneously used as a carbon source and a nitrogen source.
Wherein, in the step 2), the precursor of the noble metal precursor solution can be one or more metal salts of ruthenium, palladium, platinum, rhodium and iridium, such as hydrochloride, sulfate, nitrate, etc.; the transition metal precursor may be one or more metal salts of iron, copper, manganese, nickel and tungsten, such as hydrochloride, sulfate, nitrate, and the like. The proportion content of the precious metal and transition metal precursor to the biomass powder in the step 2) is 1-30 wt%.
In the step 4), the roasting temperature is 200-1500 ℃, preferably 500-100 ℃, the inert gas is one or more of nitrogen, argon and helium, and the heat preservation time is preferably 5-30 hours.
The one-pot preparation method does not adopt an activating agent or other nitrogen source materials, only adopts a biomass material and only needs one step to complete metal loading.
According to another object of the invention, the method for preparing the ethylene glycol and the propylene glycol by using the water-phase biomass raw material or/and the carbohydrate as the raw material and hydrogenating in the presence of the bio-based nitrogen-doped porous carbon-supported bimetallic catalyst is provided.
Preferably, the biomass raw material or/and the carbohydrate is one or more of sorbitol, glucose, xylitol, xylose, cellulose, hemicellulose, wood and bamboo.
The method comprises the following steps: adding a certain amount of biomass, the supported catalyst and deionized water into a kettle-type high-pressure reactor, sealing, filling 0.1-10MPa of hydrogen, reacting at the temperature of 100-350 ℃, cooling to room temperature after reacting for 0.5-48 hours, filtering reaction liquid, and separating the catalyst. The obtained liquid product is rectified to separate mixed dihydric alcohol such as ethylene glycol, propylene glycol and the like.
Preferably, the amount of the supported catalyst is 0.1 to 100wt%, preferably 1 to 20wt% of the amount of the biomass; the water dosage is 10-200 times of the biomass dosage, preferably 10-100 times; the reaction pressure is 0.1-20MPa, preferably 1-8 MPa; the reaction temperature is 50-250 ℃, and preferably 100-200 ℃; the reaction time is from 0.5 to 48 hours, preferably from 1 to 10 hours.
Preferably, the method for preparing the nitrogen-doped porous carbon-supported bimetallic catalyst by using the water-phase biomass selective hydrogenation method according to the invention has the reaction temperature of preferably 120-250 ℃, the hydrogen pressure of preferably 1-8MPa and the reaction time of preferably 1-10 hours, the yield of the ethylene glycol and the propylene glycol can reach 85 percent, and the specific surface area of the adopted bio-based nitrogen-doped porous carbon-supported bimetallic catalyst is about 350-850m2The nitrogen content is about 4-10%, and the roasting temperature in the preparation method of the bio-based nitrogen-doped porous carbon supported bimetallic catalyst is 500-900 ℃.
Advantageous effects
Compared with the prior art, the invention has the following advantages:
1. cheap and renewable biomass is used as a raw material to prepare the porous nitrogen-doped carbon material, and nitrogen elements are not required to be doped by adding nitrogen-containing organic matters as nitrogen sources. In addition, the porous nitrogen-doped supported bimetallic catalyst is synthesized by one step through a one-pot method, and the multi-step methods of isometric impregnation and the like for supporting metal elements are avoided. In addition, the used raw materials are renewable resources, are widely distributed, are green and environment-friendly, are simple and easy to obtain, and have low price. The synthesis method is an environment-friendly one-step hydrothermal synthesis method, and the nitrogen-doped porous carbon supported bimetallic catalyst with large specific surface area, rich porosity and good nano metal dispersibility is prepared.
2. The metal-loaded catalyst provided by the invention has excellent catalytic activity, stability and selectivity when used for catalyzing biomass selective hydrogenation in a water phase system. And the product and the catalyst are separated simply, the yield of the ethylene glycol and the propylene glycol in the product can reach more than 85%, the reaction steps are few, the condition is mild, the operation is simple, and the application prospect is wide.
Drawings
FIG. 1 is a TEM test chart of a nitrogen-doped porous carbon supported bimetallic catalyst Ru-W/NC-800 prepared in preparation example 1 of the invention.
FIG. 2 is a BET result of the nitrogen-doped porous carbon-supported bimetallic catalysts Ru-W/NC-700 (preparation example 4), Ru-W/NC-800 (preparation example 1) and Ru-W/NC-900 (preparation example 5) prepared in preparation example 1 of the present invention.
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 invention takes nitrogen-doped biomass as a raw material, and hydrothermally synthesizes the nitrogen-doped porous carbon loaded double catalyst by a one-pot method, wherein the catalyst is composed of 0.5-20 wt% of noble metal particles, 1-30 wt% of transition metal elements and 50-98.5 wt% of bio-based nitrogen-doped porous carbon material carriers, and can be used for preparing low-polyol products such as ethylene glycol, propylene glycol and the like by selective hydrogenolysis of biomass such as sorbitol, xylitol, xylose, cellulose, hemicellulose, bamboo and the like. All raw materials of the catalyst are renewable resources, are widely distributed, are green and environment-friendly, are simple and easy to obtain, are rich in resources and low in price, and the catalyst can be recycled and has good stability. According to the supported bimetallic catalyst synthesized by the one-pot method, the sorbitol raw material is taken as an example, the yield of ethylene glycol and propylene glycol prepared by selective hydrogenolysis of biomass-based sorbitol under mild conditions can reach more than 85%, and the conversion rate of sorbitol is more than 99%.
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.
Characterization of the instrument used:
1) transmission electron microscope: model number H-7650, Hitachi, Inc
2) An element analyzer: model number Vario-EL-cube, Elementary, Germany
3) Physical adsorption instrument: model number is Autosorb iQ, and manufacturer is Kangta corporation of America
Synthesis of catalyst
Preparation example 1: preparation of nitrogen-doped porous carbon material supported Ru-W catalyst (Ru-W/NC-800) synthesized by one-pot method
1kg of cleaned bamboo shoots was cut into pieces and dried to obtain a solid ground into powder. 2g of the powder was taken and mixed with 18mL of deionized water, 0.28mL of RuCl3Mixing the solutions (5 wt%), adding 0.0972g Ammonium Metatungstate (AMT), mixing the above mixture, transferring to hydrothermal kettle, reacting at 180 deg.C for 6 hr, filtering, washingWashed and dried to give a brown solid. And then placing the obtained solid in a tubular furnace, roasting to 800 ℃ in a nitrogen atmosphere, and preserving heat for 1 hour to obtain the nitrogen-doped porous carbon supported catalyst, which is expressed by Ru-W/NC-800.
Fig. 1 is a TEM image of a nitrogen-doped porous carbon-supported Ru-W catalyst prepared according to this example, in which Ru nanoparticles are uniformly dispersed on the surface of a carbon material with a particle size of about 3nm, as shown in fig. 1. The specific surface area is 435m2In terms of BET analysis, it was found that the catalyst had a hierarchical pore structure and that the influence of different calcination temperatures on the specific surface areas of the catalysts Ru-W/NC-700 (preparation example 4), Ru-W/NC-800 (preparation example 1) and Ru-W/NC-900 (preparation example 5) (see FIG. 2).
Preparation example 2: preparation of nitrogen-doped porous carbon material supported Ru-W catalyst (HRu-W/NC) synthesized by multi-step method
Taking 2g of bamboo powder, uniformly mixing with 18mL of deionized water, transferring into a hydrothermal kettle, reacting at 180 ℃ for 6 hours, filtering, washing and drying to obtain brown solid hydrothermal carbon.
1g of hydrothermal carbon was taken and mixed with 4mL of deionized water, 0.28mL of RuCl3The solution (5 wt%) was mixed with 0.0972g AMT and allowed to stand at 25 ℃ for 3 hours. Drying at 50 deg.C for 12h, grinding the above mixture, placing in a tube furnace, calcining in nitrogen atmosphere, and keeping the temperature at 800 deg.C for 1 hr. And (4) taking out the sample after the temperature of the tubular furnace is reduced to room temperature, thus obtaining the nitrogen-doped porous carbon supported catalyst synthesized by the multi-step method, which is represented by HRu-W/NC.
Preparation example 3: preparation for synthesizing commercial active carbon supported Ru-W catalyst (Ru-W @ AC) by isovolumetric impregnation method
1g of commercial activated carbon (from Norit) was taken in with 4mL of deionized water, 0.28mL of RuCl3The solution (5 wt%) was mixed with 0.0972g AMT, allowed to stand at 25 ℃ for 3 hours, dried at 50 ℃ for 12 hours, ground and then calcined in a tube furnace under nitrogen atmosphere, and held at 800 ℃ for 1 hour. And (3) taking out the sample after the temperature of the tubular furnace is reduced to room temperature to obtain the catalyst loaded with the same volume of the impregnated activated carbon, wherein the catalyst is expressed by Ru-W @ AC.
Preparation example 4: preparation of nitrogen-doped porous carbon material supported Ru-W catalyst (Ru-W/NC-700) synthesized by one-pot method
A doped porous carbon-supported catalyst having a specific surface area of 557m was prepared in the same manner as in preparation example 1, except that the carbonization temperature was changed to 700 deg.C2(see FIG. 2), expressed as Ru-W/NC-700.
Preparation example 5: preparation for synthesizing nitrogen-doped porous carbon material supported Ru-W catalyst (Ru-W/NC-900) by one-pot method
Nitrogen-doped porous carbon-supported catalyst having a specific surface area of 413m was prepared in the same manner as in preparation example 1, except that the carbonization temperature was changed to 900 deg.C2(see FIG. 2), expressed as Ru-W/NC-900.
Preparation example 6: preparation for synthesizing nitrogen-doped porous carbon material-supported Ru catalyst (Ru/NC-800) by one-pot method
A nitrogen-doped porous carbon-supported catalyst, which is expressed as Ru/NC-800, was prepared in the same manner as in preparation example 1, except that AMT was not added.
Preparation example 7: preparation of nitrogen-doped porous carbon material supported W catalyst (W/NC-800) synthesized by one-pot method
A nitrogen-doped porous carbon-supported catalyst, which is represented by W/NC-800, was prepared in the same manner as in preparation example 1, except that ruthenium trichloride was not added.
Example 1: a method for preparing ethylene glycol and propylene glycol by selective hydrogenolysis of sorbitol catalyzed by a nitrogen-doped carbon material loaded nanometer ruthenium and tungsten bimetallic catalyst. The method comprises the following steps:
putting 2g of sorbitol and 0.2g of calcium hydroxide into a kettle-type high-pressure reactor, adding 0.1g of the Ru-W catalyst in the preparation example 1 and 20mL of deionized water, sealing, introducing 4MPa of hydrogen, reacting at 200 ℃, reacting for 6 hours, cooling to room temperature, filtering the reaction solution, and carrying out gas chromatography and liquid chromatography analysis on the reaction solution. The results show 100% conversion of sorbitol in the aqueous phase and 85% yield of ethylene glycol and propylene glycol.
Example 2:
putting 2g of sorbitol and 0.2g of calcium hydroxide into a kettle-type high-pressure reactor, adding 0.1g of the Ru-W catalyst prepared in preparation example 4 and 20mL of deionized water, sealing, introducing 4MPa of hydrogen, reacting at 200 ℃, reacting for 6 hours, cooling to room temperature, filtering the reaction solution, and carrying out gas chromatography and liquid chromatography analysis on the reaction solution. The results show that the conversion of sorbitol in the aqueous phase is above 99% and the yields of ethylene glycol and propylene glycol are 63%.
Example 3:
2g of sorbitol and 0.2g of calcium hydroxide were placed in a kettle-type high-pressure reactor, 0.1g of the Ru-W catalyst prepared in preparation example 5 and 20mL of deionized water were added, the reaction was carried out at 200 ℃ by introducing 4MPa of hydrogen gas after sealing, the reaction was carried out for 6 hours, the reaction was cooled to room temperature, the reaction solution was filtered, and gas chromatography and liquid chromatography were carried out on the reaction solution. The results show that the conversion of sorbitol in the aqueous phase is above 99% and the yields of ethylene glycol and propylene glycol are 72%.
Example 4:
putting 2g of sorbitol and 0.2g of calcium hydroxide into a kettle-type high-pressure reactor, adding 0.1g of the Ru-W catalyst prepared in preparation example 2 and 20mL of deionized water, sealing, introducing 4MPa of hydrogen, reacting at 200 ℃, reacting for 6 hours, cooling to room temperature, filtering the reaction solution, and carrying out gas chromatography and liquid chromatography analysis on the reaction solution. The results show that the conversion of sorbitol in the aqueous phase is 90% and the yields of ethylene glycol and propylene glycol are greater than 51%.
Example 5:
2g of sorbitol and 0.2g of calcium hydroxide were placed in a kettle-type high-pressure reactor, 0.1g of the commercial carbon material-supported Ru-W catalyst prepared in preparation example 3 and 20mL of deionized water were added, the reaction was carried out at 200 ℃ with 4MPa of hydrogen gas being introduced after sealing, the reaction was carried out for 6 hours, the reaction was cooled to room temperature, the reaction solution was filtered, and gas chromatography and liquid chromatography were carried out on the reaction solution. The results show that the conversion of sorbitol in the aqueous phase is 80% and the yields of ethylene glycol and propylene glycol are 35%.
Example 6:
putting 2g of sorbitol and 0.2g of calcium hydroxide into a kettle-type high-pressure reactor, adding 0.1g of the Ru catalyst prepared in preparation example 6 and 20mL of deionized water, sealing, introducing 4MPa of hydrogen, reacting at 200 ℃, reacting for 6 hours, cooling to room temperature, filtering the reaction solution, and carrying out gas chromatography and liquid chromatography analysis on the reaction solution. The results show that the conversion of sorbitol in the aqueous phase is 52% and the yields of ethylene glycol and propylene glycol are 35%.
Example 7
Putting 2g of sorbitol and 0.2g of calcium hydroxide into a kettle-type high-pressure reactor, adding 0.1g of the W catalyst prepared in preparation 7 and 20mL of deionized water, sealing, introducing 6MPa of hydrogen, reacting at 200 ℃, reacting for 6 hours, cooling to room temperature, filtering the reaction solution, and carrying out gas chromatography and liquid chromatography analysis on the reaction solution. The results show 90% conversion of sorbitol in the aqueous phase and 15% yields of ethylene glycol and propylene glycol.
Example 8
Putting 4g of xylitol and 0.3g of calcium hydroxide into a kettle-type high-pressure reactor, adding 0.1g of the Ru-W catalyst prepared in the preparation example 1 and 40mL of deionized water, sealing, introducing 4MPa of hydrogen, reacting at 200 ℃, reacting for 3 hours, cooling to room temperature, filtering the reaction solution, and carrying out gas chromatography and liquid chromatography analysis on the reaction solution. The results show that the conversion of xylitol in the aqueous phase is 95% and the yields of ethylene glycol and propylene glycol are 82%.
Example 9
2g of glucose and 0.2g of calcium hydroxide were placed in a kettle-type high-pressure reactor, 0.1g of the Ru-W catalyst prepared in preparation example 1 and 20mL of deionized water were added, the reaction was carried out at 200 ℃ with 4MPa of hydrogen gas being introduced after sealing, the reaction was carried out for 30 hours, the reaction solution was cooled to room temperature, the reaction solution was filtered, and gas chromatography and liquid chromatography were carried out on the reaction solution. The results show 100% conversion of glucose in the aqueous phase and 80% yield of ethylene glycol and propylene glycol.
Example 10
0.5g of cellulose and 0.2g of calcium hydroxide were placed in a kettle-type high-pressure reactor, 0.2g of the Ru-W catalyst prepared in preparation example 1 and 50mL of deionized water were added, the reaction was carried out at 240 ℃ with introduction of 5MPa hydrogen gas after sealing for 2 hours, the reaction was cooled to room temperature, the reaction solution was filtered, and gas chromatography and liquid chromatography analyses were carried out on the reaction solution. The results show a cellulose conversion of 98% and yields of ethylene glycol and propylene glycol of 75%.
Example 11
Ball-milling 5g of bamboo powder in a planetary ball mill at 800 rpm for 20 hours, placing 1g of the ball-milled bamboo powder and 0.6g of calcium hydroxide in a kettle-type high-pressure reactor, adding 0.4g of the Ru-W catalyst prepared in preparation example 1 and 100mL of deionized water, sealing, introducing 6MPa hydrogen, reacting at 240 ℃, reacting for 4 hours, cooling to room temperature, filtering the reaction solution, and carrying out gas chromatography and liquid chromatography analysis on the reaction solution. The results show that the conversion rate of cellulose in the bamboo powder in the water phase is 80%, the conversion rate of hemicellulose is 95%, and the yield of ethylene glycol and propylene glycol is 65%.
Example 12
After the completion of the reaction, the heterogeneous catalyst of example 1 was centrifuged and used in a circulation experiment, and other reaction conditions were the same as those of example 1. After 50 times of circulation of the reaction, the conversion rate of the sorbitol is 95 percent and the yield of the reaction product is not obviously changed by measuring experimental results by using gas chromatography and liquid chromatography. The catalyst is stable and easy to recycle.
The experimental results of the examples 1 and 4 show that compared with a multi-step synthesis method, the one-pot synthesis method of the nitrogen-doped porous carbon supported bimetallic catalyst is simple, the particle size of the metal ruthenium on the carrier is uniformly dispersed, more active sites are provided, and the catalytic activity is high. The experimental results of examples 1 and 5 show that the nitrogen element in the bifunctional catalyst carrier has a great effect on improving the catalytic activity of the catalyst in a catalyst-catalyzed aqueous-phase polyol system, and the nitrogen element on the carrier can adjust not only the acid-base sites on the surface of the carrier, but also the electron transfer between the active sites of the catalyst, so as to improve the catalytic activity of the catalyst.
Compared with the experimental data of the examples 1, 6 and 7, the transition metal element loaded on the nitrogen-doped porous carbon can improve the conversion rate of the sorbitol, provide an acid site, adsorb a reactant and selectively break a C-C bond in the sorbitol, and the noble metal is used as a hydrogenation active site to improve the selectivity of a target product. The experiments show that the hydrogenation reaction of biomasses such as sorbitol and the like can be obviously improved through the synergistic effect of the noble metal and the transition metal, and the distribution of hydrogenation products of sorbitol can be modulated, so that ethylene glycol and propylene glycol become main products. The experimental results of examples 1 to 10 show that the synergistic catalytic action of the bimetal on the nitrogen-doped porous carbon can efficiently catalyze the selective hydrogenolysis reaction of biomass such as sorbitol, xylitol and the like, so that the conversion rate and the product selectivity of reactants are remarkably improved, and the reaction temperature and pressure are reduced. Wherein, the selective hydrogenation conversion rate of sorbitol is more than 99 percent, and the yield of ethylene glycol and propylene glycol is more than 85 percent.
Claims (6)
1. A method for preparing ethylene glycol and propylene glycol by using biomass or/and carbohydrate as raw materials and hydrogenating in the presence of a bio-based nitrogen-doped porous carbon supported bimetallic catalyst, wherein the method comprises the following steps: adding a certain amount of biomass or/and carbohydrate raw materials into a kettle-type high-pressure reactor, sealing the supported bimetallic catalyst and deionized water, filling hydrogen with the pressure of 0.1-10MPa, and adding hydrogen into the reactor at the pressure of 100-oC, reacting for 0.5-48 hours, cooling to room temperature, filtering reaction liquid, separating the catalyst, and rectifying the obtained liquid product to separate out mixed dihydric alcohol of ethylene glycol and propylene glycol; the biomass or/and carbohydrate raw material is one or more of sorbitol, glucose, xylitol, xylose, cellulose, hemicellulose, wood and bamboo;
the dosage of the supported bimetallic catalyst is 0.1-100wt% of the dosage of the biomass or/and carbohydrate raw material; the water consumption is 10-200 times of the biomass or/and carbohydrate raw material;
in the method, the yield of the ethylene glycol and the propylene glycol is 85 percent, and the specific surface area of the adopted bio-based nitrogen-doped porous carbon supported bimetallic catalyst is 350-850m2Per g, the nitrogen content is 4-10%;
the bio-based nitrogen-doped porous carbon supported bimetallic catalyst is composed of 0.5-20 wt% of noble metal particles, 1-30 wt% of transition metal elements and 50-98.5 wt% of bio-based nitrogen-doped porous carbon material carriers;
the specific surface area of the bio-based nitrogen-doped porous carbon material carrier is150-1500 m2Per g, nitrogen content is 1-10 wt%;
the noble metal particles are palladium, platinum or ruthenium; the transition metal element is tungsten;
the supported bimetallic catalyst is prepared by a one-pot method, and the one-pot method comprises the following steps:
1) drying the biomass material, and grinding into fine powder;
2) dispersing the fine powder obtained in the step 1), the noble metal and the transition metal precursor solution into water;
3) transferring the mixture obtained in the step 2) into a reaction kettle, and heating the mixture to 150 ℃ under the hydrothermal reaction condition of 250- oC, preserving the heat for 1 to 56 hours, cooling and washing to obtain a brown solid;
4) drying and grinding the brown solid obtained in the step 3), and then roasting in a tubular furnace under the protection of inert atmosphere at the roasting temperature of 500-oC, preserving the heat for 1-100 hours; and after the temperature of the tubular furnace is reduced to the room temperature, taking out the sample to obtain the nitrogen-doped porous carbon supported bimetallic catalyst prepared by the one-pot method.
2. The process for the hydrogenation of ethylene glycol and propylene glycol according to claim 1, wherein the supported bimetallic catalyst is used in an amount of 1-20 wt.% of the biomass or/and carbohydrate feedstock; the water consumption is 10-100 times of the biomass or/and carbohydrate raw material.
3. The method for preparing ethylene glycol and propylene glycol through hydrogenation according to claim 1, wherein the biomass material is at least one of spinach and bamboo shoots which are used as a carbon source and a nitrogen source simultaneously in the step 1) of the one-pot preparation method of the supported bimetallic catalyst.
4. The method for preparing ethylene glycol and propylene glycol through hydrogenation according to claim 1, wherein in step 2) of the one-pot preparation method of the supported bimetallic catalyst, the noble metal precursor solution is hydrochloride, sulfate or nitrate of one or more of ruthenium, palladium and platinum; the precursor of the transition metal is hydrochloride, sulfate and nitrate of tungsten; the proportion content of the noble metal and transition metal precursor to the fine powder in the step 2) is 1-30 wt%.
5. The method for preparing ethylene glycol and propylene glycol through hydrogenation according to claim 1, wherein the inert atmosphere in step 4) of the one-pot preparation method of the supported bimetallic catalyst is one or more of nitrogen, argon and helium, and the holding time is 5-30 hours.
6. The process for the hydrogenation of ethylene glycol and propylene glycol according to claim 3, wherein said process does not employ an activator or other nitrogen source material, but only employs a biomass material and supports the metal in only one step.
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| CN114606512B (en) * | 2022-03-30 | 2023-08-22 | 青岛科技大学 | Ru doped W 4.6 N 4 Particle @ nitrogen doped graphene tube hydrogen evolution electrocatalyst |
| CN115155639B (en) * | 2022-07-18 | 2023-10-20 | 北京林业大学 | Ultralow-load ruthenium catalyst and preparation method and application thereof |
| CN115487811A (en) * | 2022-08-31 | 2022-12-20 | 东南大学 | Nitrogen-doped carbon film coated iron-based catalyst, preparation method and aromatic amine synthesis method |
| CN115608399B (en) * | 2022-09-30 | 2023-11-14 | 杭州电子科技大学 | Porous carbon-supported RuCuO x Preparation method of composite catalyst |
| CN117861676A (en) * | 2022-10-10 | 2024-04-12 | 中国石油化工股份有限公司 | Double-catalytic center catalyst, preparation method and application thereof, and preparation method of dihydric alcohol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622327A (en) * | 2016-12-20 | 2017-05-10 | 中国科学院青岛生物能源与过程研究所 | N-doped porous carbon supported metal catalyst, and preparation method and application thereof |
| CN107754840A (en) * | 2017-10-20 | 2018-03-06 | 天津工业大学 | One-step method prepares the N doping platinum nickel carbon electrochemical catalyst for Catalytic oxidation of ethanol |
| WO2018166566A1 (en) * | 2017-03-15 | 2018-09-20 | Thyssenkrupp Ag | Method for chemical conversion of sugars or sugar alcohols to glycols |
| CN108689786A (en) * | 2018-05-08 | 2018-10-23 | 中国科学院青岛生物能源与过程研究所 | A method of borrowing hydrogen reduction coupling synthesizing imine and aminated compounds |
| CN108889300A (en) * | 2018-06-04 | 2018-11-27 | 中国科学院生态环境研究中心 | A kind of preparation method and applications of novel hydro-thermal charcoal carried nanometer bi-metal catalyst |
-
2019
- 2019-04-19 CN CN201910317149.5A patent/CN109999880B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622327A (en) * | 2016-12-20 | 2017-05-10 | 中国科学院青岛生物能源与过程研究所 | N-doped porous carbon supported metal catalyst, and preparation method and application thereof |
| WO2018166566A1 (en) * | 2017-03-15 | 2018-09-20 | Thyssenkrupp Ag | Method for chemical conversion of sugars or sugar alcohols to glycols |
| CN107754840A (en) * | 2017-10-20 | 2018-03-06 | 天津工业大学 | One-step method prepares the N doping platinum nickel carbon electrochemical catalyst for Catalytic oxidation of ethanol |
| CN108689786A (en) * | 2018-05-08 | 2018-10-23 | 中国科学院青岛生物能源与过程研究所 | A method of borrowing hydrogen reduction coupling synthesizing imine and aminated compounds |
| CN108889300A (en) * | 2018-06-04 | 2018-11-27 | 中国科学院生态环境研究中心 | A kind of preparation method and applications of novel hydro-thermal charcoal carried nanometer bi-metal catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Ir-N@C催化剂在选择性制备直链醇中的应用;王振东;《现代化工》;20180531;第38卷;全文 * |
| The synergistic effects of Ru and WOx for aqueous-phase hydrogenation of glucose to lower diols;Yi Liu等;《Applied Catalysis B: Environmental》;20180927;第242卷;第100-108页 * |
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