CN112206772A - Preparation and application of catalyst for synthesizing methyl glycolate - Google Patents
Preparation and application of catalyst for synthesizing methyl glycolate Download PDFInfo
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- CN112206772A CN112206772A CN202011100846.4A CN202011100846A CN112206772A CN 112206772 A CN112206772 A CN 112206772A CN 202011100846 A CN202011100846 A CN 202011100846A CN 112206772 A CN112206772 A CN 112206772A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 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 claims abstract description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- CETRJNFIKWWGQO-UHFFFAOYSA-N methanol;oxalic acid Chemical compound OC.OC(=O)C(O)=O CETRJNFIKWWGQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical group CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to preparation and application of a catalyst for synthesizing methyl glycolate, in particular to a preparation method and application of a catalyst for preparing methyl glycolate through high-efficiency oxalate gas-phase hydrogenation, and belongs to the technical field of catalyst preparation. According to the preparation and application of the methyl glycolate catalyst, the silver nanoparticles are loaded on the nano silicon dioxide in an anhydrous solvent phase system through the use of a novel reducing agent, silver salt does not need to be subjected to ammoniation treatment, the filtrate does not have silver loss, the average particle size of the prepared active component silver is 19nm, the dispersity of the silver is greatly improved, and the catalytic activity of the catalyst is enhanced. The catalyst for preparing methyl glycolate by hydrogenating oxalate has the advantages of high catalytic activity, high selectivity and good stability. The conversion rate of the oxalic ester is 100 percent, and the selectivity of the methyl glycolate is more than 96 percent, so the method has wide application prospect.
Description
Technical Field
The invention relates to preparation and application of a catalyst for synthesizing methyl glycolate, in particular to a preparation method and application of a catalyst for preparing methyl glycolate through high-efficiency oxalate gas-phase hydrogenation, and belongs to the technical field of catalyst preparation.
Background
At present, Methyl Glycolate (MG), also called methyl glycolate or methyl glycolate, has both alpha-H, hydroxyl and ester functional groups, so that the chemical properties of alcohol and ester can be realized, the reactions such as hydrolysis, oxidative dehydrogenation, hydrogenation, ammoniation, carbonylation and the like can be performed, the method can be used for preparing cleaning agent glycolic acid through hydrolysis, preparing spice intermediate methyl glyoxylate through oxidative dehydrogenation, preparing chemical raw material ethylene glycol through hydrogenation, preparing methyl malonate through carbonylation, preparing DL-glycine through ammonolysis and the like, and is an important chemical raw material, and related synthesis and application are always concerned.
At present, methyl glycolate is mainly prepared by a one-step oxidation esterification method which takes glyoxal or glyoxal and methanol as reaction raw materials, a coupling method which takes methyl formate and formaldehyde or polyformaldehyde as raw materials, a formaldehyde carbonylation esterification method, a chloroacetic acid method, a dimethyl oxalate hydrogenation reduction method and the like. The raw materials of the one-step esterification method, the coupling method and the esterification method are toxic and difficult to separate and are difficult to industrially amplify, strong alkaline substances are used in the chloroacetic acid method, the chloroacetic acid method has serious corrosion to equipment, and the process for preparing the methyl glycolate by using the dimethyl oxalate from the synthesis gas by using coal with relatively rich resources as the raw material has competitive advantages by combining the energy structure characteristics of China. The method has the advantages of high yield of methyl glycolate, and the process conforms to the energy structure of China, and is a process route suitable for large-scale industrial production.
In the gas-phase hydrogenation process of oxalate, the catalyst is difficult to drive under high load for a long time due to insufficient strength and poor dispersibility of active components.
In view of the above-mentioned drawbacks, the present inventors have made active research and innovation to create a preparation and application of a catalyst for synthesizing methyl glycolate, so that the catalyst has industrial utility value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method and application of a catalyst for synthesizing methyl glycolate. According to the preparation and application of the methyl glycolate catalyst, the silver nanoparticles are loaded on the nano silicon dioxide in an anhydrous solvent phase system through the use of a novel reducing agent, silver salt does not need to be subjected to ammoniation treatment, the filtrate does not have silver loss, the average particle size of the prepared active component silver is 19nm, the dispersity of the silver is greatly improved, and the catalytic activity of the catalyst is enhanced. The catalyst for preparing methyl glycolate by hydrogenating oxalate has the advantages of high catalytic activity, high selectivity and good stability. The conversion rate of the oxalic ester is 100 percent, and the selectivity of the methyl glycolate is more than 96 percent, so the method has wide application prospect.
The invention relates to a preparation method of a catalyst for synthesizing methyl glycolate, which comprises the following specific preparation steps of:
(1) firstly, adding silver salt into a solvent, stirring and dissolving, adding a certain dispersant after complete dissolution, slowly adding a porous nano-silica carrier into the mixed solution, and stirring to obtain a mixed solution;
(2) adding a reducing agent into a solvent, adding the reducing agent into the mixed solution at a certain speed, stirring and reacting at a certain temperature, and filtering out a filter cake;
(3) and drying the prepared filter cake for 3-10 hours at the temperature of 50-90 ℃, grinding the dried material, screening to particles with a certain mesh number, tabletting and forming, and roasting at the temperature of 300-580 ℃ for 2-15 hours to obtain the catalyst.
Further, the particle size range of the porous nano silicon dioxide is 5-50 nm, and the specific surface area is 150-600 m2/g。
Further, in the step (1), the solvent is one or more of isopropanol, ethylene glycol, cyclohexane, dimethyl sulfoxide and ethanol which are mixed according to any proportion, and the dispersing agent is polyvinylpyrrolidone.
Further, the reducing agent is methyl glyoxylate, and the molar ratio of the methyl glyoxylate to the silver is 1-10: 1.
Further, the reaction temperature in the step (2) is 0-110 ℃, and the reaction time is 2-15 hours.
Further, the certain speed in the step (2) is set to be 0.1-10 mL/min for the speed of the peristaltic pump.
The synthesis method of methyl glycolate takes oxalate methanol as a raw material and prepares methyl glycolate by reaction in the presence of the catalyst.
Further, the specific synthesis steps are as follows:
weighing the catalyst, grinding and screening to obtain 10-50-mesh particles, filling the particles into a fixed bed reactor, reducing the particles for 10-50 h at the temperature of 120-380 ℃ by using hydrogen with the flow rate of 150-600 mL/min, cooling to 190-240 ℃, controlling the reaction pressure to be 2.2Mpa and the hydrogen-ester ratio to be 40-110, pumping an oxalate methanol solution with the mass concentration of 25% into the reactor by a high-pressure constant flow pump at the speed of 0.3mL/min for reaction to obtain a reaction liquid, namely methyl glycolate, and carrying out quantitative detection and analysis by using a corrected gas chromatography.
By the scheme, the invention at least has the following advantages:
according to the preparation and application of the methyl glycolate catalyst, the silver nanoparticles are loaded on the nano silicon dioxide in an anhydrous solvent phase system through the use of a novel reducing agent, silver salt does not need to be subjected to ammoniation treatment, the filtrate does not have silver loss, the average particle size of the prepared active component silver is 19nm, the dispersity of the silver is greatly improved, and the catalytic activity of the catalyst is enhanced. The catalyst for preparing methyl glycolate by hydrogenating oxalate has the advantages of high catalytic activity, high selectivity and good stability. The conversion rate of the oxalic ester is 100 percent, and the selectivity of the methyl glycolate is more than 96 percent, so the method has wide application prospect.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate a certain embodiment of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an XRD spectrum of a nano-silica supported silver catalyst;
FIG. 2 is a TEM photograph of a high purity silica support;
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
(1) Firstly, adding silver salt into a solvent, stirring and dissolving to prepare a solution with the concentration of 0.01-0.30M for later use, wherein the mass ratio of silver to a catalyst is 1-20%;
(2) dissolving a dispersing agent into the solution to obtain a dispersing solution, wherein the adding amount of the dispersing agent accounts for 1-15% of the weight of the catalyst;
(3) slowly adding a porous nano-silica carrier into the dispersion liquid, and stirring to obtain a mixed liquid, wherein the adding amount of the carrier accounts for 75-98% of the weight of the catalyst;
(4) slowly adding a reducing agent into a solvent to obtain a reducing agent solution, wherein the volume ratio of the solvent to the reducing agent is 20-200: 1;
(5) placing the mixed solution in a temperature-controllable oil bath, stirring for 30-50 min, slowly adding a reducing agent solution into the mixed solution, controlling the temperature to be 0-110 ℃, and stirring to react for 4-15 h to obtain slurry;
(6) filtering the slurry to obtain a filter cake, drying the filter cake at the temperature of 50-90 ℃ for 3-10 h, grinding the obtained solid into powder, tabletting and forming, and roasting in a muffle furnace at the temperature of 300-550 ℃ for 2-15 h to obtain the catalyst;
application of methyl glycolate catalyst:
weighing the catalyst, grinding and screening to obtain 10-50-mesh particles, filling the particles into a fixed bed reactor, reducing the particles for 10-50 h at the temperature of 120-380 ℃ by using hydrogen with the flow rate of 150-600 mL/min, cooling to 190-240 ℃, controlling the reaction pressure to be 2.2Mpa and the hydrogen-ester ratio to be 40-110, pumping an oxalate methanol solution with the mass concentration of 25% into the reactor by a high-pressure constant flow pump at the speed of 0.3mL/min for reaction to obtain a reaction liquid, namely methyl glycolate, and carrying out quantitative detection and analysis by using a corrected gas chromatography.
The working principle of the invention is as follows:
through the use of a novel reducing agent, silver nanoparticles are loaded on the nano silicon dioxide in an anhydrous solvent phase system, silver salt does not need ammoniation treatment, the filtrate does not have silver loss, the average particle size of the prepared active component silver is 19nm, the dispersity of the silver is greatly improved, and the catalytic activity of the silver is enhanced. The catalyst for preparing methyl glycolate by hydrogenating oxalate has the advantages of high catalytic activity, high selectivity and good stability.
Example 1
Adding 0.36g of silver nitrate into a solvent, stirring and dissolving to prepare a 0.2M solution, adding 0.3g of polyvinylpyrrolidone dispersant to dissolve the solution, weighing 11g of modified hydrophilic porous nano-silica carrier, slowly adding the modified hydrophilic porous nano-silica carrier into the solution, stirring until the modified hydrophilic porous nano-silica carrier is completely dissolved, slowly adding 0.5g of reducing agent into 100mL of the solvent, placing the mixed material into an oil bath with controllable temperature, stirring for 30-50 min, slowly adding the prepared reducing agent into a mixed solution oil bath reaction kettle, controlling the temperature to be 0-110 ℃, and stirring and reacting for 4-15 h. And (3) filtering the slurry obtained through reaction to obtain a filter cake, drying the filter cake at the temperature of 50-90 ℃ for 3-10 hours, grinding the dried solid block material into powder, tabletting and forming, and roasting in a muffle furnace at the temperature of 300-550 ℃ for 2-15 hours to obtain the catalyst 1# with the active component of 2%.
Example 2
Adding 0.72g of silver nitrate into a solvent, stirring and dissolving to prepare a 0.2M solution, adding 0.6g of polyvinylpyrrolidone dispersant to dissolve the solution, weighing 11g of modified hydrophilic porous nano-silica carrier, slowly adding the modified hydrophilic porous nano-silica carrier into the solution, stirring until the modified hydrophilic porous nano-silica carrier is completely dissolved, slowly adding 1.0g of reducing agent into 100mL of the solvent, placing the mixed material into an oil bath with controllable temperature, stirring for 30-50 min, slowly adding the prepared reducing agent into a mixed solution oil bath reaction kettle, controlling the temperature to be 0-110 ℃, and stirring and reacting for 4-15 h. And (3) filtering the slurry obtained by reaction to obtain a filter cake, drying the filter cake at the temperature of 50-90 ℃ for 3-10 h, grinding the dried solid block material into powder, tabletting and forming, and roasting in a muffle furnace at the temperature of 300-550 ℃ for 2-15 h to obtain the catalyst 2# with 4% of active component.
Example 3
Adding 1.45g of silver nitrate into a solvent, stirring and dissolving to prepare a 0.2M solution, adding 1.2g of polyvinylpyrrolidone dispersant, dissolving the solution, weighing 11g of modified hydrophilic porous nano-silica carrier, slowly adding the modified hydrophilic porous nano-silica carrier into the solution, stirring until the modified hydrophilic porous nano-silica carrier is completely dissolved, slowly adding 2.0g of a reducing agent into 200mL of the solvent, placing the mixed material into an oil bath with controllable temperature, stirring for 30-50 min, slowly adding the prepared reducing agent into a mixed solution oil bath reaction kettle, controlling the temperature to be 0-110 ℃, and stirring and reacting for 4-15 h. And (3) filtering the slurry obtained through the reaction to obtain a filter cake, drying the filter cake at the temperature of 50-90 ℃ for 3-10 hours, grinding the dried solid block material into powder, tabletting and forming, and roasting in a muffle furnace at the temperature of 300-550 ℃ for 2-15 hours to obtain the catalyst 3# with 8% of active component.
Example 4
Adding 2.16g of silver nitrate into a solvent, stirring and dissolving to prepare a 0.2M solution, adding 1.8g of polyvinylpyrrolidone dispersant to dissolve the solution, weighing 11g of modified hydrophilic porous nano-silica carrier, slowly adding the modified hydrophilic porous nano-silica carrier into the solution, stirring until the modified hydrophilic porous nano-silica carrier is completely dissolved, slowly adding 2.5g of a reducing agent into 200mL of the solvent, placing the mixed material into an oil bath with controllable temperature, stirring for 30-50 min, slowly adding the prepared reducing agent into a mixed solution oil bath reaction kettle, controlling the temperature to be 0-110 ℃, and stirring and reacting for 4-15 h. And (3) filtering the slurry obtained through the reaction to obtain a filter cake, drying the filter cake at the temperature of 50-90 ℃ for 3-10 hours, grinding the dried solid block material into powder, tabletting and forming, and roasting in a muffle furnace at the temperature of 300-550 ℃ for 2-15 hours to obtain the catalyst 4# with 12% of active component.
Comparative example 1: the effective silver doping amount is the same as that of the inventive example 3, and the carrier adopts activated carbon instead of the modified hydrophilic porous nano-silica carrier of the invention, and the catalyst is also prepared for where methyl glycolate is used;
comparative example 2: the effective silver doping amount is the same as that of the inventive example 3, and the alumina is used as the carrier instead of the modified hydrophilic porous nano-silica carrier of the invention, and the catalyst is also prepared for where methyl glycolate is used;
evaluation of catalyst Performance
Weighing the 2g of catalyst precursor, grinding and screening to obtain 10-20 mesh particles, filling the particles into a fixed bed reactor, reducing the particles for 10-50 h at 180-380 ℃ by using hydrogen with the flow rate of 150-600 mL/min, cooling to 190-240 ℃, controlling the reaction pressure to be 2.2Mpa and the hydrogen-ester ratio to be 40-110, pumping an oxalate methanol solution with the mass concentration of 25% into the reactor by a high-pressure constant flow pump at the speed of 0.3mL/min for reaction, and carrying out quantitative detection and analysis by using a corrected gas chromatography.
TABLE 1 results of catalyst Performance measurements
| Detecting items | Catalyst and process for preparing same | Conversion of dimethyl oxalate (%) | Methyl glycolate selectivity (%) |
| Example 1 | 2Ag/SiO2 | 96 | 94 |
| Example 2 | 4Ag/SiO2 | 97 | 95 |
| Example 3 | 8Ag/ |
100 | 96 |
| Example 4 | 12Ag/SiO2 | 98 | 94 |
| Comparative example 1 | 8Ag/AC | 95 | 85 |
| Comparative example 2 | 8Ag/Al2O3 | 88 | 86 |
As can be seen from the detection results in the above table, in comparative example 1, the catalyst is prepared by replacing the modified hydrophilic porous nano-silica carrier with activated carbon, and finally the conversion rate of dimethyl oxalate and the selectivity of methyl glycolate are both significantly reduced, in comparative example 2, the catalyst is prepared by replacing the modified hydrophilic porous nano-silica carrier with alumina, and finally the conversion rate of dimethyl oxalate and the selectivity of methyl glycolate are both significantly reduced, so that the use of the modified hydrophilic porous nano-silica carrier provided by the invention indeed improves the service performance of the catalyst, and has a wide application prospect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a catalyst for synthesizing methyl glycolate, wherein the silver content of the catalyst is 1-20%, and the preparation method is characterized by comprising the following specific preparation steps:
(1) firstly, adding silver salt into a solvent, stirring and dissolving, adding a certain dispersant after complete dissolution, slowly adding a porous nano-silica carrier into the mixed solution, and stirring to obtain a mixed solution;
(2) adding a reducing agent into a solvent, adding the reducing agent into the mixed solution at a certain speed, stirring and reacting at a certain temperature, and filtering out a filter cake;
(3) and drying the prepared filter cake for 3-10 hours at the temperature of 50-90 ℃, grinding the dried material, screening to particles with a certain mesh number, tabletting and forming, and roasting at the temperature of 300-580 ℃ for 2-15 hours to obtain the catalyst.
2. The process for the preparation of a catalyst for the synthesis of methyl glycolate as claimed in claim 1, characterized in that: the particle size range of the porous nano silicon dioxide is 5-50 nm, and the specific surface area is 150-600 m2/g。
3. The process for the preparation of a catalyst for the synthesis of methyl glycolate as claimed in claim 1, characterized in that: in the step (1), the solvent is one or more of isopropanol, ethylene glycol, cyclohexane, dimethyl sulfoxide and ethanol which are mixed according to any proportion, and the dispersant is polyvinylpyrrolidone.
4. The process for the preparation of a catalyst for the synthesis of methyl glycolate as claimed in claim 1, characterized in that: the reducing agent is methyl glyoxylate, and the molar ratio of the methyl glyoxylate to the silver is 1-10: 1.
5. The process for the preparation of a catalyst for the synthesis of methyl glycolate as claimed in claim 1, characterized in that: in the step (2), the reaction temperature is 0-110 ℃, and the reaction time is 2-15 h.
6. The process for the preparation of a catalyst for the synthesis of methyl glycolate as claimed in claim 1, characterized in that: and (3) setting the speed of the peristaltic pump to be 0.1-10 mL/min at a certain speed in the step (2).
7. The synthesis method of methyl glycolate is characterized by comprising the following steps: the oxalate methanol is used as a raw material and reacts in the presence of the catalyst of any one of claims 1 to 6 to prepare methyl glycolate.
8. The method for synthesizing the ethylene glycol according to claim 7, which is characterized by comprising the following specific steps:
weighing the catalyst, grinding and screening to obtain 10-50-mesh particles, filling the particles into a fixed bed reactor, reducing the particles for 10-50 h at the temperature of 120-380 ℃ by using hydrogen with the flow rate of 150-600 mL/min, cooling to 190-240 ℃, controlling the reaction pressure to be 2.2Mpa and the hydrogen-ester ratio to be 40-110, pumping an oxalate methanol solution with the mass concentration of 25% into the reactor by a high-pressure constant flow pump at the speed of 0.3mL/min for reaction to obtain a reaction liquid, namely methyl glycolate, and carrying out quantitative detection and analysis by using a corrected gas chromatography.
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| CN114602500A (en) * | 2022-03-14 | 2022-06-10 | 江苏金聚合金材料有限公司 | Preparation method and application of high-dispersion copper-silver alloy catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109402A (en) * | 1984-12-28 | 1986-07-23 | 孟山都公司 | The preparation method of glyphosate and glyphosate derivatives |
| CN102553579A (en) * | 2011-05-27 | 2012-07-11 | 中国科学院福建物质结构研究所 | Preparation method of high-dispersity supported nano metal catalyst |
| CN104923219A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Methyl glycolate catalyst prepared by hydrogenation of oxalate, and preparation method and use thereof |
| CN105772739A (en) * | 2016-03-12 | 2016-07-20 | 常州大学 | Preparation method for graphene/nano-silver composite antibacterial material |
| CN110404586A (en) * | 2019-08-05 | 2019-11-05 | 无锡威孚环保催化剂有限公司 | The preparation method of high degree of dispersion metallic catalyst |
-
2020
- 2020-10-15 CN CN202011100846.4A patent/CN112206772A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109402A (en) * | 1984-12-28 | 1986-07-23 | 孟山都公司 | The preparation method of glyphosate and glyphosate derivatives |
| CN102553579A (en) * | 2011-05-27 | 2012-07-11 | 中国科学院福建物质结构研究所 | Preparation method of high-dispersity supported nano metal catalyst |
| CN104923219A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Methyl glycolate catalyst prepared by hydrogenation of oxalate, and preparation method and use thereof |
| CN105772739A (en) * | 2016-03-12 | 2016-07-20 | 常州大学 | Preparation method for graphene/nano-silver composite antibacterial material |
| CN110404586A (en) * | 2019-08-05 | 2019-11-05 | 无锡威孚环保催化剂有限公司 | The preparation method of high degree of dispersion metallic catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602500A (en) * | 2022-03-14 | 2022-06-10 | 江苏金聚合金材料有限公司 | Preparation method and application of high-dispersion copper-silver alloy catalyst |
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