CN110947382A - Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof - Google Patents

Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof Download PDF

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CN110947382A
CN110947382A CN201910794549.5A CN201910794549A CN110947382A CN 110947382 A CN110947382 A CN 110947382A CN 201910794549 A CN201910794549 A CN 201910794549A CN 110947382 A CN110947382 A CN 110947382A
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catalyst
ethylene carbonate
copper
ethylene glycol
methanol
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CN110947382B (en
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王悦
杨有为
吕静
马新宾
王美岩
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Tianjin University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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    • 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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Abstract

The invention relates to a catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate and a preparation method thereof, wherein the catalyst comprises copper, a carrier and an auxiliary agent, wherein the copper accounts for 5-59.9 wt% of the weight of the catalyst, the carrier accounts for 40-94.9 wt% of the weight of the catalyst, and the auxiliary agent accounts for 0.1-5 wt% of the mass of the catalyst. The invention adopts the catalyst with the characteristic of a special nano-tubular structure, and can highly disperse the active component copper or the oxide thereof, thereby improving the conversion rate of the ethylene carbonate and the selectivity of methanol, and simultaneously showing excellent stability in the hydrogenation process.

Description

Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and relates to a gas-phase ester hydrogenation catalyst, in particular to a catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate and a preparation method thereof.
Background
Methanol is used as an important basic chemical raw material or solvent, has important application in the industries of medicine, dye, plastic, synthetic fiber and the like, and is also used as an energy source with excellent performance and a gasoline substitute fuel due to the advantages of safety, sufficient combustion, high utilization rate and the like. CO 22The hydrogenation for producing the methanol is not only an option for producing and utilizing the methanol as an industrial product, but also brings a new solution to the global energy and environment problem. But due to CO2The method has the advantages of thermodynamic stability and kinetic inertia, harsh reaction conditions for preparing methanol by direct hydrogenation, low equilibrium conversion rate and poor selectivity of target products. By introducing CO2The process for synthesizing Ethylene Carbonate (EC) by reacting with ethylene oxide and further hydrogenating to prepare methanol has the advantages of mild reaction conditions, high conversion rate and 100% atomic utilization rate, and has good technical and economic advantages and market application potential as the ethylene glycol is co-produced while the methanol is produced.
Organic noble metal catalysts such as a Pincer type ruthenium complex and the like show good activity and selectivity in a hydrogenation reaction of ethylene carbonate, but the preparation process is complex, the price is high and the recovery is difficult. Copper-based catalysts are widely used in ester hydrogenation systems because of their good C-O/C ═ O bond selective hydrogenation capabilities. However, in the hydrogenation of ethylene carbonate, there is still a hydrogen-to-ester ratio (i.e., the molar ratio of hydrogen to ethylene carbonate, H) required for the reaction feed2the/EC) is higher, the selectivity of the product methanol is lower, the stability of the catalyst is poorer, and the like. At present, in a fixed bed reactor, a large excess of hydrogen (H) is required in the feed to the ethylene carbonate hydrogenation reaction2with/EC generally above 200) to maintain higher conversion of ethylene carbonate. However, in industrial application, such a high hydrogen-ester ratio will result in an increased hydrogen circulation amount, increased requirements for equipment parameters such as compressor, and the likeThe equipment and power costs required for the process are greatly increased. Therefore, the high-activity copper-based catalyst is designed, so that the ethylene carbonate hydrogenation reaction has higher ethylene carbonate conversion rate and methanol selectivity under lower hydrogen-ester ratio, has good stability and realizes CO2The key point of the efficient utilization of the methanol is to produce the methanol.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a high-activity high-selectivity ethylene carbonate hydrogenation catalyst and a preparation method thereof aiming at the problems of high hydrogen ester ratio and low methanol selectivity in the technology of preparing methanol and ethylene glycol by hydrogenating ethylene carbonate.
The technical scheme adopted by the invention is as follows:
the catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate mainly comprises copper, oxides thereof and silicon dioxide, wherein the copper accounts for 5-59.9 wt% of the weight of the catalyst; silica in 40-94.9 wt.% of the catalyst weight; the auxiliary agent accounts for 0.1-5 wt% of the weight of the catalyst.
The catalyst structure is a nano-tube structure with a specific surface area of 450-500m2(ii)/g; the diameter of the nanotube is 3-5nm, and the length of the nanotube is 40-300 nm.
More preferred embodiments are: the copper content of the catalyst is 30-48 wt.%, the silicon oxide content of the catalyst is 50-68 wt.%, the assistant content of the catalyst is 0.1-2 wt.%, and the specific surface area of the catalyst is 460-470m2/g。
The invention also aims to provide a preparation method of the catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate, which comprises the following steps:
step 1, mixing copper precursor salt (copper acetate or copper nitrate) with deionized water (water temperature is 30-50 ℃), wherein the content of copper added is 5-59.9 wt.% in terms of metal oxide, and uniformly stirring to obtain a clarified solution, namely the copper precursor salt solution.
And 2, adding an alkaline agent (ammonia water, ammonium carbonate or sodium hydroxide) into the copper precursor salt solution, and stirring for 0.5-5h under an alkaline condition. Keeping the temperature of the solution at 30-80 ℃ during stirring, and keeping the pH value of the solution at 8.5-13.5 during stirring. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
And 3, dropwise adding a silicon dioxide silicon source (sodium silicate, silicon dioxide sol or tetraethoxysilane) into the product obtained in the step 2 (1 drop per second), continuously dissolving the silicon dioxide silicon source in an alkaline environment, reacting the copper precursor salt solution with the silicon dioxide silicon source, gradually depositing and curling to form a nanotube structure, and keeping the pH value of the solution at 11-12 in the dropwise adding process. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
After the dropwise addition is finished, the solution is stirred and aged in a water bath (the system is kept sealed or a reflux mode is adopted during aging), the temperature of the solution is kept between 30 and 90 ℃ during aging, the aging time is 4 to 30 hours, and the pH value of the solution is 8.5 to 13.5. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
When the alkaline agent is ammonia water: after aging, adjusting the temperature to 80 ℃ or above, and evaporating ammonia until the pH value is 7-8 to finish the removal of the alkaline agent.
When the alkaline agent is ammonium carbonate or sodium hydroxide: and after aging, adding dilute nitric acid into the solution for neutralization until the pH value is 7-8 to complete the removal of the alkaline agent.
And 4, filtering the product obtained in the step 3, washing the obtained precipitate with deionized water (filtering washing or centrifugal washing) to remove copper ions, and washing until the pH value of the washing waste liquid is 6.4-7.
Drying the washed precipitate at 50-120 deg.c for 4-12 hr to obtain the catalyst precursor with nanotube structure.
And 5, mixing the auxiliary agent precursor salt (nitrate or acetate) with deionized water to obtain a salt solution with the concentration of 0.002-1.5 mol/L. Dripping the assistant precursor salt solution into the catalyst precursor powder, uniformly stirring, and drying at 25-100 ℃ for 10-60 h.
And step 6, roasting the product obtained in the step 5 at the temperature of 300-700 ℃ for 3-12h to obtain a catalyst finished product.
The catalyst needs to be subjected to online reduction before use, and specifically comprises the following steps: the reduction temperature is 150-400 ℃, the reduction atmosphere is hydrogen, and the hydrogen flow required by the reduction of each gram of catalyst is 40-400 mL/min.
More preferred embodiments are: the copper precursor salt is copper nitrate, the auxiliary agent precursor salt is nitrate, the silicon dioxide silicon source is silica sol, the alkaline agent is ammonia water, and the drying method is a common drying method.
The invention also aims to provide a using method of the catalyst, in the reaction of synthesizing methanol and ethylene glycol by hydrogenating ethylene carbonate, the reaction pressure is 2-5MPa, the reaction temperature is 150-240 ℃, the hydrogen-ester ratio is 20-200, and the liquid hourly space velocity is 0.1-4h-1Wherein the liquid hourly space velocity refers to the space velocity of ethylene carbonate.
Among the above methods of use, the more preferred embodiment is: the promoter precursor salt contained platinum, which accounted for 0.2 wt.% of the catalyst weight. The hydrogen-to-ethylene carbonate ratio of hydrogen to vaporized ethylene carbonate is 160-190, preferably 180.
The invention has the advantages and positive effects that:
1. the catalyst adopts metal copper as an active component, and the prepared catalyst has the characteristics of high catalytic activity, easily obtained preparation raw materials, low cost, easy industrial production and the like by utilizing a special nano-tubular structure.
2. The catalyst adopts trace noble metal as an auxiliary agent, the prepared catalyst is used for the gas-solid phase reaction of ethylene carbonate, is easy to recover, greatly reduces the using amount of the noble metal compared with the catalyst made of organic noble metal, effectively improves the reaction activity and the methanol selectivity of the catalyst on the premise of economy and environmental protection, simultaneously reduces the proportion of hydrogen and ethylene carbonate, can greatly reduce the circulation amount of the hydrogen in industry, saves the power consumption of a gas compressor and improves the processing capacity of a reactor with unit volume.
3. The invention adopts the catalyst with the characteristic of a special nano-tubular structure, and can highly disperse the active component copper or the oxide thereof, thereby improving the conversion rate of the ethylene carbonate and the selectivity of methanol, and simultaneously showing excellent stability in the hydrogenation process.
Drawings
Fig. 1 is a transmission electron microscope image of a nanotube-shaped catalyst used in the present invention, wherein a is a transmission electron microscope image before reduction of the catalyst, and B is a transmission electron microscope image after reduction of the catalyst.
FIG. 2 is an X-ray powder diffraction pattern of a reduced nanotubular catalyst useful in the present invention.
FIG. 3 shows the evaluation results of catalyst stability in the preparation of methanol and ethylene glycol by hydrogenation of ethylene carbonate.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to these examples. The experimental methods not specified in the examples are generally commercially available according to the conventional conditions and the conditions described in the manual, or according to the general-purpose equipment, materials, reagents and the like used under the conditions recommended by the manufacturer, unless otherwise specified.
The invention discloses a catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate, which is innovative in that: the main chemical components of the catalyst are copper and oxides thereof and silicon dioxide, wherein the copper accounts for 5-59.9 wt% of the weight of the catalyst; silica in 40-94.9 wt.% of the catalyst weight; the auxiliary agent accounts for 0.1-5 wt% of the weight of the catalyst.
The catalyst structure is a nano-tube structure with a specific surface area of 450-500m2(ii)/g; the diameter of the nanotube is 3-5nm, and the length of the nanotube is 40-300 nm.
The preferred scheme is as follows: the copper content of the catalyst is 30-48 wt.%, the silicon oxide content of the catalyst is 50-68 wt.%, the assistant content of the catalyst is 0.1-2 wt.%, and the specific surface area of the catalyst is 460-470m2/g。
The preparation method of the catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate comprises the following steps:
step 1, mixing copper precursor salt (copper acetate or copper nitrate) with deionized water (water temperature is 30-50 ℃), wherein the content of copper added is 5-59.9 wt.% in terms of metal oxide, and uniformly stirring to obtain a clarified solution, namely the copper precursor salt solution.
And 2, adding an alkaline agent (ammonia water, ammonium carbonate or sodium hydroxide) into the copper precursor salt solution, and stirring for 0.5-5h under an alkaline condition. Keeping the temperature of the solution at 30-80 ℃ during stirring, and keeping the pH value of the solution at 8.5-13.5 during stirring. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
And 3, dropwise adding a silicon dioxide silicon source (sodium silicate, silicon dioxide sol or tetraethoxysilane) into the product obtained in the step 2 (1 drop per second), continuously dissolving the silicon dioxide silicon source in an alkaline environment, reacting the copper precursor salt solution with the silicon dioxide silicon source, gradually depositing and curling to form a nanotube structure, and keeping the pH value of the solution at 11-12 in the dropwise adding process. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
After the dropwise addition is finished, the solution is stirred and aged in a water bath (the system is kept sealed or a reflux mode is adopted during aging), the temperature of the solution is kept between 30 and 90 ℃ during aging, the aging time is 4 to 30 hours, and the pH value of the solution is 8.5 to 13.5. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
When the alkaline agent is ammonia water: after aging, adjusting the temperature to 80 ℃ or above, and evaporating ammonia until the pH value is 7-8 to finish the removal of the alkaline agent.
When the alkaline agent is ammonium carbonate or sodium hydroxide: and after aging, adding dilute nitric acid into the solution for neutralization until the pH value is 7-8 to complete the removal of the alkaline agent.
And 4, filtering the product obtained in the step 3, washing the obtained precipitate with deionized water (filtering washing or centrifugal washing) to remove copper ions, and washing until the pH value of the washing waste liquid is 6.4-7.
Drying the washed precipitate at 50-120 deg.c for 4-12 hr to obtain the catalyst precursor with nanotube structure.
And 5, mixing the auxiliary agent precursor salt (nitrate or acetate) with deionized water to obtain a salt solution with the concentration of 0.002-1.5 mol/L. Dripping the assistant precursor salt solution into the catalyst precursor powder, uniformly stirring, and drying at 25-100 ℃ for 10-60 h.
And step 6, roasting the product obtained in the step 5 at the temperature of 300-700 ℃ for 3-12h to obtain a catalyst finished product.
More preferred embodiments are: the copper precursor salt is copper nitrate, the auxiliary agent precursor salt is nitrate, the silicon dioxide silicon source is silica sol, the alkaline agent is ammonia water, and the drying method is a common drying method.
The use method of the catalyst comprises the following steps: in the reaction of synthesizing methanol and ethylene glycol by hydrogenating ethylene carbonate, the reaction pressure is 2-5MPa, the reaction temperature is 150-240 ℃, the hydrogen-ester ratio is 20-200, and the liquid hourly space velocity is 0.1-4h-1Wherein the liquid hourly space velocity refers to the space velocity of ethylene carbonate. More preferred embodiments are: the promoter precursor salt contained platinum, which accounted for 0.2 wt.% of the catalyst weight. The hydrogen-to-ethylene carbonate ratio of hydrogen to vaporized ethylene carbonate was 180.
Example 1
Preparation of the catalyst:
40g of copper nitrate trihydrate was weighed and dissolved in 100mL of deionized water (water temperature 30 ℃) and stirred uniformly to obtain a clear solution.
Adding 139mL ammonia water, stirring at 30 deg.C for half an hour, and keeping the pH value of the solution at 8.5-13.5 during stirring. In order to avoid large changes of the pH value, the reaction system is placed in a sealed environment.
44.5mL of 30 wt.% silica sol was metered in (1 drop per second) dropwise, the pH being maintained at 11-12 during the addition. After the dropwise addition, stirring and aging are carried out in a water bath at 50 ℃ for 4 hours (the system is kept sealed during aging), and the pH value of the solution is 8.5-13.5. Heating to 80 deg.C, and distilling ammonia until pH is 7-8.
After filtering, the obtained precipitate is subjected to common washing, and the washing is finished when the pH value of the washing waste liquid is about 6.4-7. And drying the washed precipitate at 110 ℃ for 4h to obtain the catalyst precursor with the nanotube structure.
And roasting the catalyst precursor at 450 ℃ for 4h to obtain the catalyst.
Catalyst on-line reduction and catalytic effect evaluation:
the gas-phase ethylene carbonate hydrogenation reaction is carried out in a fixed bed reactor.
Sieving the calcined catalyst tablet to 40-60 mesh, filling 0.5g catalyst, and keeping the catalyst in H of 3MPa2Reducing at 300 ℃ in atmosphere, wherein the gas flow rate is 100mL/min, raising the temperature from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping the temperature for 4h, reducing the temperature to 180 ℃, gasifying ethylene carbonate, mixing the ethylene carbonate with hydrogen, and introducing the ethylene carbonate into a reaction tube, wherein the hydrogen-ester ratio is 200, and the mass space velocity of the ethylene carbonate is 0.5h-1The reaction was carried out at 3 MPa. Analysis of the product by gas chromatography gave ethylene carbonate, Ethylene Glycol (EG), methanol (MeOH) and ethanol (EtOH). The results of the catalyst performance evaluation are shown in Table 1.
Comparative example 1
Cu/SiO2Preparation of a catalyst precursor:
40g of copper nitrate trihydrate was weighed and dissolved in 100mL of deionized water (water temperature 50 ℃) and stirred uniformly to obtain a clear solution.
Adding 139mL of ammonia water, stirring at 50 ℃ for 2h, and keeping the pH value of the solution at 8.5-13.5 during stirring. In order to avoid large changes of the pH value, the reaction system is placed in a sealed environment.
44.5mL of 30 wt.% silica sol was metered in (1 drop per second) dropwise, the pH being maintained at 11-12 during the addition. After the dropwise addition, stirring and aging in a water bath at 70 ℃ for 20 hours (in the aging process, a reflux mode is adopted), wherein the pH value of the solution is 8.5-13.5. Heating to 80 deg.C, and distilling ammonia until pH is 7-8.
After filtering, the obtained precipitate is subjected to common washing, and the washing is finished when the pH value of the washing waste liquid is about 6.4-7. And drying the washed precipitate at 80 ℃ for 12h to obtain the catalyst precursor with the nanotube structure.
Preparation of the catalyst:
0.0385g of Ru (NH) was weighed out3)6(NO3)3Dissolved in 4.5g of deionized water and added dropwise to 2g of Cu/SiO2And (2) uniformly stirring the precursor powder, drying the precursor powder for 48 hours at room temperature (the 'drying at 30-100 ℃ for 10-60 hours' in the step 5 is modified into 'drying at 25-100 ℃ for 10-60 hours'), and roasting the precursor powder for 10 hours at 300 ℃ to obtain the catalyst.
Evaluation of catalyst:
the catalyst on-line reduction and catalyst evaluation methods were the same as in example 1, and the catalyst performance evaluation results are shown in Table 1.
Comparative example 2
Cu/SiO2Preparation of a catalyst precursor:
Cu/SiO2the catalyst precursor was prepared as in comparative example 1.
Preparation of the catalyst:
0.0380g of Rh (NH) was weighed out3)6(NO3)3Dissolved in 4.5g of deionized water and added dropwise to 2g of Cu/SiO2And (3) uniformly stirring the precursor powder, drying the precursor powder for 14 hours at the temperature of 100 ℃, and roasting the precursor powder for 3 hours at the temperature of 700 ℃ to obtain the catalyst.
Evaluation of catalyst:
the catalyst on-line reduction and catalyst evaluation methods were the same as in example 1, and the catalyst performance evaluation results are shown in Table 1.
Comparative example 3
Cu/SiO2Preparation of a catalyst precursor:
Cu/SiO2the catalyst precursor was prepared as in comparative example 1.
Preparation of the catalyst:
weighing 0.0281g Pd (NH)3)4(NO3)2Dissolved in 4.5g of deionized water and added dropwise to 2g of Cu/SiO2And (3) uniformly stirring the precursor powder, drying the precursor powder for 50 hours at the temperature of 60 ℃, and roasting the precursor powder for 4 hours at the temperature of 450 ℃ to obtain the catalyst.
Evaluation of catalyst:
the catalyst on-line reduction and catalyst evaluation methods were the same as in example 1, and the catalyst performance evaluation results are shown in Table 1.
Example 2
Cu/SiO2Preparation of a catalyst precursor:
Cu/SiO2the catalyst precursor was prepared as in comparative example 1.
Preparation of the catalyst:
0.0198g of Pt (NH) were weighed out3)4(NO3)2Dissolved in 4.5gIn ionized water, 2g of Cu/SiO was added dropwise2And (3) uniformly stirring the precursor powder, drying the precursor powder at room temperature for 48 hours, and roasting the precursor powder at the temperature of 450 ℃ for 4 hours to obtain the catalyst.
Evaluation of catalyst:
the catalyst on-line reduction and catalyst evaluation methods were the same as in example 1, and the catalyst performance evaluation results are shown in Table 1. It can be seen that the catalyst with the addition of suitable minor amounts of noble metal promoter shows higher conversion of ethylene carbonate and selectivity to methanol. Among them, the catalyst added with the platinum promoter shows the best catalytic performance.
TABLE 1 ethylene carbonate hydrogenation performance of different promoter catalysts
Figure RE-GDA0002377244770000071
Examples 3 to 5
The catalyst was prepared in the same manner as in example 2 by changing Pt (NH)3)4(NO3)2The addition amounts of (a) and (b) respectively give catalysts of different Pt loadings: (0.1 wt.%, 0.2 wt.%, 1.0 wt.%), catalyst on-line reduction and catalyst performance evaluation methods were the same as in example 1, and the mass space velocity of ethylene carbonate was changed to 1.0h-1. The results of the catalyst performance evaluation are shown in Table 2. It can be seen that the addition of a suitable content of auxiliary agent can increase the conversion of ethylene carbonate and the selectivity of methanol. The catalyst performance was best when the platinum promoter addition was 0.2 wt.%.
TABLE 2 ethylene carbonate hydrogenation performance of different Pt loading catalysts
Figure RE-GDA0002377244770000081
Examples 6 to 9
The catalyst preparation method, the catalyst on-line reduction and evaluation conditions were the same as in example 4, the hydrogen-ester ratios for the catalyst performance evaluation were changed to 190, 180, 170 and 160, respectively, and the other were unchanged, and the catalyst performance evaluation results are shown in table 3.
From Table 3 canIt is seen that the platinum modified Cu/SiO of the present invention2The catalyst can still show higher conversion rate of the ethylene carbonate and product selectivity under the condition of lower hydrogen-ester ratio. When the hydrogen-ester ratio is 180, the selectivity of methanol can reach 79.5 percent, and the selectivity of glycol can reach 99.5 percent. The stability evaluation of example 7 is shown in figure 3, which shows that the catalyst of the invention exhibits excellent stability.
TABLE 3 hydrogenation reaction performance of ethylene carbonate at different hydrogen-ester ratios
Figure RE-GDA0002377244770000082

Claims (10)

1. A catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate is characterized in that: the catalyst comprises copper, a carrier and an auxiliary agent, wherein the copper accounts for 5-59.9 wt% of the weight of the catalyst, the carrier accounts for 40-94.9 wt% of the weight of the catalyst, and the auxiliary agent accounts for 0.1-5 wt% of the mass of the catalyst.
2. The catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate according to claim 1 is characterized in that: the specific surface area of the catalyst is 450-500m2(ii)/g; the catalyst has a nanotube structure, the diameter of the nanotube is 3-5nm, and the length of the nanotube is 40-300 nm.
3. The catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate according to claim 1 is characterized in that: the copper accounts for 30-48 wt% of the weight of the catalyst, and the carrier accounts for 50-68 wt% of the weight of the catalyst.
4. The catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate according to claim 1 is characterized in that: the auxiliary agent accounts for 0.1-2 wt% of the weight of the catalyst.
5. The catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate according to claim 1, 2, 3 or 4, is characterized in that: the carrier is silicon dioxide, and the auxiliary agent contains ruthenium, rhodium, palladium or platinum.
6. The preparation method of the catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate according to claim 5, which comprises the following steps: the method comprises the following steps:
⑴ mixing the copper precursor salt with water to obtain copper precursor salt solution;
⑵, adding an alkaline agent into the copper precursor salt solution obtained in the step ⑴, and aging after adding a silicon source;
⑶ removing the alkaline agent in the product of step ⑵, filtering to obtain precipitate, washing the precipitate, and drying to obtain a catalyst precursor;
⑷ and mixing the precursor salt of the auxiliary agent with water, adding the mixture into the precursor of the catalyst, drying and roasting to obtain the finished product of the catalyst.
7. The preparation method of the catalyst for the co-production of methanol and ethylene glycol by the hydrogenation of ethylene carbonate according to claim 7, wherein the catalyst comprises the following steps: the copper precursor salt solution is a copper acetate salt solution or a copper nitrate salt solution; the alkaline agent is ammonia water, ammonium carbonate or sodium hydroxide; the silicon dioxide silicon source is sodium silicate, silica sol or ethyl orthosilicate.
8. The preparation method of the catalyst for the co-production of methanol and ethylene glycol by the hydrogenation of ethylene carbonate according to claim 7 or 8, wherein the catalyst comprises the following steps: the aid precursor salt solution is a nitrate solution or an acetate solution.
9. The use method of the catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate according to claim 5 is characterized in that: the promoter precursor salt contained platinum, which accounted for 0.2 wt.% of the catalyst weight.
10. The use method of the catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate according to claim 5 is characterized in that: the hydrogen to vaporized ethylene carbonate hydrogen ester ratio is 160-190, preferably 180.
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