WO2022253171A1 - Silver-ruthenium bimetallic/sio2-zro2 composite support catalyst and preparation method therefor and application thereof - Google Patents

Silver-ruthenium bimetallic/sio2-zro2 composite support catalyst and preparation method therefor and application thereof 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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PCT/CN2022/095930
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Chinese (zh)
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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
    • B01J35/60—
    • B01J35/615—
    • B01J35/635—
    • B01J35/647—
    • 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%.

Abstract

The present invention relates to a silver-ruthenium bimetallic/SiO2-ZrO2 composite support catalyst and a preparation method therefor, and further relates to a method for preparing methyl glycolate from dimethyl oxalate using the catalyst. The bimetallic-composite support catalyst of the present invention obtained by supporting silver and ruthenium bimetallic active components on a SiO2-ZrO2 composite support can efficiently convert DMO to MGA at low temperature, the DMO conversion rate is high, the MGA selectivity is high, and with the prolongation of reaction time, a high DMO conversion rate and a high MGA selectivity are maintained when the reaction time reaches 1500 h.

Description

银-钌双金属/SiO 2-ZrO 2复合载体催化剂及其制备方法和应用 Silver-ruthenium bimetal/SiO 2-ZrO 2 Composite carrier catalyst and its preparation method and application 技术领域technical field
本发明涉及一种银-钌双金属/SiO 2-ZrO 2复合载体催化剂及其制备方法，还涉及使用该催化剂由草酸二甲酯制备乙醇酸甲酯的方法。 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.
背景技术Background technique
乙醇酸甲酯(MGA)分子结构独特，兼有醇和酯的化学性质，是当前高端农药、医药、化工环保领域亟需化学品，是合成纤维素、橡胶、树脂等的优良溶剂。此外，乙醇酸甲酯能够发生羰化反应、水解反应、氧化反应等，成为一种重要的化工原料。目前乙醇酸甲酯的传统合成方法有很多，而这些传统工艺中大多存在不足，例如乙二醛与甲醇一步合成法制备MGA，原料中的乙二醛毒性太大，并且价格高，不适用于工业化生产；甲醛与氢氰酸加成法，原料氢氰酸有剧毒，即使收率较高也不适合大规模生产；偶联法，大多采用液体和固体强酸催化，存在严重的腐蚀及反应压力高的缺陷。目前，在我国多采用氯代乙酸水解再酯化的方法，存在腐蚀重、污染重、原料有限等问题。Methyl glycolate (MGA) 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. At present, 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.
开发利用我国丰富的煤炭和天然气资源，发展C1化学具有重要的战略意义和经济价值，因此，从煤制乙醇酸甲酯引起广泛重视。目前，从合成气制草酸二甲酯(简称DMO)技术比较成熟，主要研究集中在草酸二甲酯加氢制备MGA上。It is of great strategic significance and economic value to exploit my country's abundant coal and natural gas resources and to develop C1 chemistry. Therefore, the production of methyl glycolate from coal has attracted widespread attention. At present, the technology of producing dimethyl oxalate (DMO for short) from syngas is relatively mature, and the main research focuses on the preparation of MGA by hydrogenation of dimethyl oxalate.
郭向前等人(广州化工，第43卷，第8期，2015-09，91-93页)采用沉淀沉积法制备了负载在二氧化硅上的CuO-Ag 2O/SiO 2固体催化剂，用于草酸二甲酯加氢制备乙醇酸甲酯反应。在反应温度230℃，压力2.0MPa，氢酯比30：1，液时空速0.8h -1条件下，草酸二甲酯转化率可以达到92.3％，乙醇酸甲酯选择性可以达到83.6％，反应连续运行500h，草酸二甲酯转化率稳定在90％左右，乙醇酸甲酯选 择性稳定在80％左右。该催化剂的反应温度高，而Cu基催化剂在高温下稳定性比较差，因此该催化剂的寿命还没有达到工业化的水平。 Guo Xiangqian et al. (Guangzhou Chemical Industry, Vol. 43, No. 8, 2015-09, Pages 91-93) prepared CuO-Ag 2 O/SiO 2 solid catalyst supported on silica by precipitation deposition method for Hydrogenation of dimethyl oxalate to methyl glycolate. Under the conditions of reaction temperature 230°C, pressure 2.0MPa, hydrogen-ester ratio 30:1, and liquid hourly space velocity 0.8h -1 , the conversion rate of dimethyl oxalate can reach 92.3%, and the selectivity of methyl glycolate can reach 83.6%. After continuous operation for 500 hours, the conversion rate of dimethyl oxalate is stable at about 90%, and the selectivity of methyl glycolate is stable at about 80%. The reaction temperature of the catalyst is high, while the Cu-based catalyst has poor stability at high temperature, so the service life of the catalyst has not yet reached the level of industrialization.
CN108620107A报道了一种用于草酸二甲酯加氢合成乙醇酸甲酯的催化剂及其制备方法和应用。所述催化剂以NiM双元素颗粒为活性组分，TiO 2为载体；所述NiM双元素颗粒的第一种元素为金属Ni，第二种元素M为非金属B、P中的任何一种；所述载体TiO 2的表面积为2-200m 2/g，孔体积为2-200cm 3/g，孔径为0.05-5nm；所述催化剂中金属Ni含量为5重量％-25重量％，元素M含量为2重量％-10重量％。 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公开了一种草酸二甲酯加氢合成乙醇酸甲酯的催化剂及其制备方法，所述催化剂以金属铜为主活性组分，银和锰为助活性组分，Al 2O 3为载体；其中金属铜含量为催化剂质量的25％～50％，金属银含量为催化剂质量的5％～15％，金属锰含量为催化剂质量的8％～20％，Al 2O 3含量为催化剂质量的15％～40％。 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%.
龚海燕等人(化学反应与工程，第30卷，第2期，2014-04，17-23页)采用蒸氨法制备了铜负载在二氧化硅上的CuO/SiO 2固体催化剂，用于草酸二甲酯加氢制备乙醇酸甲酯反应。在氢酯比40～60、压力2～2.5MPa、反应温度453～473K、空速0.3～0.7mg/(g-Cat·h)的较佳工艺条件下草酸二甲酯的转化率大于80％，乙醇酸甲酯的选择性大于80％。该催化剂的活性不够高，没有稳定性报道。 Gong Haiyan et al. (Chemical Reaction and Engineering, Vol. 30, No. 2, 2014-04, 17-23 pages) prepared CuO/SiO 2 solid catalyst with copper supported on silica by ammonia distillation method, which is used for Hydrogenation of dimethyl oxalate to methyl glycolate. The conversion rate of dimethyl oxalate is greater than 80% under the optimal process conditions of hydrogen-ester ratio of 40-60, pressure of 2-2.5MPa, reaction temperature of 453-473K, and space velocity of 0.3-0.7mg/(g-Cat h). , the selectivity of methyl glycolate is greater than 80%. The activity of this catalyst is not high enough, and there is no stability report.
天津大学的欧阳梦瑶(学位论文，2016，5)用水热晶化法合成出了多级孔纳米氧化硅球(KCC-1)作为载体，用等体积浸渍法制备了Ag/KCC-1催化剂，考察了Ag的负载量对催化草酸酯加氢合成乙醇酸甲酯的催化性能的影响规律。研究发现当银的负载量为15％时，催化剂具有较高的活性金属银表面积，因此表现出较好的催化活性。在1.75h -1空速时，MGA的收率最高为90.2％，DMO的转化率为97.8％，MGA的选择性为92.2％。然而，在该方法中，银含量太高，且载体制备过程复杂。 Ouyang Mengyao from Tianjin University (dissertation, 2016, 5) synthesized hierarchical porous nano-silica spheres (KCC-1) as a carrier by hydrothermal crystallization method, and prepared Ag/KCC-1 catalyst by equal volume impregnation method , the effect of Ag loading on the catalytic performance of oxalate hydrogenation to methyl glycolate was investigated. It was found that when the loading amount of silver was 15%, the catalyst had a higher surface area of active metal silver, and thus exhibited better catalytic activity. At a space velocity of 1.75h -1 , the highest yield of MGA was 90.2%, the conversion rate of DMO was 97.8%, and the selectivity of MGA was 92.2%. However, in this method, the silver content is too high, and the carrier preparation process is complicated.
目前，草酸二甲酯加氢制备乙醇酸甲酯的工艺主要采用银基催化剂或铜基 催化剂。采用银催化剂时，草酸二甲酯生成MGA的选择性很高，但是，银在高温下容易烧结，催化剂稳定性差，在低温下活性较低。采用铜基催化剂时，在较高反应温度下，活性高，但是MGA容易生成乙二醇，副产物多，另外由于有大量副产物甲醇的生成，容易造成载体的硅流失，催化剂失活速率快，且失活催化剂不可再生，因此需要开发一种低温活性高，催化剂寿命长的工业化催化剂。At present, the technology of preparing methyl glycolate by hydrogenation of dimethyl oxalate mainly adopts silver-based catalyst or copper-based catalyst. When silver catalyst is used, 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. When a copper-based catalyst is used, the activity is high at a relatively high reaction temperature, but MGA is easy to generate ethylene glycol and has many by-products. In addition, 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.
发明内容Contents of the invention
鉴于上述现有技术状况，本发明的发明人在DMO加氢制MGA用催化剂方面进行了广泛而又深入的研究，以期发现一种能够克服现有技术所存在的上述缺点的DMO加氢制MGA用催化剂。本发明人发现，将银和钌双金属活性成分负载在一种SiO 2-ZrO 2复合载体上得到的双金属-复合载体催化剂，具有高的比表面积和高的金属分散性，可以在低温下将DMO高效地转化为MGA，DMO转化率高，MGA选择性高，随反应时间延长，达到1500h时保持高的DMO转化率和高的MGA选择性。 In view of the above-mentioned state of the art, 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.
本发明的一个目的是提供一种双金属/复合载体Ag-Ru/SiO 2-ZrO 2催化剂，该催化剂具有高的比表面积，在用于由DMO加氢制MGA时，能够在较低的反应温度下将DMO转化为MGA。在保持高的DMO转化率和高的MGA选择性的同时，该催化剂具有超长寿命。 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.
本发明的另一个目的是提供一种制备双金属/复合载体催化剂的方法。该方法制得的Ag-Ru/SiO 2-ZrO 2催化剂在用于由DMO加氢制MGA时，能够在降低的反应温度下将DMO转化为MGA。在保持高的DMO转化率和高的MGA选择性的同时，该催化剂具有超长寿命。 Another object of the present invention is to provide a method for preparing bimetallic/composite supported catalysts. When 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.
本发明的最后一个目的是提供一种采用本发明催化剂由DMO加氢制备MGA的方法。该方法能够在较低的反应温度和压力下，实现高的DMO转化率和高的MGA选择性，同时还能保持高的稳定性。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.
实现本发明的上述目的的实施方案可概括如下：The embodiment that realizes above-mentioned object of the present invention can be summarized as follows:
1.一种催化剂，尤其是制乙醇酸甲酯的催化剂，其包含复合载体SiO 2-ZrO 2和负载在该复合载体上的双金属活性成分银-钌，其中所述催化剂的比表面积为100-1000m 2/g，优选为150-700m 2/g，更优选为300-500m 2/g。 1. 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.
2.根据实施方案1所述的催化剂，其中所述催化剂的孔容为0.1-2.5cm 3/g，优选为0.2-2.0cm 3/g，更优选为0.4-1.5cm 3/g，和/或孔径为1-100nm，优选为2-50nm，更优选为3-20nm。 2. The catalyst according to embodiment 1, wherein the catalyst has a pore volume of 0.1-2.5 cm 3 /g, preferably 0.2-2.0 cm 3 /g, more preferably 0.4-1.5 cm 3 /g, and/ Or the pore size is 1-100 nm, preferably 2-50 nm, more preferably 3-20 nm.
3.根据实施方案1或2所述的催化剂，其中复合载体的含量为65-97重量％，优选为80-92重量％，更优选为85-90重量％，双金属活性成分的含量以元素计为3-35重量％，优选为8-20重量％，更优选为10-15重量％，均基于催化剂的总重量。3. The catalyst according to embodiment 1 or 2, wherein the content of the composite support is 65-97% by weight, preferably 80-92% by weight, more preferably 85-90% by weight, and the content of the bimetallic active ingredient is expressed as element It is calculated as 3-35% by weight, preferably 8-20% by weight, more preferably 10-15% by weight, all based on the total weight of the catalyst.
4.根据实施方案1-3中任一项所述的催化剂，其中复合载体中ZrO 2/(SiO 2+ZrO 2)含量为3-95重量％，优选为5-70重量％，更优选为5-50重量％ 4. The catalyst according to any one of embodiments 1-3, wherein the content of ZrO 2 /(SiO 2 +ZrO 2 ) in the composite support is 3-95% by weight, preferably 5-70% by weight, more preferably 5-50% by weight
5.根据实施方案1-4中任一项所述的催化剂，其中Ag/(Ag+Ru)含量为5-95重量％，优选为20-80重量％，更优选为30-75重量％。5. The catalyst according to any one of embodiments 1-4, wherein the Ag/(Ag+Ru) content is 5-95% by weight, preferably 20-80% by weight, more preferably 30-75% by weight.
6.一种制备根据实施方案1-5中任一项所述的催化剂的方法，包括如下步骤：6. A method of preparing the catalyst according to any one of embodiments 1-5, comprising the steps of:
(1)将硅基材料和锆基材料加入到水中，并加入缓释剂，搅拌，得到均匀混合物；(1) adding the silicon-based material and the zirconium-based material into water, and adding a slow-release agent, stirring to obtain a uniform mixture;
(2)将银盐和钌盐溶解到水中，制得双金属溶液；(2) silver salt and ruthenium salt are dissolved in water, and bimetallic solution is obtained;
(3)将步骤(1)得到的均匀混合物与步骤(2)得到的双金属溶液混合，加入沉淀剂，然后蒸发，得到粘稠物；以及(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; and
(4)将步骤(3)得到的粘稠物进行洗涤、干燥、任选地压片、焙烧、任选地破碎和任选地筛分的步骤。(4) Washing, drying, optionally tableting, roasting, optionally crushing and optionally sieving the viscous material obtained in step (3).
7.根据实施方案6所述的方法，其中所述银盐为可溶性硝酸盐、氢氟酸盐和有机酸盐，优选硝酸盐，和/或所述钌盐为可溶性硝酸盐、盐酸盐、硫酸盐、碳酸盐和有机酸盐，优选可溶性硝酸盐，更优选亚硝酰基硝酸合钌。7. The method according to embodiment 6, wherein the silver salts are soluble nitrates, hydrofluorates and organic acid salts, preferably nitrates, and/or the ruthenium salts are soluble nitrates, hydrochlorides, Sulfate, carbonate and organic acid salt, preferably soluble nitrate, more preferably ruthenium nitrosyl nitrate.
8.根据实施方案6或7所述的方法，其中所述缓释剂为氯化铵、醋酸铵、尿素或乙醇。8. The method of embodiment 6 or 7, wherein the sustained release agent is ammonium chloride, ammonium acetate, urea or ethanol.
9.一种制备乙醇酸甲酯的方法，该方法包括在根据实施方案1-5中任一项所 述的催化剂或根据实施方案6-8中任一项所述方法制备的催化剂存在下，在加氢反应条件下，使草酸二甲酯与氢气接触进行加氢反应。9. A method for preparing methyl glycolate, the method 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.
10.根据实施方案9所述的方法，其中所述加氢反应条件包括：草酸二甲酯的液时空速为0.01-10g/g 催化剂.h，加氢反应的温度为100-300℃，加氢反应的压力为0.1-15MPa，氢气与草酸二甲酯的摩尔比为10：1-250：1；可优选为：草酸二甲酯的液时空速为0.5-8g/g 催化剂.h，加氢反应的温度为130-210℃，加氢反应的压力为1-5MPa，氢气与草酸二甲酯的摩尔比为20：1-100：1。 10. The method according to embodiment 9, wherein 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.
具体实施方式Detailed ways
根据本发明的第一个方面，提供了一种双金属/复合载体催化剂，该催化剂包含一种复合载体和负载在该载体上的双金属活性成分。According to the first aspect of the present invention, there is provided a bimetallic/composite carrier catalyst, which comprises a composite carrier and a bimetallic active component supported on the carrier.
本发明双金属/复合载体催化剂为负载型催化剂。The bimetallic/composite carrier catalyst of the present invention is a supported catalyst.
本发明中的载体为硅基-锆基复合载体。基于催化剂的总重量，复合载体的含量通常为65-97重量％，优选为80-92重量％，更优选为85-90重量％。复合载体中ZrO 2/(SiO 2+ZrO 2)含量为3-95重量％，优选为5-70重量％，更优选为5-50重量％。 The carrier in the present invention is a silicon-zirconium-based composite carrier. Based on the total weight of the catalyst, 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.
在本发明的催化剂中，双金属活性成分主要分布在载体的孔道内。基于催化剂的总重量，双金属活性成分的含量以元素计通常为3-35重量％，优选为8-20重量％，更优选为10-15重量％。在本发明的催化剂中，Ag/(Ag+Ru)含量为5-95重量％，优选为20-80重量％，更优选为30-75重量％。In the catalyst of the present invention, 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.
在本发明的一个实施方案中，所述催化剂的比表面积为100-1000m 2/g，优选为150-700m 2/g，更优选为300-500m 2/g。在本发明的一个优选实施方案中，所述催化剂的孔容为0.1-2.5cm 3/g，优选为0.2-2.0cm 3/g，更优选为0.4-1.5cm 3/g。在本发明的另一个优选实施方案中，孔径为1-100nm，优选为2-50nm，更优选为3-20nm。 In one embodiment of the present invention, 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. In a preferred embodiment of the present invention, 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. In another preferred embodiment of the present invention, the pore size is 1-100 nm, preferably 2-50 nm, more preferably 3-20 nm.
本发明人发现，在硅基载体中添加第二载体组分，可以成功抑制脱硅和银聚集，提高催化剂的使用寿命。The inventors found that adding the second carrier component to the silicon-based carrier can successfully suppress desiliconization and silver aggregation, and improve the service life of the catalyst.
根据本发明的第二个方面，提供了一种制备本发明催化剂的方法，包括如下步骤：According to a second aspect of the present invention, there is provided a method for preparing the catalyst of the present invention, comprising the steps of:
(1)将硅基材料和锆基材料加入到水中，并加入缓释剂，搅拌，得到均匀混合物；(1) adding the silicon-based material and the zirconium-based material into water, and adding a slow-release agent, stirring to obtain a uniform mixture;
(2)将银盐和钌盐溶解到水中，制得双金属溶液；(2) silver salt and ruthenium salt are dissolved in water, and bimetallic solution is obtained;
(3)将步骤(1)得到的均匀混合物与步骤(2)得到的双金属溶液混合，加入沉淀剂，然后蒸发，得到粘稠物；以及(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; and
(4)将步骤(3)得到的粘稠物进行洗涤、干燥、任选地压片、焙烧、任选地破碎和任选地筛分的步骤。(4) Washing, drying, optionally tableting, roasting, optionally crushing and optionally sieving the viscous material obtained in step (3).
根据本发明，在步骤(1)中，将催化剂的载体材料加入到水(优选去离子水)中的方式是常规的，例如可以将载体材料在5-55℃(优选室温(25℃))和搅拌条件下加入到水中，以形成均匀混合物。According to the present invention, in 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.
在本发明的步骤(1)中，对水的用量没有特别要求，水的用量可为100-2000重量％，优选为150-1500重量％，均基于载体材料的总重量。In the step (1) of the present invention, there is no special requirement on the amount of water used, and the amount of water used can be 100-2000 wt%, preferably 150-1500 wt%, all based on the total weight of the carrier material.
在本发明的一个实施方案中，步骤(1)中的硅基材料可为固体氧化硅粉末、硅溶胶或硅酸酯。锆基材料可为氧化锆粉末、锆酸四丁酯或硝酸锆。In one embodiment of the present invention, 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.
在步骤(1)中，在载体材料加入到水中之后，加入缓释剂，对此有利的是使用氯化铵、醋酸铵、尿素或乙醇作为该步骤的缓释剂。In 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.
例如，优选步骤(1)中所有物料的加入均在搅拌如机械搅拌下进行，以确保分布均匀及稳定。通常而言，将反应混合物继续搅拌5-120分钟，搅拌转速为50-600rpm，以使得到的混合物充分的均匀稳定。For example, 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. Generally speaking, 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.
根据本发明，在步骤(2)中，将双金属盐溶解到水(优选去离子水)中，制得双金属盐溶液。According to the present invention, in step (2), the bimetallic salt is dissolved in water (preferably deionized water) to prepare a bimetallic salt solution.
所述银盐为可溶性硝酸盐、氢氟酸盐和有机酸盐，优选硝酸盐。所述钌盐为可溶性硝酸盐、盐酸盐、硫酸盐、碳酸盐和有机酸盐，优选可溶性硝酸盐，更优选亚硝酰基硝酸合钌。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.
根据本发明，在步骤(3)中，将步骤(1)得到的均匀混合物与步骤(2)得到的双金属溶液混合，然后加入沉淀剂，得到粘稠物。According to the present invention, in 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.
在本发明的一个实施方案中，沉淀剂包括氨和铵盐或其混合物，优选氨和铵盐，更优选氨水、硝酸铵和碳酸铵。In one embodiment of the present invention, 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.
为了使得金属更充分地、更均匀地分布于载体的孔道内，通常有利的是，在将步骤(1)得到的均匀混合物与步骤(2)得到的双金属溶液混合和加入沉淀剂之后，将所得混合物在20-80℃下搅拌20-120min。更有利的是，在将步骤(1)得到的均匀混合物与步骤(2)得到的双金属溶液混合和加入沉淀剂之后，将所得混合物在30-70℃下搅拌30-60min。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.
在本发明的一个优选实施方案中，加入沉淀剂氨水。然后，将所得混合物蒸氨，以除去氨水，并在孔道内留下金属组分。蒸氨的条件没有特别限制，优选所述蒸氨的条件包括：蒸氨温度为50-130℃；蒸氨时间为0.5-50小时。进一步优选蒸氨温度为60-120℃；蒸氨时间为2-48小时。特别优选蒸氨温度为80-110℃；蒸氨时间为2-12小时。蒸氨可以在搅拌如机械搅拌下进行，搅拌的速度可以为200-600rpm。经过蒸氨，得到粘稠物。In a preferred embodiment of the present invention, 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.
根据本发明，在步骤(4)中，将步骤(3)得到的粘稠物进行洗涤、干燥、任选地压片、焙烧、任选地破碎和任选地筛分的步骤。According to the present invention, in 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.
本发明对于步骤(4)中的洗涤没有特别的限制，通常采用水洗涤一次或多次，直到洗液呈中性。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.
本发明对于步骤(4)中的干燥条件没有特别限制，优选所述干燥条件包括：干燥的温度为50-160℃；干燥的时间为3-48小时。进一步优选干燥的温度为60-150℃；干燥的时间为6-24小时。特别优选干燥的温度为100-150℃；干燥的时间为6-20小时。本发明对于步骤(4)中的干燥的方法没有特别限制，例如可以采用普通加热干燥、微波干燥和/或喷雾干燥，优选为喷雾干燥。The present invention has no special limitation on the drying conditions in step (4). Preferably, 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.
在步骤(4)中，进行焙烧步骤。焙烧的温度可以为150-800℃，焙烧的时间可以为1-12小时。优选的是，焙烧的温度为200-600℃，焙烧的时间为2-10小时。 进一步优选的是，焙烧的温度为250-500℃，焙烧的时间为3-6小时。In step (4), a firing step is performed. The firing temperature can be 150-800° C., and the firing time can be 1-12 hours. Preferably, 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.
在本发明方法的步骤(4)中，在焙烧之前，任选地将干燥得到的物料按照常规的方法进行成型。成型的方法例如可以为压片成型、滚球成型或挤出成型，此时可任选地加入粘接剂，以利于加工成型。In step (4) of the method of the present invention, 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. In this case, an adhesive can be optionally added to facilitate processing and molding.
在本发明的一个实施方案中，也可将步骤(4)得到的催化剂在破碎后进一步成型，加工成所需成型体。在成型过程中，根据成型加工的难易程度、催化剂所需的强度，可以加入粘接剂。通常而言，将步骤(4)得到的催化剂破碎后与粘接剂混合、研磨、然后压片，得到催化剂片剂。如果想要获得催化剂颗粒，还可将所得催化剂片剂破碎和筛分。In one embodiment of the present invention, the catalyst obtained in step (4) can also be further molded after crushing to be processed into a desired molded body. In the molding process, according to the difficulty of molding processing and the strength required by the catalyst, a binder can be added. Generally speaking, 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.
根据本发明的最后方面，提供了一种制备乙醇酸甲酯的方法，该方法包括在本发明复合载体催化剂存在下，在加氢反应条件下，使草酸二甲酯与氢气接触进行加氢反应。According to the last aspect of the present invention, there is provided a method for preparing methyl glycolate, the method 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 .
根据本发明的制备方法，所述加氢反应条件可以包括：草酸二甲酯的液时空速为0.01-10g/g 催化剂.h，加氢反应的温度为100-300℃，加氢反应的压力为0.1-15MPa，氢气与草酸二甲酯的摩尔比为10：1-250：1。可优选为：草酸二甲酯的液时空速为0.5-8g/g 催化剂.h，加氢反应的温度为130-210℃，加氢反应的压力为1-5MPa，氢气与草酸二甲酯的摩尔比为20：1-100：1。 According to the preparation method of the present invention, 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.
如果本发明的双金属/复合载体催化剂尚未活化，需要在用于催化草酸二甲酯加氢制乙醇酸甲酯之前将其加氢还原。加氢还原的条件是常规的。通常而言，还原气体为氢气或包含氢气和对该还原反应呈惰性的气体的混合气。还原温度通常为100-300℃，优选150-250℃。还原时间通常为2-48小时，优选3-24小时。If the bimetal/composite carrier catalyst of the present invention has not been activated, it 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. Generally speaking, 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.
本发明的草酸二甲酯加氢合成乙醇酸甲酯可以在任何能够实现上述反应条件的反应器中进行，例如可以在固定床反应器、流化床反应器或浆态床反应器中进行，优选在固定床反应器中进行。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.
通过使用本发明催化剂来催化DMO加氢合成乙醇酸甲酯，能够在低温低压 下实现高的DMO转化率和高的MGA选择性。By using the catalyst of the present invention to catalyze DMO hydrogenation to synthesize methyl glycolate, high DMO conversion rate and high MGA selectivity can be realized at low temperature and low pressure.
实施例Example
下面借助实施例和对比例详细描述本发明，但本发明的范围并不限于这些实施例。The present invention is described in detail below by means of examples and comparative examples, but the scope of the present invention is not limited to these examples.
以下实施例和对比例中，采用气相色谱法进行体系中各组分的分析，通过校正归一法进行定量。In the following examples and comparative examples, the analysis of each component in the system was carried out by gas chromatography, and the quantification was carried out by calibration and normalization method.
N 2物理吸附采用Micromeritics ASAP 2020在-196℃(液氮温度)下进行分析，用于测定催化剂的比表面积、孔容、平均孔径等参数。首先，将催化剂样品于300℃下抽真空至70mmHg，在此条件下预处理6h用以除去吸附在催化剂表面上的微量水和杂质。然后，采用静态法测量吸附-脱附等温线。催化剂的比表面积由BET(Bnmauer-Emmet-Teller)理论结合吸附等温线计算得到；催化剂的孔容由BJH(Barrett-Joyner-Halenda)理论和脱附等温线求得；催化剂的平均孔径由BJH(Barrett-Joyner-Halenda)理论求得。 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. First, 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.
用I.C.P法测定催化剂各个成分的含量。The content of each component of the catalyst was determined by the I.C.P method.
实施例1Example 1
1.催化剂的制备：1. Preparation of catalyst:
(1)称取硅粉A380(德国EVONIK公司)20g和锆酸四丁酯(日本Kanto Chemical公司)7.8g，溶解在200mL去离子水中，加入4g尿素，在室温(即25℃，下同)和搅拌速度150rpm下搅拌120分钟，得到载体混合物。(1) Weigh 20g of silicon powder A380 (EVONIK, Germany) and 7.8g of tetrabutyl zirconate (Kanto Chemical, Japan), dissolve them in 200mL of deionized water, add 4g of urea, and heat at room temperature (25°C, the same below) Stir at a stirring speed of 150 rpm for 120 minutes to obtain a carrier mixture.
(2)室温避光下，将2.75g硝酸银和2.4g亚硝酰基硝酸合钌(日本Kanto Chemical公司)溶解到300mL水中。(2) Dissolve 2.75 g of silver nitrate and 2.4 g of ruthenium nitrosyl nitrate (Kanto Chemical Company, Japan) in 300 mL of water at room temperature in the dark.
(3)室温和搅拌下将步骤(1)得到的载体混合物和步骤(2)得到的双金属盐溶液混合，然后在温度为30℃和搅拌速度为600rpm下加入80g 28重量％氨水并搅拌30分钟；然后在85℃下和300rpm搅拌下蒸氨3小时，形成粘稠物。(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 ℃ 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.
(4)将步骤(3)得到的粘稠物用去离子水洗涤，直到洗液呈中性，然后在 120℃下干燥12小时，即得到双金属/复合载体粉末，共28g。将得到的双金属/复合载体粉末压片成型、焙烧、破碎和筛分，得到粒径为20-40目的颗粒催化剂，即双金属/复合载体催化剂Ag-Ru/SiO 2-ZrO 2-1。 (4) 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.
经测定，所得催化剂的比表面积为410.25m 2/g，孔容为0.83cm 3/g，平均孔径为7.82nm，银以银元素计在催化剂中的含量为7重量％。钌以钌元素计在催化剂中的含量为3重量％。硅以氧化硅计在催化剂中的含量为80重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It is determined that 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, and 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, and the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
2.催化剂的评价：2. Catalyst evaluation:
将上面制备的催化剂颗粒1.5ml，放入内径为10毫米且高40厘米的立管式固定床反应器内。反应评价前，将该催化剂还原，还原条件为：15体积％的H 2和85体积％的N 2混合气体，以120ml/min的流速从反应器顶部流过催化剂床层，从反应器的底部排出，还原温度为200℃，还原时间为12小时。还原结束后，用纯氢置换还原气体，升高反应系统压力达到1.5MPa，催化剂床层温度降低到150℃，开始通入DMO的20重量％甲醇溶液，其中氢气和草酸二甲酯在进入反应器前混合，然后从反应器的顶部进入管式反应器中，经反应后，产物从反应器的底部排出。反应条件如下：氢气与草酸二甲酯(DMO)的摩尔比为40:1，草酸二甲酯的液时空速为2.0g/ml.h，反应温度为150℃，反应压力为1.5MPa。经3小时的反应后取样分析，确定DMO的转化率与产物分布。反应结果见表1。 1.5 ml of the catalyst particles prepared above were put into a vertical tube fixed-bed reactor with an inner diameter of 10 mm and a height of 40 cm. Before reaction evaluation, 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. After the reduction, replace the reducing gas with pure hydrogen, increase the pressure of the reaction system to 1.5MPa, reduce the temperature of the catalyst bed to 150°C, and start to feed 20% by weight of DMO in methanol solution, wherein hydrogen and dimethyl oxalate are entering the reaction Mix before the reactor, and then enter the tubular reactor from the top of the reactor, after the reaction, the product is discharged from the bottom of the reactor. The 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.
实施例2Example 2
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中的硅粉A380投料由20g改为17g和锆酸四丁酯由7.8g改为15.2g；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;
在步骤(2)中的投料变更如下：硝酸银由2.75g改为2.7g和亚硝酰基硝酸 合钌由2.4g改为2.3g，最终得到Ag-Ru/SiO 2-ZrO 2-2催化剂。 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.
经测定，所得催化剂的比表面积为439.14m 2/g，孔容为0.93cm 3/g，平均孔径为8.9nm，银以银元素计在催化剂中的含量为7重量％。钌以钌元素计在催化剂中的含量为3重量％。硅以氧化硅计在催化剂中的含量为70重量％，锆以氧化锆计在催化剂中的含量为20重量％。 It was determined that 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, 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 was 70% by weight calculated as silicon oxide, and the content of zirconium in the catalyst was 20% by weight calculated as zirconium oxide.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
实施例3Example 3
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中硅粉A380的投料由20g改为14.5g和锆酸四丁酯由7.8g改为12.5g；Substantially the same as Example 1, the difference is: in 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;
在步骤(2)中的投料变更如下：硝酸银由2.75g改为2.7g和亚硝酰基硝酸合钌由2.4g改为2.3g，最终得到Ag-Ru/SiO 2-ZrO 2-3催化剂。 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.
经测定，所得催化剂的比表面积为458.8m 2/g，孔容为0.89cm 3/g，平均孔径为7.71nm，银以银元素计在催化剂中的含量为7重量％。钌以钌元素计在催化剂中的含量为3重量％。硅以氧化硅计在催化剂中的含量为60重量％，锆以氧化锆计在催化剂中的含量为30重量％。 It is determined that 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, and 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, and the content of zirconium in the catalyst was 30% by weight calculated as zirconium oxide.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
实施例4Example 4
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中硅粉A380的投料由20g 改为22.0g和锆酸四丁酯由7.8g改为4.0g；Substantially the same as Example 1, the difference is: in 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;
在步骤(2)中的投料变更如下：硝酸银由2.75g改为2.85g和亚硝酰基硝酸合钌由2.4g改为2.43g，最终得到Ag-Ru/SiO 2-ZrO 2-4催化剂。 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.
经测定，所得催化剂的比表面积为384.95m 2/g，孔容为0.92cm 3/g，平均孔径为9.55nm，银以银元素计在催化剂中的含量为7重量％。钌以钌元素计在催化剂中的含量为3重量％。硅以氧化硅计在催化剂中的含量为85重量％，锆以氧化锆计在催化剂中的含量为5重量％。 It is determined that 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, and 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, and the content of zirconium in the catalyst was 5% by weight calculated as zirconium oxide.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
实施例5Example 5
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中硅粉A380的投料由20g改为18.0g和锆酸四丁酯由7.8g改为7.0g；Substantially the same as Example 1, the difference is: in 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;
在步骤(2)中的投料变更如下：硝酸银由2.75g改为2.14g和亚硝酰基硝酸合钌由2.4g改为2.85g，最终得到Ag-Ru/SiO 2-ZrO 2-5催化剂。 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.
经测定，所得催化剂的比表面积为402.71m 2/g，孔容为0.68cm 3/g，平均孔径为6.72nm，银以银元素计在催化剂中的含量为6重量％。钌以钌元素计在催化剂中的含量为4重量％。硅以氧化硅计在催化剂中的含量为80重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It was determined that 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.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
实施例6Example 6
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中硅粉A380的投料由20g改为18.0g和锆酸四丁酯由7.8g改为7.0g；Substantially the same as Example 1, the difference is: in 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;
在步骤(2)中的投料变更如下：硝酸银由2.75g改为1.80g和亚硝酰基硝酸合钌由2.4g改为3.60g，最终得到Ag-Ru/SiO 2-ZrO 2-6催化剂。 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.
经测定，所得催化剂的比表面积为384.06m 2/g，孔容为0.89cm 3/g，平均孔径为9.22nm，银以银元素计在催化剂中的含量为5重量％。钌以钌元素计在催化剂中的含量为5重量％。硅以氧化硅计在催化剂中的含量为80重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It is determined that 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, and 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, and the content of zirconium in the catalyst was 10% by weight calculated as zirconium oxide.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
实施例7Example 7
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中硅粉A380的投料由20g改为18.0g和锆酸四丁酯由7.8g改为7.0g；Substantially the same as Example 1, the difference is: in 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;
在步骤(2)中的投料变更如下：硝酸银由2.75g改为1.42g和亚硝酰基硝酸合钌由2.4g改为4.24g，最终得到Ag-Ru/SiO 2-ZrO 2-7催化剂。 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.
经测定，所得催化剂的比表面积为365.37m 2/g，孔容为0.83cm 3/g，平均孔径为9.11nm，银以银元素计在催化剂中的含量为4重量％。钌以钌元素计在催化剂中的含量为6重量％。硅以氧化硅计在催化剂中的含量为80重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It was determined that 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, and 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.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
对比例1Comparative example 1
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中的投料变更为硅粉A38022.0g和锆酸四丁酯0g；Substantially the same as Example 1, the difference is: the feeding intake in step (1) is changed to silicon powder A380 22.0g and tetrabutyl zirconate 0g;
在步骤(2)中的投料变更为硝酸银2.69g和亚硝酰基硝酸合钌2.3g，最终得到Ag-Ru/SiO 2-A1催化剂。 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.
经测定，所得催化剂的比表面积为295.82m 2/g，孔容为0.57cm 3/g，平均孔径为7.67nm，银以银元素计在催化剂中的含量为7重量％。钌以钌元素计在催化剂中的含量为3重量％。硅以氧化硅计在催化剂中的含量为90重量％，锆以氧化锆计在催化剂中的含量为0重量％。 It is determined that 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, and 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, and the content of zirconium in the catalyst was 0% by weight calculated as zirconia.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
对比例2Comparative example 2
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中的投料变更为硅粉A38020.0g和锆酸四丁酯7.8g；Substantially the same as Example 1, the difference is: the feeding intake in step (1) is changed to silicon powder A380 20.0g and tetrabutyl zirconate 7.8g;
在步骤(2)中的投料变更为硝酸银3.95g和亚硝酰基硝酸合钌0g，最终得到Ag/SiO 2-ZrO 2-A2催化剂。 The feeding in 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.
经测定，所得催化剂的比表面积为330.5m 2/g，孔容为0.60cm 3/g，平均孔径为7.28nm，银以银元素计在催化剂中的含量为10重量％。钌以钌元素计在催化剂中的含量为0重量％。硅以氧化硅计在催化剂中的含量为80重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It is determined that 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, and 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, and the content of zirconium in the catalyst is 10% by weight calculated as zirconia.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
对比例3Comparative example 3
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中的投料变更为硅粉A38021.0g和锆酸四丁酯7.9g；Substantially the same as Example 1, the difference is: the feed intake in step (1) is changed to silicon powder A380 21.0g and tetrabutyl zirconate 7.9g;
在步骤(2)中的投料变更为硝酸银0g和亚硝酰基硝酸合钌5.6g，最终得到Ru/SiO 2-ZrO 2-A3催化剂。 The feeding in 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.
经测定，所得催化剂的比表面积为307.17m 2/g，孔容为0.61cm 3/g，平均孔径为7.95nm，钌以钌元素计在催化剂中的含量为7重量％。硅以氧化硅计在催化剂中的含量为83重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It is determined that 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, and 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, and the content of zirconium in the catalyst was 10% by weight calculated as zirconium oxide.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
对比例4Comparative example 4
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中的投料变更为硅粉A38020.0g和锆酸四丁酯7.8g；Substantially the same as Example 1, the difference is: the feeding intake in step (1) is changed to silicon powder A380 20.0g and tetrabutyl zirconate 7.8g;
在步骤(2)中的投料变更为24.0g三水合硝酸铜和亚硝酰基硝酸合钌0g，最终得到Cu/SiO 2-ZrO 2-A4催化剂。 The feeding in 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.
经测定，所得催化剂的比表面积为303.36m 2/g，孔容为0.54cm 3/g，平均孔径为7.1nm，铜以铜元素计在催化剂中的含量为20重量％。锆以氧化锆计在催化剂中的含量为10重量％。 It is determined that 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, and 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.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
对比例5Comparative example 5
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中的投料变更为硅粉A38024.0g和锆酸四丁酯0g；Substantially the same as Example 1, the difference is: the feed intake in step (1) is changed to silicon powder A380 24.0g and tetrabutyl zirconate 0g;
在步骤(2)中的投料变更为硝酸银0g和亚硝酰基硝酸合钌5.6g，最终得到Ru/SiO 2-A5催化剂。 The feeding in 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.
经测定，所得催化剂的比表面积为292.3m 2/g，孔容为0.50cm 3/g，平均孔径为6.9nm，钌以钌元素计在催化剂中的含量为7重量％。硅以氧化硅计在催化剂中的含量为93重量％。 It is determined that 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, and the content of ruthenium in the catalyst is 7% by weight calculated as ruthenium element. The content of silicon in the catalyst, calculated as silicon oxide, was 93% by weight.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
实施例8Example 8
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(1)中将4g尿素改为4g醋酸铵，最终得到Ag-Ru/SiO 2-ZrO 2-8催化剂。 It is basically the same as Example 1, except that in step (1), 4g of urea is changed to 4g of ammonium acetate to finally obtain an Ag-Ru/SiO 2 -ZrO 2 -8 catalyst.
经测定，所得催化剂的比表面积为417.49m 2/g，孔容为0.73cm 3/g，平均孔径为7.02nm，银以银元素计在催化剂中的含量为7重量％。钌以钌元素计在催化剂中的含量为3重量％。硅以氧化硅计在催化剂中的含量为80重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It was determined that 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.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
实施例9Example 9
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(3)中将氨水改为40g硝酸铵，最终得到Ag-Ru/SiO 2-ZrO 2-9催化剂 Basically the same as Example 1, the difference is: In step (3), ammonia water is changed to 40g ammonium nitrate, and Ag-Ru/SiO 2 -ZrO 2 -9 catalyst is finally obtained
经测定，所得催化剂的比表面积为413.2m 2/g，孔容为0.68cm 3/g，平均孔径为6.62nm，银以银元素计在催化剂中的含量为7重量％。钌以钌元素计在催化剂中的含量为3重量％。硅以氧化硅计在催化剂中的含量为80重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It was determined that 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.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
实施例10Example 10
1.催化剂的制备：1. Preparation of catalyst:
与实施例1基本相同，不同的是：在步骤(3)中将80g 28％氨水改为40g碳酸铵，最终得到Ag-Ru/SiO 2-ZrO 2-10催化剂 Basically the same as Example 1, the difference is: in step (3), change 80g of 28% ammonia water into 40g of ammonium carbonate, and finally obtain Ag-Ru/SiO 2 -ZrO 2 -10 catalyst
经测定，所得催化剂的比表面积为428.2m 2/g，孔容为0.84cm 3/g，平均孔径为7.88nm，银以银元素计在催化剂中的含量为7重量％。钌以钌元素计在催化剂中的含量为3重量％。硅以氧化硅计在催化剂中的含量为80重量％，锆以氧化锆计在催化剂中的含量为10重量％。 It was determined that 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, 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.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1。反应结果见表1。The catalyst was evaluated similarly to Example 1. The reaction results are shown in Table 1.
表1Table 1
Figure PCTCN2022095930-appb-000001
Figure PCTCN2022095930-appb-000001
实施例11Example 11
1.催化剂的制备：1. Preparation of catalyst:
使用实施例1的催化剂。The catalyst of Example 1 was used.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例1，反应条件相同，但反应时间延长。达到1500h时DMO的转化率为90.13％，MGA的选择性为94.93％。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%.
实施例12Example 12
1.催化剂的制备：1. Preparation of catalyst:
使用实施例4的催化剂。The catalyst of Example 4 was used.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例4，反应条件相同，但反应时间延长。达到1500h时DMO的转化率为91.07％，MGA的选择性为93.77％。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%.
实施例13Example 13
1.催化剂的制备：1. Preparation of catalyst:
使用实施例7的催化剂。The catalyst of Example 7 was used.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于实施例7，反应条件相同，但反应时间延长。达到1500h时DMO的转化率为92.54％，MGA的选择性为93.69％。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%.
对比实施例6Comparative Example 6
1.催化剂的制备：1. Preparation of catalyst:
使用对比实施例5的催化剂。The catalyst of Comparative Example 5 was used.
2.催化剂的评价：2. Catalyst evaluation:
催化剂的评价类似于对比实施例5，反应条件相同，但反应时间延长。达到150h时DMO的转化率为69.22％，MGA的选择性为44.32％。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%.

Claims (10)

  1. 一种催化剂，尤其是制乙醇酸甲酯的催化剂，其包含复合载体SiO 2-ZrO 2和负载在该复合载体上的双金属活性成分银-钌，其中所述催化剂的比表面积为100-1000m 2/g，优选为150-700m 2/g，更优选为300-500m 2/g。 A catalyst, especially a catalyst for producing methyl glycolate, comprising a composite carrier SiO 2 -ZrO 2 and a bimetallic active component silver-ruthenium loaded on the composite carrier, wherein the specific surface area of the catalyst is 100-1000m 2 /g, preferably 150-700m 2 /g, more preferably 300-500m 2 /g.
  2. 根据权利要求1所述的催化剂，其中所述催化剂的孔容为0.1-2.5cm 3/g，优选为0.2-2.0cm 3/g，更优选为0.4-1.5cm 3/g，和/或孔径为1-100nm，优选为2-50nm，更优选为3-20nm。 The catalyst according to claim 1, wherein 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, and/or pore diameter 1-100 nm, preferably 2-50 nm, more preferably 3-20 nm.
  3. 根据权利要求1或2所述的催化剂，其中复合载体的含量为65-97重量％，优选为80-92重量％，更优选为85-90重量％，双金属活性成分的含量以元素计为3-35重量％，优选为8-20重量％，更优选为10-15重量％，均基于催化剂的总重量。The catalyst according to claim 1 or 2, wherein the content of the composite carrier is 65-97% by weight, preferably 80-92% by weight, more preferably 85-90% by weight, and the content of the bimetal active component is calculated as 3-35% by weight, preferably 8-20% by weight, more preferably 10-15% by weight, all based on the total weight of the catalyst.
  4. 根据权利要求1-3中任一项所述的催化剂，其中复合载体中ZrO 2/(SiO 2+ZrO 2)含量为3-95重量％，优选为5-70重量％，更优选为5-50重量％。 The catalyst according to any one of claims 1-3, wherein the ZrO 2 /(SiO 2 +ZrO 2 ) content in the composite carrier is 3-95% by weight, preferably 5-70% by weight, more preferably 5- 50% by weight.
  5. 根据权利要求1-4中任一项所述的催化剂，其中Ag/(Ag+Ru)含量为5-95重量％，优选为20-80重量％，更优选为30-75重量％。The catalyst according to any one of claims 1-4, wherein the Ag/(Ag+Ru) content is 5-95% by weight, preferably 20-80% by weight, more preferably 30-75% by weight.
  6. 一种制备根据权利要求1-5中任一项所述的催化剂的方法，包括如下步骤：A method for preparing the catalyst according to any one of claims 1-5, comprising the steps of:
    (1)将硅基材料和锆基材料加入到水中，并加入缓释剂，搅拌，得到均匀混合物；(1) adding the silicon-based material and the zirconium-based material into water, and adding a slow-release agent, stirring to obtain a uniform mixture;
    (2)将银盐和钌盐溶解到水中，制得双金属溶液；(2) silver salt and ruthenium salt are dissolved in water, and bimetallic solution is obtained;
    (3)将步骤(1)得到的均匀混合物与步骤(2)得到的双金属溶液混合，加入沉淀剂，然后蒸发，得到粘稠物；以及(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; and
    (4)将步骤(3)得到的粘稠物进行洗涤、干燥、任选地压片、焙烧、任选地破碎和任选地筛分的步骤。(4) Washing, drying, optionally tableting, roasting, optionally crushing and optionally sieving the viscous material obtained in step (3).
  7. 根据权利要求6所述的方法，其中所述银盐为可溶性硝酸盐、氢氟酸盐和有机酸盐，优选硝酸盐，和/或所述钌盐为可溶性硝酸盐、盐酸盐、硫酸盐、碳酸盐和有机酸盐，优选可溶性硝酸盐，更优选亚硝酰基硝酸合钌。The method according to claim 6, wherein said silver salt is soluble nitrate, hydrofluoric acid salt and organic acid salt, preferred nitrate, and/or said ruthenium salt is soluble nitrate, hydrochloride, sulfate , carbonates and organic acid salts, preferably soluble nitrates, more preferably ruthenium nitrosyl nitrate.
  8. 根据权利要求6或7所述的方法，其中所述缓释剂为氯化铵、醋酸铵、尿 素或乙醇。The method according to claim 6 or 7, wherein the sustained release agent is ammonium chloride, ammonium acetate, urea or ethanol.
  9. 一种制备乙醇酸甲酯的方法，该方法包括在根据权利要求1-5中任一项所述的催化剂或根据权利要求6-8中任一项所述的方法制备的催化剂存在下，在加氢反应条件下，使草酸二甲酯与氢气接触进行加氢反应。A method for preparing methyl glycolate, the method comprising in the presence of the catalyzer according to any one of claims 1-5 or the catalyst prepared according to the method according to any one of claims 6-8, in Under hydrogenation reaction conditions, dimethyl oxalate is contacted with hydrogen to carry out hydrogenation reaction.
  10. 根据权利要求9所述的方法，其中所述加氢反应条件包括：草酸二甲酯的液时空速为0.01-10g/g 催化剂.h，加氢反应的温度为100-300℃，加氢反应的压力为0.1-15MPa，氢气与草酸二甲酯的摩尔比为10：1-250：1；优选的是，所述加氢反应条件包括：草酸二甲酯的液时空速为0.5-8g/g 催化剂.h，加氢反应的温度为130-210℃，加氢反应的压力为1-5MPa，氢气与草酸二甲酯的摩尔比为20：1-100：1。 The method according to claim 9, wherein 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 hydrogenation reaction The pressure is 0.1-15MPa, the molar ratio of hydrogen to dimethyl oxalate is 10:1-250:1; preferably, the hydrogenation reaction conditions include: the liquid hourly space velocity of dimethyl oxalate is 0.5-8g/ g catalyst.h , the temperature of the hydrogenation 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.
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CN116459846A (en) * 2023-05-09 2023-07-21 中国科学院兰州化学物理研究所 Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof

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JPS57123143A (en) * 1981-01-26 1982-07-31 Ube Ind Ltd Production of glycolic ester
CN102336666A (en) * 2011-07-08 2012-02-01 上海华谊（集团）公司 Method for synthesizing methyl glycollate and ethylene glycol by dimethyl oxalate hydrogenation

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JPS57123143A (en) * 1981-01-26 1982-07-31 Ube Ind Ltd Production of glycolic ester
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CN116459846A (en) * 2023-05-09 2023-07-21 中国科学院兰州化学物理研究所 Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof
CN116459846B (en) * 2023-05-09 2024-03-26 中国科学院兰州化学物理研究所 Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof

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