WO2022253171A1 - Catalyseur de support composite bimétallique/sio2-zro2 à base d'argent-ruthénium et son procédé de préparation et son application - Google Patents

Catalyseur de support composite bimétallique/sio2-zro2 à base d'argent-ruthénium et son procédé de préparation et son application Download PDF

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WO2022253171A1
WO2022253171A1 PCT/CN2022/095930 CN2022095930W WO2022253171A1 WO 2022253171 A1 WO2022253171 A1 WO 2022253171A1 CN 2022095930 W CN2022095930 W CN 2022095930W WO 2022253171 A1 WO2022253171 A1 WO 2022253171A1
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catalyst
weight
content
silver
ruthenium
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袁兴东
王丹
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高化学株式会社
袁兴东
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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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • 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
    • 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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/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
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids

Definitions

  • the invention relates to a silver-ruthenium double metal/SiO 2 -ZrO 2 composite carrier catalyst and a preparation method thereof, and also relates to a method for preparing methyl glycolate from dimethyl oxalate by using the catalyst.
  • Methyl glycolate has a unique molecular structure and has the chemical properties of both alcohols and esters. It is an urgently needed chemical in the fields of high-end pesticides, medicines, and chemical environmental protection. It is an excellent solvent for synthetic cellulose, rubber, and resins. In addition, methyl glycolate can undergo carbonylation reaction, hydrolysis reaction, oxidation reaction, etc., and becomes an important chemical raw material. At present, there are many traditional synthesis methods of methyl glycolate, and most of these traditional processes have deficiencies, such as the one-step synthesis method of glyoxal and methanol to prepare MGA.
  • the glyoxal in the raw material is too toxic and expensive, so it is not suitable for Industrialized production; the addition method of formaldehyde and hydrocyanic acid, the raw material hydrocyanic acid is highly toxic, even if the yield is high, it is not suitable for large-scale production; the coupling method is mostly catalyzed by liquid and solid strong acids, and there are serious corrosion and reactions High pressure defect.
  • the method of hydrolysis and re-esterification of chloroacetic acid is mostly used in my country, but there are problems such as heavy corrosion, heavy pollution, and limited raw materials.
  • CN108620107A reports a catalyst for hydrogenating dimethyl oxalate to synthesize methyl glycolate and its preparation method and application.
  • the catalyst uses NiM dual-element particles as an active component and TiO as a carrier; the first element of the NiM dual-element particles is metal Ni, and the second element M is any one of non-metallic B and P;
  • the surface area of the carrier TiO 2 is 2-200m 2 /g, the pore volume is 2-200cm 3 /g, and the pore diameter is 0.05-5nm;
  • the metal Ni content in the catalyst is 5%-25% by weight, and the element M content is It is 2% by weight to 10% by weight.
  • CN101700496B discloses a catalyst for synthesizing methyl glycolate by hydrogenation of dimethyl oxalate and a preparation method thereof.
  • the catalyst uses metal copper as the main active component, silver and manganese as auxiliary active components, and Al2O3 as the carrier ; wherein the metal copper content is 25% to 50% of the catalyst quality, the metal silver content is 5% to 15% of the catalyst quality, the metal manganese content is 8% to 20% of the catalyst quality, and the Al2O3 content is 5% of the catalyst quality 15% to 40%.
  • the technology of preparing methyl glycolate by hydrogenation of dimethyl oxalate mainly adopts silver-based catalyst or copper-based catalyst.
  • silver catalyst the selectivity of dimethyl oxalate to generate MGA is very high, however, silver is easy to sinter at high temperature, the catalyst stability is poor, and the activity is low at low temperature.
  • copper-based catalyst the activity is high at a relatively high reaction temperature, but MGA is easy to generate ethylene glycol and has many by-products.
  • due to the generation of a large amount of by-product methanol it is easy to cause the silicon loss of the carrier and the catalyst deactivation rate is fast. , and the deactivated catalyst cannot be regenerated, so it is necessary to develop an industrial catalyst with high activity at low temperature and long catalyst life.
  • the inventors of the present invention have carried out extensive and in-depth research on the catalyst for MGA by hydrogenation of DMO, in order to find a kind of MGA by hydrogenation of DMO that can overcome the above-mentioned shortcomings in the prior art.
  • Use a catalyst The present inventors have found that the bimetallic-composite carrier catalyst obtained by loading silver and ruthenium bimetallic active components on a SiO 2 -ZrO 2 composite carrier has a high specific surface area and high metal dispersion, and can be used at low temperature Efficiently convert DMO to MGA with high DMO conversion rate and high MGA selectivity. With the extension of reaction time, the high DMO conversion rate and high MGA selectivity are maintained when the reaction time reaches 1500h.
  • An object of the present invention is to provide a kind of double metal/composite carrier Ag-Ru/SiO 2 -ZrO 2 catalyst, this catalyst has high specific surface area, when being used for by DMO hydrogenation MGA, can react at lower temperature to convert DMO to MGA. While maintaining high DMO conversion and high MGA selectivity, the catalyst has an ultra-long lifetime.
  • Another object of the present invention is to provide a method for preparing bimetallic/composite supported catalysts.
  • the Ag-Ru/SiO 2 -ZrO 2 catalyst prepared by the method is used to prepare MGA from DMO hydrogenation, it can convert DMO into MGA at a reduced reaction temperature. While maintaining high DMO conversion and high MGA selectivity, the catalyst has an ultra-long lifetime.
  • a final object of the present invention is to provide a process for the preparation of MGA by hydrogenation of DMO using the catalyst of the present invention.
  • the method can achieve high DMO conversion and high MGA selectivity at low reaction temperature and pressure while maintaining high stability.
  • a catalyzer especially the catalyzer of producing methyl glycolate, it comprises composite support SiO 2 -ZrO 2 and the bimetallic active ingredient silver-ruthenium loaded on the composite support, wherein the specific surface area of the catalyst is 100 -1000m 2 /g, preferably 150-700m 2 /g, more preferably 300-500m 2 /g.
  • a method of preparing the catalyst according to any one of embodiments 1-5 comprising the steps of:
  • step (3) mixing the homogeneous mixture obtained in step (1) with the bimetallic solution obtained in step (2), adding a precipitating agent, and then evaporating to obtain a viscous substance;
  • a method for preparing methyl glycolate comprising in the presence of a catalyst according to any one of embodiments 1-5 or a catalyst prepared according to any one of embodiments 6-8, Under hydrogenation reaction conditions, dimethyl oxalate is contacted with hydrogen to carry out hydrogenation reaction.
  • the hydrogenation reaction conditions include: the liquid hourly space velocity of dimethyl oxalate is 0.01-10g/g catalyst.h , the temperature of the hydrogenation reaction is 100-300°C, and The pressure of the hydrogen reaction is 0.1-15MPa, the molar ratio of hydrogen to dimethyl oxalate is 10:1-250:1; it can be preferably: the liquid hourly space velocity of dimethyl oxalate is 0.5-8g/g catalyst.h , add The temperature of the hydrogen reaction is 130-210°C, the pressure of the hydrogenation reaction is 1-5MPa, and the molar ratio of hydrogen to dimethyl oxalate is 20:1-100:1.
  • a bimetallic/composite carrier catalyst which comprises a composite carrier and a bimetallic active component supported on the carrier.
  • the bimetallic/composite carrier catalyst of the present invention is a supported catalyst.
  • the carrier in the present invention is a silicon-zirconium-based composite carrier.
  • the content of the composite support is usually 65-97% by weight, preferably 80-92% by weight, more preferably 85-90% by weight.
  • the content of ZrO 2 /(SiO 2 +ZrO 2 ) in the composite carrier is 3-95% by weight, preferably 5-70% by weight, more preferably 5-50% by weight.
  • the bimetallic active components are mainly distributed in the pores of the carrier. Based on the total weight of the catalyst, the content of the bimetallic active ingredient is usually 3-35% by weight, preferably 8-20% by weight, more preferably 10-15% by weight in terms of elements. In the catalyst of the present invention, the Ag/(Ag+Ru) content is 5-95% by weight, preferably 20-80% by weight, more preferably 30-75% by weight.
  • the catalyst has a specific surface area of 100-1000 m 2 /g, preferably 150-700 m 2 /g, more preferably 300-500 m 2 /g.
  • the pore volume of the catalyst is 0.1-2.5 cm 3 /g, preferably 0.2-2.0 cm 3 /g, more preferably 0.4-1.5 cm 3 /g.
  • the pore size is 1-100 nm, preferably 2-50 nm, more preferably 3-20 nm.
  • a method for preparing the catalyst of the present invention comprising the steps of:
  • step (3) mixing the homogeneous mixture obtained in step (1) with the bimetallic solution obtained in step (2), adding a precipitating agent, and then evaporating to obtain a viscous substance;
  • step (1) the way in which the carrier material of the catalyst is added to water (preferably deionized water) is conventional, for example, the carrier material can be added at 5-55°C (preferably room temperature (25°C)) Add to water with stirring to form a homogeneous mixture.
  • water preferably deionized water
  • the carrier material can be added at 5-55°C (preferably room temperature (25°C)) Add to water with stirring to form a homogeneous mixture.
  • the amount of water used can be 100-2000 wt%, preferably 150-1500 wt%, all based on the total weight of the carrier material.
  • the silicon-based material in step (1) can be solid silicon oxide powder, silica sol or silicate.
  • the zirconium-based material can be zirconia powder, tetrabutyl zirconate or zirconium nitrate.
  • step (1) after the carrier material has been added to the water, a slow-release agent is added, for which it is advantageous to use ammonium chloride, ammonium acetate, urea or ethanol as the slow-release agent for this step.
  • step (1) it is preferred that the addition of all materials in step (1) is carried out under stirring, such as mechanical stirring, to ensure uniform and stable distribution.
  • stirring such as mechanical stirring
  • the reaction mixture is continuously stirred for 5-120 minutes at a stirring speed of 50-600 rpm, so that the obtained mixture is sufficiently uniform and stable.
  • step (2) the bimetallic salt is dissolved in water (preferably deionized water) to prepare a bimetallic salt solution.
  • the silver salts are soluble nitrates, hydrofluorides and organic acid salts, preferably nitrates.
  • the ruthenium salt is soluble nitrate, hydrochloride, sulfate, carbonate and organic acid salt, preferably soluble nitrate, more preferably ruthenium nitrosyl nitrate.
  • step (3) the homogeneous mixture obtained in step (1) is mixed with the bimetallic solution obtained in step (2), and then a precipitating agent is added to obtain a sticky substance.
  • the precipitating agent comprises ammonia and ammonium salts or mixtures thereof, preferably ammonia and ammonium salts, more preferably aqueous ammonia, ammonium nitrate and ammonium carbonate.
  • the homogeneous mixture obtained in step (1) In order to make the metal more fully and more uniformly distributed in the pores of the carrier, it is generally advantageous to mix the homogeneous mixture obtained in step (1) with the bimetallic solution obtained in step (2) and add the precipitating agent.
  • the resulting mixture was stirred at 20-80 °C for 20-120 min. More advantageously, after mixing the homogeneous mixture obtained in step (1) with the bimetallic solution obtained in step (2) and adding a precipitating agent, the resulting mixture is stirred at 30-70° C. for 30-60 min.
  • the precipitating agent ammonia water is added.
  • the resulting mixture is then distilled with ammonia to remove the ammonia and leave the metal components in the pores.
  • the conditions for distilling ammonia are not particularly limited, and the conditions for distilling ammonia preferably include: the temperature for distilling ammonia is 50-130° C.; the time for distilling ammonia is 0.5-50 hours. Further preferred ammonia distillation temperature is 60-120°C; ammonia distillation time is 2-48 hours. It is particularly preferred that the ammonia distillation temperature is 80-110°C; the ammonia distillation time is 2-12 hours. Ammonia distillation can be carried out under stirring, such as mechanical stirring, and the stirring speed can be 200-600rpm. After distilling ammonia, a viscous substance was obtained.
  • step (4) the viscous material obtained in step (3) is subjected to the steps of washing, drying, optionally tableting, roasting, optionally crushing and optionally sieving.
  • the present invention has no special limitation on the washing in step (4), and usually uses water to wash one or more times until the washing liquid is neutral.
  • the present invention has no special limitation on the drying conditions in step (4).
  • the drying conditions include: the drying temperature is 50-160° C.; the drying time is 3-48 hours. Further preferred drying temperature is 60-150°C; drying time is 6-24 hours. Particularly preferred drying temperature is 100-150°C; drying time is 6-20 hours.
  • the present invention has no particular limitation on the drying method in step (4), for example, ordinary heat drying, microwave drying and/or spray drying can be used, preferably spray drying.
  • a firing step is performed.
  • the firing temperature can be 150-800° C., and the firing time can be 1-12 hours.
  • the firing temperature is 200-600° C., and the firing time is 2-10 hours. Further preferably, the firing temperature is 250-500° C., and the firing time is 3-6 hours.
  • the dried material is optionally shaped according to a conventional method before firing.
  • the molding method can be, for example, tablet molding, rolling ball molding or extrusion molding.
  • an adhesive can be optionally added to facilitate processing and molding.
  • the catalyst obtained in step (4) can also be further molded after crushing to be processed into a desired molded body.
  • a binder can be added.
  • the catalyst obtained in step (4) is crushed, mixed with a binder, ground, and then compressed into tablets to obtain catalyst tablets. If it is desired to obtain catalyst granules, the resulting catalyst tablets can also be crushed and sieved.
  • a method for preparing methyl glycolate comprising, in the presence of the composite carrier catalyst of the present invention, under hydrogenation reaction conditions, making dimethyl oxalate contact with hydrogen to carry out hydrogenation reaction .
  • the hydrogenation reaction conditions may include: the liquid hourly space velocity of dimethyl oxalate is 0.01-10g/g catalyst.h , the temperature of the hydrogenation reaction is 100-300°C, the pressure of the hydrogenation reaction is 0.1-15MPa, the molar ratio of hydrogen to dimethyl oxalate is 10:1-250:1. It can be preferably: the liquid hourly space velocity of dimethyl oxalate is 0.5-8g/g catalyst.h , the temperature of hydrogenation reaction is 130-210°C, the pressure of hydrogenation reaction is 1-5MPa, the hydrogen and dimethyl oxalate The molar ratio is 20:1-100:1.
  • the bimetal/composite carrier catalyst of the present invention needs to be hydrogenated and reduced before being used to catalyze the hydrogenation of dimethyl oxalate to produce methyl glycolate.
  • the conditions for the hydroreduction are conventional.
  • the reducing gas is hydrogen or a mixed gas comprising hydrogen and a gas inert to the reduction reaction.
  • the reduction temperature is usually 100-300°C, preferably 150-250°C.
  • the reduction time is usually 2-48 hours, preferably 3-24 hours.
  • Dimethyl oxalate hydrogenation synthesis methyl glycolate of the present invention can be carried out in any reactor that can realize above-mentioned reaction condition, for example can carry out in fixed bed reactor, fluidized bed reactor or slurry state reactor, Preference is given to working in fixed bed reactors.
  • N2 physical adsorption was analyzed by Micromeritics ASAP 2020 at -196°C (liquid nitrogen temperature) to determine the specific surface area, pore volume, average pore diameter and other parameters of the catalyst.
  • the catalyst sample was evacuated to 70mmHg at 300°C, and pretreated under this condition for 6h to remove traces of water and impurities adsorbed on the surface of the catalyst. Then, the adsorption-desorption isotherms were measured by the static method.
  • the specific surface area of the catalyst was calculated by the BET (Bnmauer-Emmet-Teller) theory combined with the adsorption isotherm; the pore volume of the catalyst was obtained by the BJH (Barrett-Joyner-Halenda) theory and the desorption isotherm; the average pore diameter of the catalyst was calculated by the BJH ( Barrett-Joyner-Halenda) theory.
  • the content of each component of the catalyst was determined by the I.C.P method.
  • step (3) Mix the carrier mixture obtained in step (1) and the double metal salt solution obtained in step (2) under stirring at room temperature, then add 80 g of 28% by weight ammonia water and stir for 30 °C at a temperature of 30 ° C and a stirring speed of 600 rpm Minutes; then ammonia was distilled at 85°C for 3 hours with stirring at 300rpm to form a viscous substance.
  • step (3) The viscous material obtained in step (3) was washed with deionized water until the washing liquid was neutral, and then dried at 120° C. for 12 hours to obtain a bimetallic/composite carrier powder, 28 g in total.
  • the obtained bimetallic/composite support powder is pressed into tablets, calcined, crushed and sieved to obtain a granular catalyst with a particle size of 20-40 meshes, namely the bimetallic/composite support catalyst Ag-Ru/SiO 2 -ZrO 2 -1.
  • the specific surface area of the obtained catalyst is 410.25m 2 /g
  • the pore volume is 0.83cm 3 /g
  • the average pore diameter is 7.82nm
  • the silver content in the catalyst is 7% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 3% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst is 80% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
  • this catalyst reduction, reduction condition is: the H of 15 volume % and the N of 85 volume % mixed gas, flow through the catalyst bed from the top of the reactor with the flow velocity of 120ml/min, from the bottom of the reactor Discharge, the reduction temperature is 200°C, and the reduction time is 12 hours.
  • reaction conditions are as follows: the molar ratio of hydrogen to dimethyl oxalate (DMO) is 40:1, the liquid hourly space velocity of dimethyl oxalate is 2.0g/ml.h, the reaction temperature is 150°C, and the reaction pressure is 1.5MPa. After 3 hours of reaction, samples were taken and analyzed to determine the conversion rate and product distribution of DMO. The reaction results are shown in Table 1.
  • Example 2 Substantially the same as Example 1, the difference is: the silicon powder A380 feeding intake in step (1) is changed from 20g to 17g and tetrabutyl zirconate is changed from 7.8g to 15.2g;
  • step (2) The feeding changes in step (2) were as follows: silver nitrate was changed from 2.75g to 2.7g, and ruthenium nitrosyl nitrate was changed from 2.4g to 2.3g to finally obtain the Ag-Ru/SiO 2 -ZrO 2 -2 catalyst.
  • the specific surface area of the obtained catalyst was 439.14m 2 /g
  • the pore volume was 0.93cm 3 /g
  • the average pore diameter was 8.9nm
  • the silver content in the catalyst was 7% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 3% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst was 70% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst was 20% by weight calculated as zirconium oxide.
  • step (1) the feeding intake of silicon powder A380 is changed from 20g to 14.5g and tetrabutyl zirconate is changed from 7.8g to 12.5g;
  • step (2) The feeding changes in step (2) were as follows: silver nitrate was changed from 2.75g to 2.7g, and ruthenium nitrosyl nitrate was changed from 2.4g to 2.3g to finally obtain the Ag-Ru/SiO 2 -ZrO 2 -3 catalyst.
  • the specific surface area of the obtained catalyst is 458.8m 2 /g
  • the pore volume is 0.89cm 3 /g
  • the average pore diameter is 7.71nm
  • the silver content in the catalyst is 7% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 3% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst was 60% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst was 30% by weight calculated as zirconium oxide.
  • step (1) the feeding intake of silicon powder A380 is changed from 20g to 22.0g and tetrabutyl zirconate is changed from 7.8g to 4.0g;
  • step (2) The feeding changes in step (2) were as follows: silver nitrate was changed from 2.75g to 2.85g, and ruthenium nitrosyl nitrate was changed from 2.4g to 2.43g to finally obtain Ag-Ru/SiO 2 -ZrO 2 -4 catalyst.
  • the specific surface area of the obtained catalyst is 384.95m 2 /g
  • the pore volume is 0.92cm 3 /g
  • the average pore diameter is 9.55nm
  • the silver content in the catalyst is 7% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 3% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst was 85% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst was 5% by weight calculated as zirconium oxide.
  • step (1) the feeding intake of silicon powder A380 is changed from 20g to 18.0g and tetrabutyl zirconate is changed from 7.8g to 7.0g;
  • step (2) The feeding changes in step (2) were as follows: silver nitrate was changed from 2.75g to 2.14g, and ruthenium nitrosyl nitrate was changed from 2.4g to 2.85g to finally obtain Ag-Ru/SiO 2 -ZrO 2 -5 catalyst.
  • the specific surface area of the obtained catalyst was 402.71m 2 /g, the pore volume was 0.68cm 3 /g, the average pore diameter was 6.72nm, and the silver content in the catalyst was 6% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 4% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst is 80% by weight calculated as silicon oxide, and the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
  • step (1) the feeding intake of silicon powder A380 is changed from 20g to 18.0g and tetrabutyl zirconate is changed from 7.8g to 7.0g;
  • step (2) The feeding changes in step (2) were as follows: silver nitrate was changed from 2.75g to 1.80g, and ruthenium nitrosyl nitrate was changed from 2.4g to 3.60g to finally obtain the Ag-Ru/SiO 2 -ZrO 2 -6 catalyst.
  • the specific surface area of the obtained catalyst is 384.06m 2 /g
  • the pore volume is 0.89cm 3 /g
  • the average pore diameter is 9.22nm
  • the silver content in the catalyst is 5% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 5% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst was 80% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst was 10% by weight calculated as zirconium oxide.
  • step (1) the feeding intake of silicon powder A380 is changed from 20g to 18.0g and tetrabutyl zirconate is changed from 7.8g to 7.0g;
  • step (2) The feeding changes in step (2) were as follows: silver nitrate was changed from 2.75g to 1.42g, and ruthenium nitrosyl nitrate was changed from 2.4g to 4.24g to finally obtain the Ag-Ru/SiO 2 -ZrO 2 -7 catalyst.
  • the specific surface area of the obtained catalyst was 365.37m 2 /g
  • the pore volume was 0.83cm 3 /g
  • the average pore diameter was 9.11nm
  • the silver content in the catalyst was 4% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 6% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst is 80% by weight calculated as silicon oxide, and the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
  • the feeding intake in step (1) is changed to silicon powder A380 22.0g and tetrabutyl zirconate 0g;
  • step (2) The feeding in step (2) was changed to 2.69 g of silver nitrate and 2.3 g of ruthenium nitrosyl nitrate to finally obtain the Ag-Ru/SiO 2 -A1 catalyst.
  • the specific surface area of the obtained catalyst is 295.82m 2 /g
  • the pore volume is 0.57cm 3 /g
  • the average pore diameter is 7.67nm
  • the silver content in the catalyst is 7% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 3% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst was 90% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst was 0% by weight calculated as zirconia.
  • the feeding intake in step (1) is changed to silicon powder A380 20.0g and tetrabutyl zirconate 7.8g;
  • step (2) was changed to 3.95 g of silver nitrate and 0 g of ruthenium nitrosyl nitrate to finally obtain the Ag/SiO 2 -ZrO 2 -A2 catalyst.
  • the specific surface area of the obtained catalyst is 330.5m 2 /g
  • the pore volume is 0.60cm 3 /g
  • the average pore diameter is 7.28nm
  • the silver content in the catalyst is 10% by weight calculated as silver element.
  • the content of ruthenium in the catalyst, calculated as ruthenium element is 0% by weight.
  • the content of silicon in the catalyst is 80% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
  • the feed intake in step (1) is changed to silicon powder A380 21.0g and tetrabutyl zirconate 7.9g;
  • step (2) was changed to 0 g of silver nitrate and 5.6 g of ruthenium nitrosyl nitrate to finally obtain a Ru/SiO 2 -ZrO 2 -A3 catalyst.
  • the specific surface area of the obtained catalyst is 307.17m 2 /g
  • the pore volume is 0.61cm 3 /g
  • the average pore diameter is 7.95nm
  • the content of ruthenium in the catalyst is 7% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst was 83% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst was 10% by weight calculated as zirconium oxide.
  • the feeding intake in step (1) is changed to silicon powder A380 20.0g and tetrabutyl zirconate 7.8g;
  • step (2) was changed to 24.0 g of copper nitrate trihydrate and 0 g of ruthenium nitrosyl nitrate to finally obtain a Cu/SiO 2 -ZrO 2 -A4 catalyst.
  • the specific surface area of the obtained catalyst is 303.36m 2 /g
  • the pore volume is 0.54cm 3 /g
  • the average pore diameter is 7.1nm
  • the copper content in the catalyst is 20% by weight calculated as copper element.
  • the content of zirconium in the catalyst was 10% by weight calculated as zirconium oxide.
  • the feed intake in step (1) is changed to silicon powder A380 24.0g and tetrabutyl zirconate 0g;
  • step (2) was changed to 0 g of silver nitrate and 5.6 g of ruthenium nitrosyl nitrate to finally obtain Ru/SiO 2 -A5 catalyst.
  • the specific surface area of the obtained catalyst is 292.3m 2 /g
  • the pore volume is 0.50cm 3 /g
  • the average pore diameter is 6.9nm
  • the content of ruthenium in the catalyst is 7% by weight calculated as ruthenium element.
  • step (1) 4g of urea is changed to 4g of ammonium acetate to finally obtain an Ag-Ru/SiO 2 -ZrO 2 -8 catalyst.
  • the specific surface area of the obtained catalyst was 417.49m 2 /g, the pore volume was 0.73cm 3 /g, the average pore diameter was 7.02nm, and the silver content in the catalyst was 7% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 3% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst is 80% by weight calculated as silicon oxide, and the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
  • step (3) ammonia water is changed to 40g ammonium nitrate, and Ag-Ru/SiO 2 -ZrO 2 -9 catalyst is finally obtained
  • the specific surface area of the obtained catalyst was 413.2m 2 /g, the pore volume was 0.68cm 3 /g, the average pore diameter was 6.62nm, and the silver content in the catalyst was 7% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 3% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst is 80% by weight calculated as silicon oxide, and the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
  • step (3) change 80g of 28% ammonia water into 40g of ammonium carbonate, and finally obtain Ag-Ru/SiO 2 -ZrO 2 -10 catalyst
  • the specific surface area of the obtained catalyst was 428.2m 2 /g
  • the pore volume was 0.84cm 3 /g
  • the average pore diameter was 7.88nm
  • the silver content in the catalyst was 7% by weight calculated as silver element.
  • the content of ruthenium in the catalyst is 3% by weight calculated as ruthenium element.
  • the content of silicon in the catalyst is 80% by weight calculated as silicon oxide
  • the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
  • the catalyst of Example 1 was used.
  • Catalyst evaluation was similar to Example 1, with the same reaction conditions but extended reaction times. When reaching 1500h, the conversion rate of DMO is 90.13%, and the selectivity of MGA is 94.93%.
  • the catalyst of Example 4 was used.
  • the catalyst was evaluated similarly to Example 4, with the same reaction conditions but with extended reaction times. When reaching 1500h, the conversion rate of DMO is 91.07%, and the selectivity of MGA is 93.77%.
  • the catalyst of Example 7 was used.
  • the evaluation of the catalyst was similar to Example 7, the reaction conditions were the same, but the reaction time was extended. When reaching 1500h, the conversion rate of DMO is 92.54%, and the selectivity of MGA is 93.69%.
  • the evaluation of the catalyst was similar to Comparative Example 5, the reaction conditions were the same, but the reaction time was prolonged. When reaching 150h, the conversion rate of DMO is 69.22%, and the selectivity of MGA is 44.32%.

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Abstract

La présente invention concerne un catalyseur de support composite bimétallique/SiO2-ZrO2 à base d'argent-ruthénium et son procédé de préparation, et concerne en outre un procédé de préparation de glycolate de méthyle à partir d'oxalate de diméthyle au moyen du catalyseur. Le catalyseur de support composite bimétallique de la présente invention obtenu en supportant des composants actifs bimétalliques à base d'argent et de ruthénium sur un support composite SiO2-ZrO2 peut convertir efficacement un DMO en MGA à basse température, le taux de conversion de DMO est élevé, la sélectivité de MGA est élevée, et avec le prolongement du temps de réaction, un taux de conversion de DMO élevé et une sélectivité de MGA élevée sont maintenus lorsque le temps de réaction atteint 1 500 h.
PCT/CN2022/095930 2021-05-31 2022-05-30 Catalyseur de support composite bimétallique/sio2-zro2 à base d'argent-ruthénium et son procédé de préparation et son application WO2022253171A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115920944A (zh) * 2022-12-23 2023-04-07 西北化工研究院有限公司 一种草酸二甲酯加氢生成乙醇酸甲酯催化剂的制备方法
CN116459846A (zh) * 2023-05-09 2023-07-21 中国科学院兰州化学物理研究所 一种羟基酯加氢纳米Cu基催化剂及其制备方法与应用

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
CN116651445A (zh) * 2023-05-25 2023-08-29 四川大学 钌-银/炭催化剂及制备方法和应用

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JPS57123143A (en) * 1981-01-26 1982-07-31 Ube Ind Ltd Production of glycolic ester
CN102336666A (zh) * 2011-07-08 2012-02-01 上海华谊（集团）公司 一种草酸二甲酯加氢合成乙醇酸甲酯和乙二醇的制备方法

Patent Citations (2)

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JPS57123143A (en) * 1981-01-26 1982-07-31 Ube Ind Ltd Production of glycolic ester
CN102336666A (zh) * 2011-07-08 2012-02-01 上海华谊（集团）公司 一种草酸二甲酯加氢合成乙醇酸甲酯和乙二醇的制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115920944A (zh) * 2022-12-23 2023-04-07 西北化工研究院有限公司 一种草酸二甲酯加氢生成乙醇酸甲酯催化剂的制备方法
CN116459846A (zh) * 2023-05-09 2023-07-21 中国科学院兰州化学物理研究所 一种羟基酯加氢纳米Cu基催化剂及其制备方法与应用
CN116459846B (zh) * 2023-05-09 2024-03-26 中国科学院兰州化学物理研究所 一种羟基酯加氢纳米Cu基催化剂及其制备方法与应用

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