CN114011405A - Preparation method of composite oxide supported catalyst and application of composite oxide supported catalyst in preparation of methyl glycolate from ethylene glycol - Google Patents
Preparation method of composite oxide supported catalyst and application of composite oxide supported catalyst in preparation of methyl glycolate from ethylene glycol Download PDFInfo
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Abstract
The invention provides a preparation method of a composite oxide supported catalyst and application of the composite oxide supported catalyst in preparation of methyl glycolate by using ethylene glycol. The catalyst mainly comprises an active component and a composite carrier. The composite oxide carrier is a mixture of two or more oxides, the main active component is noble metal, and the noble metal accounts for 0.01-15 wt% of the composite oxide of the carrier. The catalyst supported by the composite oxide is modified by in-situ synthesis of the oxide, so that the activity of the catalyst is improved. The method has simple preparation process and easy amplification, and can ensure that the conversion rate of the glycol reaches 95 percent and the selectivity of the ethyl acetate (product) reaches 98 percent.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a preparation method of a composite oxide supported catalyst for preparing methyl glycolate by using ethylene glycol.
Background
Methyl glycolate has both chemical properties of alcohol and ester due to the alpha-H, hydroxyl and ester functional groups, can undergo a series of chemical reactions such as carbonization, amination, hydrolysis, hydrogenation, oxidative dehydrogenation and the like, and is a very important intermediate for pharmaceutical synthesis and organic synthesis. Methyl glycolate is also an excellent solvent for cellulose, resins, and rubbers.
Since the 60's of the 20 th century, many developed countries have begun to develop processes suitable for large-scale production of methyl glycolate. The method comprises the steps of addition of formaldehyde and hydrocyanic acid, free radical addition of methylal and formaldehyde, carbonylation and esterification of formaldehyde, coupling reaction of methyl formate and formaldehyde and the like. Because the processes have the defects of high raw material price, relatively serious corrosion in the production process, difficult separation of products and the like, the processes are gradually eliminated.
In recent years, ethylene glycol and methanol are used as starting materials to synthesize methyl glycolate through one-step oxidation esterification reaction. The process flow has the advantages of cheap raw materials, wide sources, simple process, environmental protection and the like, and the reaction is finished by a one-step method. In particular, the separation and purification process of the product is simple, the product purity is high, and the cost is low. With the continuous development of gold catalysts, japanese catalyst patent discloses a method for producing alpha-hydroxycarboxylic acid esters based on direct oxidative esterification of nanogold catalysts. Patent CN1720218A is to disperse and support nano-size activated gold on metal oxide by deposition precipitation method for preparing methyl glycol glycolate by one-step oxidative esterification of ethylene glycol, and to inhibit or prevent side reactions generated by alpha-hydroxycarboxylic ester. The catalytic activity of the nano Au catalyst reported by the Japanese catalyst is better, but the loading amount of gold is higher, so that the cost of the catalyst is higher.
Disclosure of Invention
Aiming at the technical problems, the invention provides a production route with simple process flow and no pollution in the production process aiming at the reaction of producing methyl glycolate by an oxidative esterification one-step method of ethylene glycol and methanol from the viewpoint of developing a green chemical production process, and the invention ensures that the conversion rate of ethylene glycol reaches 95% and the selectivity of ethyl acetate reaches 98% by enhancing the interaction between a composite oxide and a noble metal.
The technical scheme of the invention is as follows:
in one aspect, the present invention provides a method for preparing a composite oxide-supported catalyst for the preparation of methyl glycolate from ethylene glycol, the method comprising the steps of:
(1) dissolving noble metal salt in water, adding a composite oxide carrier, and then adding an alkaline aqueous solution to adjust to neutrality to obtain a mixture; the composite oxide carrier is Al2O3、MgO、SiO2、CaO、ZnO、CeO、CuO、MnO2、Fe2O3、FeO、CoO、Co3O4At least two of; the content of the noble metal is 0.01-15 wt% of the composite oxide carrier;
(2) heating the mixture obtained in the step (1) to 50-70 ℃, then dropwise adding an inorganic compound precursor, aging for 1-5h, washing with deionized water, and performing suction filtration to obtain a solid sample; the inorganic compound precursor is one or more of ethyl orthosilicate, silica sol, white carbon black, sodium silicate and soluble acetate, nitrate, chloride and sulfate of aluminum, zinc, magnesium, iron, calcium, copper, cobalt and cerium;
(3) and (3) drying the solid sample obtained in the step (2), and then roasting for 1-8h at the temperature of 300-800 ℃ in an oxygen-containing atmosphere to obtain the inorganic compound modified composite oxide supported catalyst.
Based on the scheme, preferably, the noble metal is one or more of gold, platinum, ruthenium, rhodium, palladium, osmium and iridium, and the content of the noble metal is 0.05-5 wt% of the composite oxide carrier.
Based on the above scheme, preferably, the content of the inorganic compound in the catalyst is 1 to 80 wt%, preferably 10 to 50 wt% of the composite oxide support.
Based on the above scheme, preferably, the alkaline aqueous solutionIs NaOH or Na2CO3、NaHCO3、KOH、K2CO3And one or more of ammonia water, wherein the concentration of the alkaline aqueous solution is 0.01-5 moL/L.
Based on the above scheme, preferably, the oxygen-containing atmosphere is pure oxygen or 10-50 wt% oxygen, and when the oxygen-containing atmosphere is 10-50 wt% oxygen, the filling gas is one or more of nitrogen or inert gas.
Based on the scheme, the roasting temperature of the catalyst is preferably 300-500 ℃, and the roasting time is preferably 3-5 h.
In another aspect, the invention provides the use of the above catalyst in a reaction of ethylene glycol to produce methyl glycolate.
Based on the scheme, preferably, the reaction is carried out in an autoclave, a mixed solution of methanol and ethylene glycol is added, the catalyst is dispersed in the mixed solution, the reaction is carried out in an oxygen-containing atmosphere, the reaction pressure is 0.5-5MPa, the reaction temperature is 80-120 ℃, the reaction time is 0.5-24h, and after the reaction is finished, the conversion rate of the ethylene glycol and the selectivity of the ethyl acetate are calculated; wherein the adding proportion of the methanol and the glycol is mMethanol/mEthylene glycol0.1-50; the addition amount of the catalyst is 0.1-20 wt% of the total amount of the methanol and the ethylene glycol.
Based on the scheme, the reaction pressure is preferably 0.5-3MPa, the reaction temperature is 100-120 ℃, and the reaction time is preferably 0.5-5 h; the adding proportion of the methanol and the glycol is mMethanol/mEthylene glycol2-20; the addition amount of the catalyst is 1-8 wt% of the total amount of the methanol and the glycol.
Advantageous effects
The invention loads noble metal particles on the surface of the composite oxide, modifies inorganic compounds on the surface of the catalyst, further enhances the contact area between the metal particles and the composite oxide carrier, and compared with the metal catalyst loaded by the conventional oxide or the metal catalyst modified by inorganic compounds and loaded by single oxide, the invention can further regulate and control the electronic effect of noble metal, improve the interaction between the noble metal particles and the oxide, and improve the catalytic activity, so that the conversion rate of ethylene glycol reaches 95%, and the selectivity of ethyl acetate (product) reaches 98%.
Detailed Description
Comparative example 1: 1% Au/(Al)2O3＆SiO2)
Mixing gamma-Al2O3And SiO2Mixing and dispersing in a 250mL beaker, gamma-alumina and SiO2The mass ratio of the mixture of (1) was 5: 1, and chloroauric acid was added so that the theoretical loading of gold on the mixed oxide support was 1 wt%. Adding ammonia water, and adjusting the pH value of the solution to about 7. The solution was then heated to 70 ℃ and stirring was continued for 2 hours. Then, a large amount of deionized water is used for suction filtration and washing, and the mixture is dried in an oven at 80 ℃ for 3 hours. Finally, the catalyst is roasted for 4 hours at 500 ℃ in the air atmosphere, and the obtained catalyst can be marked as 1% Au/(Al)2O3＆SiO2)。
In a 100mL autoclave equipped with a stirring paddle, 7.3g of methanol, 1.42g of ethylene glycol and 0.5g of 1% Au/(Al)2O3＆SiO2) The catalyst is charged with 50% oxygen-nitrogen mixture, the pressure is adjusted to 3MPa, the temperature is raised to 120 ℃, and the reaction is carried out for 4 hours under the condition of continuous stirring. After cooling the system, the reaction product was analyzed and showed 68% conversion of ethylene glycol and 86% selectivity to ethyl acetate (product).
Comparative example 2: 1% Au/(Al)2O3@SiO2)
Firstly, dropwise adding a certain amount of ethyl orthosilicate into gamma-alumina, stirring for 8 hours, then placing the mixture in an oven at 80 ℃ for drying for 3 hours, and then roasting at 500 ℃ for 4 hours to obtain a carrier Al2O3@SiO2Wherein Al is2O3With SiO2The mass ratio of (A) to (B) is 5: 1.
Then the prepared chloroauric acid solution is put into a 250mL beaker, and is stirred after ultrapure water is added. Adding Al into the beaker2O3@SiO2Solid such that the theoretical loading of gold on the support is 1%. The pH of the solution was adjusted to about 7 with ammonia. The solution was then heated to 70 ℃ and stirring was continued for 2 hours. With extensive deionisationAfter filtering and washing the catalyst with water, the catalyst was dried in an oven at 80 ℃ for 3 hours. The catalyst was then calcined at 500 ℃ for 4 hours in an air atmosphere and the resulting catalyst was designated 1% Au/(Al)2O3@SiO2)。
In a 100mL autoclave equipped with a stirring paddle, 7.3g of methanol and 1.42g of ethylene glycol were charged, together with 0.5g of 1% Au/(Al)2O3@SiO2) Introducing 50% oxygen-nitrogen mixture into the catalyst, adjusting the pressure to 3MPa, raising the temperature to 120 ℃ under the stirring state, and reacting for 4 hours under the continuous stirring state. After cooling the system, the reaction product was analyzed and the results showed 78% conversion of ethylene glycol and 89% selectivity to ethyl acetate (product).
Comparative example 3: 1% Au/[ (Al)2O3＆SiO2)@SiO2]
Firstly, a certain amount of ethyl orthosilicate is dripped into a mixture of gamma-alumina and silicon dioxide, and the mixture is roasted at 500 ℃ to obtain a carrier (Al)2O3＆SiO2)@SiO2Wherein the mass ratio of the gamma-alumina, the directly added silicon dioxide and the silicon dioxide obtained after roasting is 5: 1. Then the prepared chloroauric acid solution is put into a 250mL beaker, ultrapure water is added, stirring is carried out, and (Al) is added2O3＆SiO2)@SiO2So that the theoretical loading of gold on the composite oxide support is 1%. The pH value is adjusted to about 7 by ammonia water. And heating the solution to 70 ℃, then dropwise adding a certain amount of tetraethoxysilane, aging for 3 hours, washing with deionized water, and carrying out suction filtration. The sample was dried in an oven at 80 ℃ for 3 h. The catalyst was then calcined at 500 ℃ for 4 hours in an air atmosphere and the resulting catalyst was labeled 1% Au/[ (Al)2O3＆SiO2)@SiO2]。
A100 mL autoclave equipped with a stirring paddle was charged with 7.3g of methanol and 1.42g of ethylene glycol, as well as 0.5g of the above-mentioned 1% Au/[ (Al)2O3＆SiO2)@SiO2]Catalyst, 50% oxygen-nitrogen mixture, adjusting the pressure to 3Mpa, raising the temperature to 120 ℃ under stirring, and reacting for 4 hours under the condition of continuous stirring. Then will beThe system was cooled and the reaction product was analyzed, which indicated 88% conversion of ethylene glycol and 90% selectivity to ethyl acetate (product).
Example 1: [ 1% Au/(Al)2O3＆SiO2)]@SiO2
The prepared chloroauric acid solution is put into a 250ml beaker, a certain amount of ultrapure water is added, and the beaker is put on a magnetic stirrer to be stirred. Subsequently, a mixture of gamma-alumina and silica was added in proportions such that the theoretical loading of gold on the composite oxide support was 1%. The pH value of the solution is adjusted to be about 7 by ammonia water. The solution was then heated to 70 ℃ and then an amount of aluminum isopropoxide was added dropwise and aged for 3 hours. Then washing with deionized water and filtering. The sample was dried in an oven at 80 ℃ for 3 hours. The catalyst was then calcined at 550 ℃ for 4 hours in air to give the catalyst [ 1% Au/(Al)2O3＆SiO2)]@SiO2Wherein the mass ratio of the gamma-alumina, the directly added silicon dioxide and the silicon dioxide obtained after roasting is 5: 1.
A100 mL autoclave equipped with a stirring paddle was charged with 7.3g of methanol and 1.42g of ethylene glycol, and 0.5g of the above [ 1% Au/(Al)2O3＆SiO2)]@SiO2The catalyst was placed in a 100mL autoclave equipped with a stirring paddle, in a 50% oxygen-nitrogen mixture, the pressure was adjusted to 3MPa, and the temperature was raised to 120 ℃ with stirring, and this temperature was maintained for 4 hours. The system was then cooled and the reaction product analyzed, which indicated 95% conversion of ethylene glycol and 98% selectivity to ethyl acetate (product).
Example 2: [ 1% Au/(Al)2O3＆SiO2)]@MgO
The prepared chloroauric acid solution is put into a 250mL beaker, a certain amount of ultrapure water is added, and the beaker is placed on a magnetic stirrer to be stirred. Subsequently, gamma-alumina and silica were added in proportions such that the theoretical loading of gold on the composite oxide support was 1%. The pH value of the solution is adjusted to be about 7 by ammonia water. The solution was then heated to 70 ℃ and then a quantity of magnesium nitrate was added dropwise and aged for 3 hours. Followed by deionizationWashing the seed with water and filtering. The sample was dried in an oven at 80 ℃ for 3 hours. The catalyst was then calcined at 600 ℃ for 4 hours in an air atmosphere to give the catalyst [ 1% Au/(Al)2O3＆SiO2)]@ MgO, wherein Al2O3、SiO2And the mass ratio of MgO is 10: 1.
A100 mL autoclave equipped with a stirring paddle was charged with 7.3g of methanol and 1.42g of ethylene glycol, and 0.5g of the above [ 1% Au/(Al)2O3＆SiO2)]@ MgO catalyst, 50% oxygen-nitrogen mixture, pressure to 3Mpa, then with stirring to raise the temperature to 120 degrees C, the temperature is maintained for 4 hours. The system was then cooled and the reaction product analyzed, which indicated 90% conversion of ethylene glycol and 93% selectivity to ethyl acetate (product).
Example 3: [ 1% Au/(Al)2O3＆SiO2)]@ZnO
The prepared chloroauric acid solution is put into a 250mL beaker, a certain amount of ultrapure water is added, and the beaker is placed on a magnetic stirrer to be stirred. Subsequently, gamma-alumina and silica were added in proportions such that the theoretical loading of gold on the composite oxide support was 1%. The pH value of the solution is adjusted to be about 7 by ammonia water. The solution was then heated to 70 ℃ and then an amount of zinc acetate was added dropwise and aged for 3 hours. Then washing with deionized water and filtering. The sample was dried in an oven at 80 ℃ for 3 hours. The catalyst was then calcined at 600 ℃ for 4 hours in an air atmosphere to give the catalyst [ 1% Au/(Al)2O3＆SiO2)]@ ZnO, wherein Al2O3、SiO2And the mass ratio of ZnO is 5: 1: 3.
A100 mL autoclave equipped with a stirring paddle was charged with 7.3g of methanol and 1.42g of ethylene glycol, and 0.5g of the above [ 1% Au/(Al)2O3＆SiO2)]@ ZnO catalyst, then increased to 3MPa with pure oxygen pressure, after which the temperature was raised to 120 ℃ with stirring, this temperature being maintained for 4 hours. The system was then cooled and the reaction product analyzed, which indicated a 91% conversion of ethylene glycol and 93% selectivity to ethyl acetate (product).
Example 4:[1％Pd/(Al2O3＆SiO2)]@ZnO
putting the prepared ammonium chloropalladate solution into a 250mL beaker, adding a certain amount of ultrapure water, and stirring on a magnetic stirrer. Subsequently, gamma-alumina and silica were added in proportions such that the theoretical loading of palladium on the composite oxide support was 1%. The pH value of the solution is adjusted to be about 7 by ammonia water. The solution was then heated to 70 ℃ and then an amount of zinc acetate was added dropwise and aged for 3 hours. Then washing with deionized water and filtering. The sample was dried in an oven at 80 ℃ for 3 hours. The catalyst was then calcined at 500 ℃ for 4 hours in an air atmosphere to give the catalyst [ 1% Pd/(Al)2O3＆SiO2)]@ ZnO, wherein Al2O3、SiO2And the mass ratio of ZnO is 10: 3: 1.
A100 mL autoclave equipped with a stirring paddle was charged with 7.3g of methanol and 1.42g of ethylene glycol, and 0.5g of the above [ 1% Pd/(Al)2O3＆SiO2)]@ ZnO catalyst, 50% oxygen-nitrogen mixture, pressure to 3Mpa, then with stirring to raise the temperature to 120 degrees C, the temperature is maintained for 4 hours. The system was then cooled and the reaction product analyzed, which indicated a 91% conversion of ethylene glycol and 89% selectivity to ethyl acetate (product).
Example 5: [ 5% Pt/(Al)2O3＆SiO2)]@ZnO
The prepared chloroplatinic acid solution is put into a 250mL beaker, a certain amount of ultrapure water is added, and the mixture is stirred on a magnetic stirrer. Subsequently, gamma-alumina and silica were added in proportions such that the theoretical loading of platinum on the alumina support was 5%. The pH value of the solution is adjusted to be about 7 by ammonia water. The solution was then heated to 70 ℃ and then an amount of zinc acetate was added dropwise and aged for 3 hours. Then washing with deionized water and filtering. The sample was placed in an oven at 80 ℃ to dry for 24 hours. The catalyst was then calcined at 600 ℃ for 4 hours in an air atmosphere to give a catalyst [ 5% Pt/(Al)2O3＆SiO2)]@ ZnO, wherein Al2O3、SiO2And ZnO in the mass ratio of 5 to1∶2。
A100 mL autoclave equipped with a stirring paddle was charged with 7.3g of methanol and 0.365g of ethylene glycol, and 0.5g of the above [ 5% Pt/(Al)2O3＆SiO2)]@ ZnO catalyst, 50% oxygen-nitrogen mixture, pressure to 3Mpa, then with stirring to raise the temperature to 120 degrees C, the temperature is maintained for 4 hours. The system was then cooled and the reaction product analyzed, which indicated 85% conversion of ethylene glycol and 93% selectivity to ethyl acetate (product).
Example 6: [ 10% Au/(Al)2O3＆SiO2)]@ZnO
The prepared chloroauric acid solution is put into a 250mL beaker, a certain amount of ultrapure water is added, and the beaker is placed on a magnetic stirrer to be stirred. Subsequently, gamma-alumina and silica were added in proportions such that the theoretical loading of gold on the composite oxide support was 10%. The pH value of the solution is adjusted to be about 7 by ammonia water. The solution was then heated to 70 ℃ and then an amount of zinc acetate was added dropwise and aged for 3 hours. Then washing with deionized water and filtering. The sample was dried in an oven at 80 ℃ for 3 hours. The catalyst was then calcined at 600 ℃ for 4 hours in an air atmosphere to give the catalyst [ 10% Au/(Al)2O3＆SiO2)]@ ZnO, wherein Al2O3、SiO2And the mass ratio of ZnO is 5: 1.
A100 mL autoclave equipped with a stirring paddle was charged with 7.3g of methanol and 3.65g of ethylene glycol, and 0.5g of the above [ 10% Au/(Al)2O3＆SiO2)]@ ZnO catalyst, 20% oxygen-nitrogen mixture, pressure to 3Mpa, then with stirring to raise the temperature to 110 degrees C, the temperature is maintained for 3 hours. The system was then cooled and the reaction product analyzed, which indicated 95% conversion of ethylene glycol and 89% selectivity to ethyl acetate (product).
Example 7: [ 15% Au/(Al)2O3＆MgO)]@ZnO
The prepared chloroauric acid solution is put into a 250mL beaker, a certain amount of ultrapure water is added, and the beaker is placed on a magnetic stirrer to be stirred. Subsequently, the addition of gamma-alumina and magnesium oxide in proportions such that the gold is inThe theoretical loading on the composite oxide support was 15%. The pH value of the solution is adjusted to be about 7 by ammonia water. The solution was then heated to 70 ℃ and then an amount of zinc acetate was added dropwise and aged for 3 hours. Then washing with deionized water and filtering. The sample was dried in an oven at 80 ℃ for 3 hours. The catalyst was then calcined at 600 ℃ for 4 hours in an air atmosphere to give the catalyst [ 15% Au/(Al)2O3＆MgO)]@ ZnO, wherein Al2O3The mass ratio of MgO to ZnO is 2: 1.
A100 mL autoclave equipped with a stirring paddle was charged with 7.3g of methanol and 3.65g of ethylene glycol, and 2.1g of the above [ 15% Au/(Al)2O3＆MgO)]@ ZnO catalyst, 20% oxygen-nitrogen mixture, pressure to 3Mpa, then with stirring to raise the temperature to 110 degrees C, the temperature is maintained for 3 hours. The system was then cooled and the reaction products analyzed, which indicated a 92% conversion of ethylene glycol and a 92% selectivity to ethyl acetate (product).
Claims (10)
1. A method for preparing a catalyst supported by a composite oxide for preparing methyl glycolate from ethylene glycol, which is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving noble metal salt in water, adding a composite oxide carrier, and then adding an alkaline aqueous solution to adjust to neutrality to obtain a mixture; the composite oxide carrier is Al2O3、MgO、SiO2、CaO、ZnO、CeO、CuO、MnO2、Fe2O3、FeO、CoO、Co3O4At least two of; the content of the noble metal is 0.01-15 wt% of the composite oxide carrier;
(2) heating the mixture obtained in the step (1) to 50-70 ℃, then dropwise adding an inorganic compound precursor, aging for 1-5h, washing with deionized water, and performing suction filtration to obtain a solid sample; the inorganic compound precursor is one or more of ethyl orthosilicate, silica sol, white carbon black, sodium silicate and soluble acetate, nitrate, chloride and sulfate of aluminum, zinc, magnesium, iron, calcium, copper, cobalt and cerium;
(3) and (3) drying the solid sample obtained in the step (2), and then roasting for 1-8h at the temperature of 300-800 ℃ in an oxygen-containing atmosphere to obtain the inorganic compound modified composite oxide supported catalyst.
2. The method of claim 1, wherein: the noble metal is one or more of gold, platinum, ruthenium, rhodium, palladium, osmium and iridium, the content of the noble metal is 0.05-5 wt% of the composite oxide carrier, and the content of the inorganic compound is 1-80 wt% of the composite oxide carrier.
3. The method of claim 2, wherein: the content of the inorganic compound is 10-50 wt% of the composite oxide carrier.
4. The method of claim 1, wherein: the alkaline aqueous solution is NaOH and Na2CO3、NaHCO3、KOH、K2CO3And one or more of ammonia water, wherein the concentration of the alkaline aqueous solution is 0.01-5 moL/L.
5. The method of claim 1, wherein: the oxygen-containing atmosphere is pure oxygen or 10-50 wt% of oxygen, and when the oxygen-containing atmosphere is 10-50 wt% of oxygen, the filling gas is one or more of nitrogen or inert gas.
6. The method of claim 1, wherein: the roasting temperature of the catalyst is 300-500 ℃, and the roasting time is 3-5 h.
7. A composite oxide supported catalyst for preparing methyl glycolate by ethylene glycol is characterized in that: the catalyst is prepared by the process of any one of claims 1 to 6.
8. Use of a catalyst according to claim 7 in a reaction of ethylene glycol to produce methyl glycolate.
9. Use according to claim 8, characterized in that: the reaction is carried out in a high-pressure kettle, mixed liquor of methanol and glycol is added, the catalyst is dispersed in the mixed liquor, the reaction is carried out under the oxygen-containing atmosphere, the reaction pressure is 0.5-5MPa, the reaction temperature is 80-120 ℃, the reaction time is 0.5-24h, and after the reaction is finished, the conversion rate of the glycol and the selectivity of the ethyl acetate are calculated;
wherein the adding proportion of the methanol and the glycol is mMethanol/mEthylene glycol0.1-50; the addition amount of the catalyst is 0.1-20 wt% of the total amount of the methanol and the ethylene glycol.
10. Use according to claim 9, characterized in that: the reaction pressure is 0.5-3MPa, the reaction temperature is 100-120 ℃, and the reaction time is 0.5-5 h; the adding proportion of the methanol and the glycol is mMethanol/mEthylene glycol2-20; the addition amount of the catalyst is 1-8 wt% of the total amount of the methanol and the glycol.
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| CN114931950A (en) * | 2022-05-27 | 2022-08-23 | 中国科学院大连化学物理研究所 | Carrier and preparation method thereof, catalyst and preparation method and application thereof |
| CN115106082A (en) * | 2022-07-12 | 2022-09-27 | 中国科学院大连化学物理研究所 | Composite oxide loaded gold-based alloy catalyst and preparation method and application thereof |
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