CN116273049B - Preparation method and activation method of catalyst for synthesizing methyl glycolate - Google Patents
Preparation method and activation method of catalyst for synthesizing methyl glycolate Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000004913 activation Effects 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 28
- 239000004332 silver Substances 0.000 claims abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- -1 silver ions Chemical class 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910017727 AgNi Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 39
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000012456 homogeneous solution Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000007790 scraping Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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- 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
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Abstract
The invention discloses a preparation method and an activation method of a catalyst for methyl glycolate, wherein a self-reduction pyrolysis method is adopted to prepare a porous catalyst loaded with AgNi alloy, a sol-gel method is adopted, a precursor with high dispersion active sites is obtained under the assistance of ultrasonic waves, and the precursor is stably existing in an aging process. The migration and agglomeration of silver species to the surface of the catalyst in the drying process are inhibited by combining microwave heating and vacuum drying, the stably existing nano-grade AgNi alloy particles are finally obtained, active site clusters can reach 10nm, the catalyst with low load (Ag content is 0.01-4wt%) and high dispersion and excellent performance is synthesized, and the utilization rate of metal atoms is improved. The prepared catalyst can be stored conventionally, and has no risks of combustion, inactivation and the like. The catalyst is used for preparing methyl glycolate through hydrogenation of oxalate, and has the advantages of high catalytic activity, high selectivity and good stability.
Description
Technical field:
The invention relates to the technical field of catalysis, in particular to a preparation method and an activation method of a catalyst for preparing methyl glycolate from dimethyl oxalate, and belongs to the technical field of catalyst preparation.
The background technology is as follows:
Methyl Glycolate (MG) is the simplest alkyd, and is an excellent solvent for cellulose, resins, rubber, and the like. Because the catalyst has a special structure of hydroxyl and ester, the catalyst can participate in various chemical reactions such as hydrogenation, ammonolysis, hydrolysis, carbonylation, oxidative dehydrogenation and the like, and is an important fine chemical intermediate, and related synthesis and application are always attracting attention.
At present, no mature environment-friendly MG production process exists in China, and the industrial production is mainly based on a chloroacetic acid hydrolysis method and a formaldehyde molecule carbonylation reesterification method. The process for preparing methyl glycolate from synthesis gas through dimethyl oxalate has the advantages of complex process, long flow, high cost, serious environmental pollution and low target product yield, combines the energy structure characteristics of China, takes coal with relatively abundant resources as raw materials, has more competitive advantages and has quite good development prospect.
According to literature reports, catalysts adopted in oxalate catalytic hydrogenation systems mainly comprise Ru, cu, ag and the like as active components. Noble metal Ru catalyst has good catalytic activity in liquid phase hydrogenation, but has more severe reaction conditions, high catalyst cost and difficult recovery, and limits large-scale production. Cu-based catalysts have higher conversion but relatively low selectivity to methyl glycolate (typically less than 80%) and poor operating stability. As a result of intensive studies, it was found that although Ag has a full d-type electron structure, ag has a weak dissociative adsorption ability for hydrogen, and activity in DMO hydrogenation is not high, selectivity for methyl glycolate is higher under the same conditions.
The selectivity of the Ag-based catalyst to MG can reach more than 90 percent (for example, JP06135895, JP06263692, CN 102336666A), and the improvement of the silver dispersion degree is beneficial to the improvement of the reaction selectivity. The conventional preparation method adopts carriers with high specific surface area, such as molecular sieve, active carbon, white carbon black and the like, so as to obtain high silver dispersity. Patent CN111437828a describes a silver-based catalyst for methyl glycolate, which is prepared by obtaining a highly dispersed silica carrier by a tetraethyl orthosilicate hydrolysis method, and the selectivity of the prepared catalyst can reach 92% of methyl glycolate. Patent CN112206772A describes a preparation method of oxalate hydrogenation catalyst with high Ag dispersion, which uses porous nano silicon dioxide as a carrier to prepare active component Ag with average particle size of 19nm and selectivity to methyl glycolate of over 96%. The specific steps are that SiO 2 solid is directly added into AgNO 3 solution containing dispersing agent, then liquid strong reducing agent is added to reduce the AgNO 3 solution into nano silver in situ, and the target catalyst is obtained through filtration, drying and roasting. The dispersing agent used in the method is polyvinylpyrrolidone (PVP), and researches show that PVP can block catalytic active sites under certain conditions, so that the catalytic efficiency is reduced; the cost of the reducer methyl glyoxylate is expensive, which is not beneficial to industrial production; the loss of Ag element can be generated in the filtering step, and the production cost is increased. Meanwhile, dangerous waste water, organic waste gas and the like which are difficult to treat are generated in the production process, the finished catalyst is also extremely easy to oxidize and inactivate, the risks of spontaneous combustion, corrosion and the like exist, and the industrial popularization is difficult. Therefore, the development of the catalyst synthesis method with high performance, simple process and environmental friendliness has important significance.
The invention comprises the following steps:
The invention aims to provide a preparation method of a catalyst for synthesizing methyl glycolate, which aims to solve the problems that the existing high-dispersion Ag catalyst needs to adopt expensive raw materials and the production process is easy to produce environmental pollution.
The second purpose of the invention is to provide a catalyst activation method for synthesizing methyl glycolate, which aims to solve the problems that the existing finished catalyst is easy to oxidize and deactivate, has risks of spontaneous combustion, corrosion and the like, and is difficult to popularize industrially.
The first object of the present invention is implemented by the following technical scheme: the preparation method of the catalyst for synthesizing methyl glycolate comprises the following steps:
S1, according to the content of each component of a target catalyst to be prepared, dissolving a compound containing nickel and silver elements in distilled water, fully stirring, and uniformly mixing to form a solution A;
s2, adding the powdered silicon dioxide or the silica sol into an alcohol solvent, fully stirring, and uniformly mixing to form a solution B;
S3, placing the solution B in an ultrasonic water bath at 40-90 ℃, slowly dropwise adding the solution A into the solution B in a mechanical stirring state for 3-6 hours to form gel, and then aging for 1-24 hours at room temperature;
S4, placing the gel obtained in the step S3 in a microwave oven or a microwave reactor, and adopting microwave treatment with power of 100-1000W and frequency of 2400-2500 MHz under a vacuum condition to reduce the moisture content of the gel to below 15%;
S5, roasting the microwave treated product obtained in the step S4 at 300-600 ℃ for 2-10 hours, and cooling to room temperature to obtain the target catalyst Ni-Ag/SiO 2.
Preferably, in the step S1, the compounds of nickel and silver are both present in the form of an acid or a salt of a metal.
Preferably, in the step S1, the compound of nickel and silver element is nickel nitrate and silver nitrate.
Preferably, in the step S1, the concentration of nickel ions in the solution A is 0.01-2.5 mol/L, and the concentration of silver ions is 0.01-10 mol/L.
Preferably, in the step S2, the alcohol solvent is isopropanol or ethanol.
Preferably, in the S5, the content of nickel element in the catalyst is 0-10wt%, and the content of silver element is 0.01-4wt%.
The nickel or silver component of the catalyst prepared by the method is distributed on silicon dioxide in a high-dispersity way, the specific surface area of the catalyst is larger than 200m, the pore volume is larger than 1.0cm 3/g, and the particle size of silver is smaller than 15nm.
The second object of the invention is implemented by the following technical scheme: a catalyst activation method for synthesizing methyl glycolate is characterized in that the catalyst is filled in a fixed bed reactor, the catalyst is reduced in a flowing hydrogen atmosphere, the reduction pressure is 0.1-1 MPa, the hydrogen volume space velocity is 200-5000 h -1, the temperature is increased to 180-230 ℃ at the speed of 0.5-2 ℃/min, the reaction temperature is 170-220 ℃ after the reduction is finished, the activation is completed, at the moment, methanol solution of dimethyl oxalate is introduced for hydrogenation reaction, the hydrogen pressure is 0.5-3 MPa, the molar ratio of hydrogen to dimethyl oxalate is 10:1-100:1, and the mass space velocity of dimethyl oxalate is 0.2-1 h -1, so that the methyl glycolate can be produced.
In order to solve the problems that the existing high-dispersion Ag catalyst needs to adopt expensive raw materials, the production process is easy to produce environmental pollution, potential safety hazards exist and the like,
On one hand, the invention adopts a self-reduction pyrolysis method to prepare the AgNi alloy-loaded porous catalyst, adopts a sol-gel method and obtains a precursor with high dispersion active sites under the assistance of ultrasonic waves, and enables the precursor to exist stably in the aging process. The migration and agglomeration of silver species to the surface of the catalyst in the drying process are inhibited by combining microwave heating and vacuum drying, the stably existing nano-grade AgNi alloy particles are finally obtained, active site clusters can reach 10nm, the catalyst with low load (Ag content is 0.01-4wt%) and high dispersion and excellent performance is synthesized, and the utilization rate of metal atoms is improved. The method avoids filtering operation, reduces the loss of Ag element, adopts a self-reduction pyrolysis method to obtain metal active sites, avoids the use of a reducing agent, and reduces the discharge of three wastes while saving the cost.
According to the first aspect, the catalyst is stored and transported in a solid form, the potential safety hazard is reduced, the catalyst is reduced and activated when in use, the catalyst is reduced in a flowing hydrogen atmosphere, the reduction pressure is 0.1-1 MPa, the hydrogen volume space velocity is 200-5000 h -1, the temperature is increased to 180-230 ℃ at the speed of 0.5-2 ℃/min, the catalyst is reduced for 2-4 h, the catalyst is cooled to the reaction temperature of 170-220 ℃ after the reduction is finished, the methanol solution of dimethyl oxalate is introduced for hydrogenation reaction, the hydrogen pressure is 0.5-3 MPa, the molar ratio of hydrogen to dimethyl oxalate is 10:1-100:1, and the mass space velocity of dimethyl oxalate is 0.2-1 h -1.
By means of the scheme, the invention has at least the following advantages:
according to the preparation and activation method of the methyl glycolate catalyst, the high-dispersion catalyst system can be obtained by using an inexpensive reagent through ultrasonic dispersion precipitation and microwave vacuum heating, the silver salt does not need ammoniation treatment, the filtrate does not have silver loss, the average particle size of the silver serving as an active component is 10nm, the dispersion degree of the silver is greatly improved, and the catalytic activity of the silver is enhanced; the prepared catalyst can be stored conventionally, and has no risks of combustion, inactivation and the like. The catalyst is used for preparing methyl glycolate through hydrogenation of oxalate, and has the advantages of high catalytic activity, high selectivity and good stability. The oxalate conversion rate is more than 95%, the methyl glycolate selectivity is more than 90%, and the method has wide application prospect.
The specific embodiment is as follows:
Example 1:
9.9g Ni (NO 3)2·6H2O、0.3g AgNO3 was dissolved in 50ml deionized water to form a homogeneous solution A; 17.3g powdered silica was mixed with 150g ethanol and stirred thoroughly to form solution B.
Solution B was heated to 40 ℃ and placed in an ultrasonic water bath and mechanical stirring was turned on. Slowly dropwise adding the solution A into the solvent B, controlling the dropwise adding time to be about 40min, and continuously stirring for 6h after the dropwise adding is finished. The generated materials are placed in a disc-type container and placed in a vacuum microwave heater, 1000w power is started to heat the materials, the disc continuously rotates in the heating process to enable the materials to be heated uniformly, and meanwhile, a fixed scraping plate above the disc continuously retreads the materials in the disc. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst C1. The average silver species particle size of the C1 catalyst was analyzed to be 10nm.
Example 2:
1.26g of AgNO 3 was dissolved in 50ml of deionized water to form a homogeneous solution A; 19.2g of powdered silica was mixed with 150g of ethanol and stirred well to form solution B.
Solution B was heated to 40 ℃ and placed in an ultrasonic water bath and mechanical stirring was turned on. Slowly dropwise adding the solution A into the solvent B, controlling the dropwise adding time to be about 40min, and continuously stirring for 6h after the dropwise adding is finished. The generated materials are placed in a disc-type container and placed in a vacuum microwave heater, 1000w power is started to heat the materials, the disc continuously rotates in the heating process to enable the materials to be heated uniformly, and meanwhile, a fixed scraping plate above the disc continuously retreads the materials in the disc. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst C2.
Example 3
9.9G Ni (NO 3)2·6H2O、1.26g AgNO3 was dissolved in 50ml deionized water to form a homogeneous solution A; 16.66g powdered silica was mixed with 150g ethanol and stirred thoroughly to form solution B.
Solution B was heated to 40 ℃ and placed in an ultrasonic water bath and mechanical stirring was turned on. Slowly dropwise adding the solution A into the solvent B, controlling the dropwise adding time to be about 40min, and continuously stirring for 6h after the dropwise adding is finished. The generated materials are placed in a disc-type container and placed in a vacuum microwave heater, 1000w power is started to heat the materials, the disc continuously rotates in the heating process to enable the materials to be heated uniformly, and meanwhile, a fixed scraping plate above the disc continuously retreads the materials in the disc. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst C3. The average silver species particle size of the C3 catalyst was analyzed to be 18nm.
Example 4
4.95G Ni (NO 3)2·6H2O、0.63g AgNO3 was dissolved in 50ml deionized water to form a homogeneous solution A; 18.33g powdered silica was mixed with 150g ethanol and stirred thoroughly to form solution B.
Solution B was heated to 40 ℃ and placed in an ultrasonic water bath and mechanical stirring was turned on. Slowly dropwise adding the solution A into the solvent B, controlling the dropwise adding time to be about 40min, and continuously stirring for 6h after the dropwise adding is finished. The generated materials are placed in a disc-type container and placed in a vacuum microwave heater, 1000w power is started to heat the materials, the disc continuously rotates in the heating process to enable the materials to be heated uniformly, and meanwhile, a fixed scraping plate above the disc continuously retreads the materials in the disc. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst C4.
Example 5
4.95G Ni (NO 3)2·6H2 O) was dissolved in 50ml deionized water to form a homogeneous solution A, and 18.73g powdered silica was mixed with 150g ethanol and stirred thoroughly to form solution B.
Solution B was heated to 40 ℃ and placed in an ultrasonic water bath and mechanical stirring was turned on. Slowly dropwise adding the solution A into the solvent B, controlling the dropwise adding time to be about 40min, and continuously stirring for 6h after the dropwise adding is finished. The generated materials are placed in a disc-type container and placed in a vacuum microwave heater, 1000w power is started to heat the materials, the disc continuously rotates in the heating process to enable the materials to be heated uniformly, and meanwhile, a fixed scraping plate above the disc continuously retreads the materials in the disc. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst C5.
Example 6
0.99G Ni (NO 3)2·6H2O、0.63g AgNO3 is dissolved in 50ml deionized water to form a homogeneous solution A; 19.35g powdered silica is mixed with 150g ethanol and stirred thoroughly to form solution B.
Solution B was heated to 40 ℃ and placed in an ultrasonic water bath and mechanical stirring was turned on. Slowly dropwise adding the solution A into the solvent B, controlling the dropwise adding time to be about 40min, and continuously stirring for 6h after the dropwise adding is finished. The generated materials are placed in a disc-type container and placed in a vacuum microwave heater, 1000w power is started to heat the materials, the disc continuously rotates in the heating process to enable the materials to be heated uniformly, and meanwhile, a fixed scraping plate above the disc continuously retreads the materials in the disc. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst C6.
Comparative example 1
9.9G Ni (NO 3)2·6H2O、0.3g AgNO3 was dissolved in 50ml deionized water to form a homogeneous solution A; 17.3g powdered silica was mixed with 150g ethanol and stirred thoroughly to form solution B.
Solution B was heated to 40 ℃ and mechanical stirring was turned on. Slowly dropwise adding the solution A into the solvent B, controlling the dropwise adding time to be about 40min, and continuously stirring for 6h after the dropwise adding is finished. The resulting material was heated in an oil bath at 120℃with stirring. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst D1.
Comparative example 2
9.9G Ni (NO 3)2·6H2O、1.26g AgNO3 was dissolved in 50ml deionized water to form a homogeneous solution A; 16.66g powdered silica was mixed with 150g ethanol and stirred thoroughly to form solution B.
Solution B was heated to 40 ℃ and mechanical stirring was turned on. Slowly dropwise adding the solution A into the solvent B, controlling the dropwise adding time to be about 30-60min, and continuously stirring for 6h after the dropwise adding is finished. The resulting material was heated in an oil bath at 120℃with stirring. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst D2.
Comparative example 3
9.9G Ni (NO 3)2·6H2O、1.26g AgNO3 and 0.9g PVP were dissolved in 50ml deionized water to form a homogeneous solution A, and 16.66g powdered silica was slowly added to solution A and stirred well.
The generated materials are placed in a disc-type container and placed in a vacuum microwave heater, 1000w power is started to heat the materials, the disc continuously rotates in the heating process to enable the materials to be heated uniformly, and meanwhile, a fixed scraping plate above the disc continuously retreads the materials in the disc. And (3) placing the dried powder material into a muffle furnace, roasting for 2h at 350 ℃, and cooling to room temperature to obtain the target catalyst D3. The average silver species particle size of the D3 catalyst was analyzed to be 25nm.
To illustrate the catalytic effect of the catalyst, the catalyst evaluations in the above examples and comparative examples were carried out by the following methods: 2g of catalyst is filled in a fixed bed reactor, the catalyst is reduced in a flowing hydrogen atmosphere, the reducing pressure is 0.1MPa, the hydrogen volume space velocity is 2000h -1, the temperature is increased to 230 ℃ at the speed of 2 ℃/min, the reduction is carried out for 4 hours, the reaction temperature is cooled to 170-220 ℃ after the reduction is finished, the methanol solution of dimethyl oxalate is introduced for hydrogenation reaction, the reaction pressure is 1.5MPa, the molar ratio of hydrogen to dimethyl oxalate is 50:1, and the mass space velocity of dimethyl oxalate is 0.6h -1.
Experimental data are as follows:
| Catalyst | Temperature, DEG C | Conversion, percent | Selectivity,% |
| C1 | 170 | 96 | 92 |
| C1 | 180 | 99 | 90 |
| C2 | 180 | 95 | 99 |
| C2 | 190 | 99 | 95 |
| C3 | 180 | 99 | 98 |
| C4 | 180 | 98 | 92 |
| C5 | 230 | 99 | 92 |
| C6 | 200 | 99 | 93 |
| D1 | 180 | 85 | 89 |
| D1 | 200 | 99 | 70 |
| D2 | 180 | 88 | 90 |
| D2 | 200 | 99 | 82 |
| D3 | 180 | 79 | 92 |
| D3 | 200 | 86 | 85 |
In the table, the temperature is the reaction temperature for producing methyl glycolate by using each catalyst, and the conversion and the selectivity refer to the conversion of dimethyl oxalate as a raw material and the selectivity of methyl glycolate as a product when methyl glycolate is produced by using each catalyst, respectively.
As shown in the table, when methyl glycolate is produced by using the catalyst C1-C4, the conversion rate of dimethyl oxalate can reach more than 95% and the selectivity of the product methyl glycolate can reach more than 90% when the reaction temperature is controlled between 170 and 190 ℃; when catalysts C5 and C6 are used for producing methyl glycolate, when the reaction temperature reaches 200-230 ℃, the conversion rate of raw material dimethyl oxalate and the selectivity of product methyl glycolate are both higher, and the conversion rate and the selectivity of product methyl glycolate reach more than 99% and 92% respectively;
When methyl glycolate is produced by using the catalysts D1-D3, the conversion rate of raw material dimethyl oxalate and the selectivity of the product methyl glycolate cannot reach higher level at the same time even if the reaction temperature is controlled at 180 and 200 ℃, and the production requirement is difficult to meet.
Therefore, the method can obtain a high-dispersion catalyst system by using an inexpensive reagent through ultrasonic dispersion precipitation and a microwave vacuum heating method, silver salt does not need ammoniation treatment, filtrate does not have silver loss, and the average grain size of the silver serving as an active component is 10nm, so that the dispersion degree of the silver is greatly improved, and the catalytic activity of the silver is enhanced; the conversion rate of the dimethyl oxalate used for producing raw materials and the selectivity of the methyl glycolate product are both high.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. A preparation method of a catalyst for synthesizing methyl glycolate is characterized by comprising the following steps: the method comprises the following steps:
s1, according to the content of each component of a target catalyst to be prepared, dissolving a compound containing nickel and silver elements in distilled water, fully stirring, and uniformly mixing to form a solution A, wherein the concentration of nickel ions in the solution A is 0.01-2.5 mol/L, and the concentration of silver ions is 0.01-10 mol/L;
s2, adding the powdered silicon dioxide or the silica sol into an alcohol solvent, fully stirring, and uniformly mixing to form a solution B;
S3, placing the solution B in an ultrasonic water bath at 40-90 ℃, slowly dropwise adding the solution A into the solution B in a mechanical stirring state for 3-6 hours to form gel, and then aging for 1-24 hours at room temperature;
s4, placing the gel obtained in the step S3 in a microwave oven or a microwave reactor, and adopting microwave treatment with power of 100-1000W and frequency of 2400-2500 MHz under a vacuum condition to reduce the moisture content of the gel to below 15%;
S5, roasting the microwave treated product obtained in the step S4 at 300-600 ℃ for 2-10 hours, and cooling to room temperature to obtain the target catalyst Ni-Ag/SiO 2.
2. The method for preparing the catalyst for synthesizing methyl glycolate according to claim 1, wherein the method comprises the following steps: in the step S1, the compounds of nickel and silver are both present in the form of metal salts.
3. The method for preparing the catalyst for synthesizing methyl glycolate according to claim 2, wherein the method comprises the following steps: in the step S1, the compound of nickel and silver element is nickel nitrate and silver nitrate.
4. The method for preparing the catalyst for synthesizing methyl glycolate according to claim 1, wherein the method comprises the following steps: in the step S2, the alcohol solvent is isopropanol or ethanol.
5. The method for preparing the catalyst for synthesizing methyl glycolate according to claim 1, wherein the method comprises the following steps: in the S5, the content of nickel element in the catalyst is 0-10wt% and the content of silver element is 0.01-4wt%.
6. A method for activating a catalyst for synthesizing methyl glycolate prepared by the method according to any one of claims 1 to 5, characterized in that: and (3) filling the catalyst into a fixed bed reactor, reducing in a flowing hydrogen atmosphere at a reducing pressure of 0.1-1 MPa, wherein the hydrogen volume space velocity is 200-5000 h -1, increasing the temperature to 180-230 ℃ at a speed of 0.5-2 ℃/min, reducing for 2-4 h, cooling to the reaction temperature after the reduction is finished, and completing activation.
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