CN113101915A - Catalyst for synthesizing glycollic acid by hydrolyzing methyl glycolate and preparation method thereof - Google Patents
Catalyst for synthesizing glycollic acid by hydrolyzing methyl glycolate and preparation method thereof Download PDFInfo
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- CN113101915A CN113101915A CN202110369522.9A CN202110369522A CN113101915A CN 113101915 A CN113101915 A CN 113101915A CN 202110369522 A CN202110369522 A CN 202110369522A CN 113101915 A CN113101915 A CN 113101915A
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- methyl glycolate
- glycolic acid
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims abstract description 155
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- 239000006104 solid solution Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000377 silicon dioxide Substances 0.000 claims description 36
- 238000001556 precipitation Methods 0.000 claims description 24
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 6
- 238000003786 synthesis reaction Methods 0.000 claims 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- 239000001099 ammonium carbonate Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 40
- 229910052681 coesite Inorganic materials 0.000 description 34
- 229910052906 cristobalite Inorganic materials 0.000 description 34
- 229910052682 stishovite Inorganic materials 0.000 description 34
- 229910052905 tridymite Inorganic materials 0.000 description 34
- 238000005070 sampling Methods 0.000 description 19
- 238000004811 liquid chromatography Methods 0.000 description 18
- 238000011068 loading method Methods 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- JTXJZBMXQMTSQN-UHFFFAOYSA-N amino hydrogen carbonate Chemical compound NOC(O)=O JTXJZBMXQMTSQN-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 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
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity 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
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- 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
- B01J37/031—Precipitation
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for synthesizing glycollic acid by hydrolyzing methyl glycolate and a preparation method thereof, and particularly relates to the field of catalytic materials, wherein the catalyst comprises an active component of a III group metal oxide or a composite oxide solid solution and a carrier of other metal oxides, wherein the active component accounts for 5-40 wt% of the weight of the carrier, and the rest is used as the carrier. Compared with the preparation of the gallium-aluminum catalyst by the impregnation method, the preparation process is simple, the gallium-aluminum solid solution catalyst prepared by the in-situ synthesis method has high stability and good activity, the gallium-aluminum solid solution catalyst shows excellent performance in the reaction of preparing glycolic acid by hydrolyzing methyl glycolate, the conversion rate of methyl glycolate is more than 99%, the selectivity of glycolic acid is more than 98%, and the gallium-aluminum solid solution catalyst has the advantages of high activity and high selectivity and is suitable for a fixed bed reactor, and has good cycle performance.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a catalyst for synthesizing glycollic acid by hydrolyzing methyl glycolate and a preparation method thereof.
Background
Glycolic acid is an important fine chemical and organic intermediate, and is widely applied in the fields of chemical cleaning, cosmetics, biodegradable materials and the like by virtue of the structural particularity. At present, the demand gap of glycolic acid in China is large, and glycolic acid and related products mainly depend on imports.
Glycolic acid production processes mainly comprise chloroacetic acid hydrolysis, hydroxyacetonitrile hydrolysis, formaldehyde carbonylation and the like, wherein the glycolic acid ester hydrolysis process has small pollution to the environment and simple and safe operation process, and is a method for preparing glycolic acid which accords with the modern green and environment-friendly concept, so that the glycolic acid production process is widely researched.
In Keggin et al, self-made keggin-type phosphotungstic acid (H) is adopted3[PW12O40]·21H2O) is used as a catalyst, and the hydrolysis performance test result of the methyl glycolate is as follows: the reaction was carried out at 80 ℃ for 4 hours, and the conversion of methyl glycolate was 56.34% and the selectivity of glycolic acid was 98.66%. The technology for preparing glycollic acid by catalyzing and hydrolyzing methyl glycolate in a fixed bed reactor by Sunpien and the like of Shanghai Shihua research institute is researched, and the mass space velocity (1-3) h is obtained-1The reaction temperature is 70-85 ℃, the amount ratio of water ester substances is 5-10, the hydrolysis conversion rate of methyl glycolate is close to 100%, and the quality of a glycolic acid aqueous solution product meets the requirements of enterprise standards. But still has a great gap from the actual industrial production.
Compared with basic research, the existing patents for preparing glycolic acid by hydrolyzing methyl glycolate pay more attention to practicability. CN103508878 relates to a method for preparing high-purity glycolic acid crystals from methyl glycolate, which comprises mixing methyl glycolate and water according to the mass ratio of 1 (1-20), and carrying out hydrolysis reaction at 20-100 ℃ and normal pressure for 0.5-4hr to obtain a hydrolysis solution containing glycolic acid; then carrying out reduced pressure distillation on the hydrolysate containing the glycolic acid at the temperature of 30-90 ℃ to obtain a mother solution containing high-concentration glycolic acid; and cooling and crystallizing the mother liquor at normal pressure to obtain high-purity glycolic acid crystals with the purity of more than 99.5 wt%. However, the method has the problems of long flow and high energy consumption.
CN104177250A relates to a method for preparing high-purity glycolic acid crystals from methyl glycolate, which comprises the steps of reactive distillation, evaporation concentration, decoloration, crystallization, drying and the like to obtain the glycolic acid crystals. However, the reactive distillation requires a total reflux step, so that stable and continuous operation of the column cannot be realized, the residence time in the column bottom is too long, excessive impurities are generated, and the scheme requires an evaporation concentration step, so that the complexity of the flow is increased.
The CN104829445A invention uses methyl glycolate and water as raw materials, hydrolysis reaction is carried out in a fixed bed reactor, the product at the outlet of the fixed bed reactor enters a reaction rectifying tower, methanol and water condensate are continuously extracted from the top of the reaction rectifying tower, and glycolic acid aqueous solution is continuously extracted from the bottom of the tower. CN209442896U provides a glycolic acid preparation device of methyl glycolate hydrolysis method, the device is a catalytic distillation tower, the tower comprises a rectification section, a reaction section and a stripping section, the strategy of feeding at different section positions and distilling different products at different outlets is adopted, the hydrolysis and separation process flow of glycolic acid prepared by methyl glycolate hydrolysis is shortened, the production efficiency is improved, the industrial production of glycolic acid prepared by methyl glycolate hydrolysis scale industrial production is realized, but the design requirement of equipment is high.
Disclosure of Invention
In order to overcome the defects of the prior art, the embodiment of the invention provides a catalyst for synthesizing glycolic acid by hydrolyzing methyl glycolate and a preparation method thereof, and the technical problems to be solved by the invention are as follows: how to solve the problem of poor cycle performance of the catalyst during the hydrolysis reaction of the methyl glycolate.
In order to achieve the purpose, the invention provides the following technical scheme: a catalyst for synthesizing glycollic acid by hydrolyzing methyl glycolate is composed of the active component of the group III metal oxide or composite oxide solid solution and the carrier of other metal oxide, in which the active component accounts for 5-40 wt% and the rest is carrier.
A preparation method of a catalyst for synthesizing glycolic acid by hydrolyzing methyl glycolate comprises the following specific preparation steps:
s1: preparing one or more salt precursors in a III group metal precursor into an ethanol solution;
s2: adding a certain amount of other metal oxides, fully stirring and mixing, dropwise adding ethanol solution of a precipitator for coprecipitation, controlling the pH of the precipitate to be 8-10, controlling the precipitation temperature to be 30-80 ℃, and aging for 2-12h after precipitation is finished;
s3: filtering and washing with ethanol to obtain a catalyst precursor;
s4: and drying the catalyst precursor in a vacuum drying oven overnight, and roasting at 400-800 ℃ to obtain the catalyst.
In a preferred embodiment, the group iii metal in the active composition is provided as one or two composite metals of aluminum, gallium and indium.
In a preferred embodiment, the group iii metal precursor in the active composition is a nitrate, and the concentration of the metal nitrate salt solution is set to 0.1 to 0.5 mol/L.
In a preferred embodiment, the molar ratio of the group iii metal precursor aluminum to gallium is in the range of 4: 1-1: 4 in the middle.
In a preferred embodiment, the precipitant is one of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia carbonate or ammonia bicarbonate, and the solution concentration of the precipitant is 0.1-2.0mol/L, wherein the precipitant is preferably ammonia water or ammonia carbonate.
In a preferred embodiment, the group III metal precursor is a nitrate or isopropoxide, and the concentration of the precursor is maintained between 0.1 and 0.5 mol/L.
In a preferred embodiment, the metal oxide is mainly silicon dioxide, titanium dioxide, zirconium dioxide and magnesium oxide, and the mass fraction of the metal oxide is between 60 and 95 percent.
The application of a catalyst for synthesizing glycollic acid by hydrolyzing methyl glycolate is characterized in that the catalyst is used for catalyzing the hydrolysis reaction of methyl glycolate, a certain amount of catalyst is taken to react in a three-necked bottle, and the reaction conditions are as follows: the reaction temperature is 40-100 ℃, 10mmol of methyl glycolate, 50-100mmol of water and the dosage of the catalyst is 50-200 mg.
The invention has the technical effects and advantages that:
compared with the gallium-aluminum catalyst prepared by the impregnation method, the preparation process is simple, the gallium-aluminum solid solution catalyst prepared by the in-situ synthesis method has high stability and good activity, the gallium-aluminum solid solution catalyst has excellent performance in the reaction of preparing glycolic acid by hydrolyzing methyl glycolate, the conversion rate of methyl glycolate is more than 99%, and the selectivity of glycolic acid is more than 98%, wherein the solid solution catalyst containing the III group metal oxide not only improves the reaction activity and selectivity, but also has good cycle performance by the test of recycling.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a catalyst for synthesizing glycollic acid by hydrolyzing methyl glycolate, which comprises an active composition of a III group metal oxide or a composite oxide solid solution and a carrier of other metal oxides, wherein the active composition accounts for 5-40 wt% of the weight percentage, and the rest is set as the carrier;
a preparation method of a catalyst for synthesizing glycolic acid by hydrolyzing methyl glycolate comprises the following specific preparation steps:
s1: preparing one or more salt precursors in a III group metal precursor into an ethanol solution;
s2: adding a certain amount of other metal oxides, fully stirring and mixing, dropwise adding ethanol solution of a precipitator for coprecipitation, controlling the pH of the precipitate to be 8-10, controlling the precipitation temperature to be 30-80 ℃, and aging for 2-12h after precipitation is finished;
s3: filtering and washing with ethanol to obtain a catalyst precursor;
s4: and drying the catalyst precursor in a vacuum drying oven overnight, and roasting at 400-800 ℃ to obtain the catalyst.
And specifically in this embodiment: by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 2: ga in an amount of 15% by mass of solid solution oxide2Al/SiO2Catalyst, recordIs Ga2Al/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling at regular time and carrying out liquid chromatography for product analysis, wherein the conversion rate of methyl glycolate is 71% and the selectivity of glycolic acid is 99% when the reaction is carried out for 4 hours.
Example 2:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 2: ga in an amount of 15% by mass of solid solution oxide2Al/SiO2Catalyst, denoted Ga2Al/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 80 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, the product was analyzed by liquid chromatography with regular sampling, and when the reaction was carried out for 4 hours, the conversion of methyl glycolate was 89%, and the selectivity of glycolic acid was 98%.
Example 3:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, the mass loading of solid solution oxide is 5 percent of GaAl/SiO2Catalyst, noted 5GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling at regular time and carrying out liquid chromatography for product analysis, wherein the conversion rate of methyl glycolate is 56% and the selectivity of glycolic acid is 99% when the reaction is carried out for 4 hours.
Example 4:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, the mass loading of solid solution oxide is 10 percent of GaAl/SiO2Catalyst, noted 10GaAl/SiO2For the reaction of preparing glycollic acid by hydrolyzing methyl glycolate in a suitable three-necked bottleAdding 0.5g of catalyst, reacting at the reaction temperature of 60 ℃ under normal pressure, wherein the using amount of methyl glycolate is 10mmol, the water-ester ratio is 10: l, the product was analyzed by liquid chromatography with time sampling, and at 4 hours of the reaction, the conversion of methyl glycolate was 67% and the selectivity of glycolic acid was 99%.
Example 5:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/SiO2Catalyst, noted 15GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling at regular time and carrying out liquid chromatography for product analysis, wherein the conversion rate of methyl glycolate is 76% and the selectivity of glycolic acid is 99% when the reaction is carried out for 4 hours.
Example 6:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, the mass loading of the solid solution oxide is 20 percent of GaAl/SiO2Catalyst, noted as 20GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, the product was analyzed by liquid chromatography with regular sampling, and when the reaction was carried out for 4 hours, the conversion of methyl glycolate was 82%, and the selectivity of glycolic acid was 97%.
Example 7:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/SiO2Catalyst, noted 15GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 80 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling the liquid phase at regular intervalsProduct analysis was performed by chromatography, and at 4 hours of reaction, the conversion of methyl glycolate was 94% and the selectivity of glycolic acid was 99%.
Example 8:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/SiO2Catalyst, noted 15GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 80 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, and the water-ester ratio is 6: l, sampling at regular time and carrying out liquid chromatography for product analysis, wherein the conversion rate of methyl glycolate is 92% and the selectivity of glycolic acid is 99% when the reaction is carried out for 4 hours.
Example 9:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/SiO2Catalyst, noted 15GaAl/SiO2And the method is used for the reaction for preparing the glycollic acid by hydrolyzing the methyl glycolate, and 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 80 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, and the water-ester ratio is 5: l, sampling liquid chromatography at regular time for product analysis, and when the reaction is carried out for 4 hours, the conversion rate of methyl glycolate is 90 percent, and the selectivity of glycolic acid is 99 percent.
Example 10:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, the mass loading of the solid solution oxide is 30 percent of GaAl/SiO2Catalyst, noted as 30GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, the product was analyzed by liquid chromatography with regular sampling, and when the reaction was carried out for 4 hours, the conversion of methyl glycolate was 81% and the selectivity of glycolic acid was 97%.
Example 11:
detecting the supported gallium-aluminum catalyst prepared by an impregnation method to obtain a product of Ga, Al, 1: 1, solid solution oxide mass loading of 15% GaAl-SiO2Catalyst, noted 15GaAl-SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, the product was analyzed by liquid chromatography with regular sampling, and at 4 hours of reaction, the conversion of methyl glycolate was 46% and the selectivity of glycolic acid was 99%.
Example 12:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 2, the mass loading of the solid solution oxide is 15 percent of GaAl2/SiO2Catalyst, noted 15GaAl2/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, the product was analyzed by liquid chromatography with regular sampling, and when the reaction was carried out for 4 hours, the conversion of methyl glycolate was 63% and the selectivity of glycolic acid was 98%.
Example 13:
the supported gallium-indium solid solution catalyst prepared by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h is detected to obtain a product with Ga: In ═ 1: 1, the solid solution oxide has 15 percent of GaIn/SiO2Catalyst, as 15GaIn/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling at regular time and carrying out liquid chromatography for product analysis, wherein the conversion rate of methyl glycolate is 58% and the selectivity of glycolic acid is 98% when the reaction is carried out for 4 hours.
Example 14:
the solid solution catalyst loaded with gallium and indium is prepared by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8 hours and roasting at 600 ℃ for 6 hoursAnd detecting to obtain Ga, Al, 1: 1, solid solution oxide mass loading of 15% GaAl/TiO2Catalyst, noted 15GaAl/TiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, the product was analyzed by liquid chromatography with time sampling, and at 4 hours of the reaction, the conversion of methyl glycolate was 67% and the selectivity of glycolic acid was 98%.
Example 15:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 600 ℃ for 6h, the supported gallium-indium solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/ZrO2Catalyst, noted 15GaAl/ZrO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 60 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, the product was analyzed by liquid chromatography with regular sampling, and when the reaction was carried out for 4 hours, the conversion of methyl glycolate was 63% and the selectivity of glycolic acid was 98%.
Example 16:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 400 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/SiO2Catalyst, noted 15GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 80 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling at regular time and carrying out liquid chromatography for product analysis, wherein the conversion rate of methyl glycolate is 58% and the selectivity of glycolic acid is 99% when the reaction is carried out for 4 hours.
Example 17:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 500 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/SiO2Catalyst, noted 15GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 80 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling at regular time and carrying out liquid chromatography for product analysis, wherein the conversion rate of methyl glycolate is 66% and the selectivity of glycolic acid is 99% when the reaction is carried out for 4 hours.
Example 18:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 700 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/SiO2Catalyst, noted 15GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 80 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling at regular time and carrying out liquid chromatography for product analysis, wherein the conversion rate of methyl glycolate is 89% and the selectivity of glycolic acid is 99% when the reaction is carried out for 4 hours.
Example 19:
by adopting a modified colloidal precipitation method, crystallizing at 80 ℃ for 8h, and roasting at 800 ℃ for 6h, the supported gallium-aluminum solid solution catalyst is detected to obtain a product with Ga: Al being 1: 1, solid solution oxide mass loading of 15% GaAl/SiO2Catalyst, noted 15GaAl/SiO2For the reaction for preparing glycolic acid by hydrolyzing methyl glycolate, 0.5g of catalyst is added into a suitable three-necked bottle, the reaction temperature is 80 ℃, the reaction is carried out under normal pressure, the using amount of the methyl glycolate is 10mmol, the water-ester ratio is 10: l, sampling liquid chromatography at regular time for product analysis, and when the reaction is carried out for 4 hours, the conversion rate of methyl glycolate is 85 percent, and the selectivity of glycolic acid is 99 percent.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (9)
1. A catalyst for synthesizing glycollic acid by hydrolyzing methyl glycolate is characterized in that: the carrier comprises active components of group III metal oxide or composite oxide solid solution and other metal oxides, wherein the active components account for 5-40 wt% of the carrier according to the weight percentage, and the rest is set as the carrier.
2. A method for preparing a catalyst for the synthesis of glycolic acid by the hydrolysis of methyl glycolate according to claim 1, characterized in that: the preparation method comprises the following specific steps:
s1: preparing one or more salt precursors in a III group metal precursor into an ethanol solution;
s2: adding a certain amount of other metal oxides, fully stirring and mixing, dropwise adding ethanol solution of a precipitator for coprecipitation, controlling the pH of the precipitate to be 8-10, controlling the precipitation temperature to be 30-80 ℃, and aging for 2-12h after precipitation is finished;
s3: filtering and washing with ethanol to obtain a catalyst precursor;
s4: and drying the catalyst precursor in a vacuum drying oven overnight, and roasting at 400-800 ℃ to obtain the catalyst.
3. The method for preparing a catalyst for the synthesis of glycolic acid by the hydrolysis of methyl glycolate as claimed in claim 2, characterized in that: the group III metal in the active composition is set to be one or two composite metals of aluminum, gallium and indium.
4. The method for preparing a catalyst for the synthesis of glycolic acid by the hydrolysis of methyl glycolate as claimed in claim 2, characterized in that: the III group metal precursor in the active composition is nitrate, and the concentration of the metal nitrate salt solution is set to be 0.1-0.5 mol/L.
5. The catalyst for the hydrolysis of methyl glycolate to glycolic acid according to claim 4, wherein: the molar ratio of the aluminum to the gallium of the group III metal precursor is 4: 1-1: 4 in the middle.
6. The method for preparing a catalyst for the synthesis of glycolic acid by the hydrolysis of methyl glycolate as claimed in claim 2, characterized in that: the precipitator is one of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia carbonate or ammonium bicarbonate, the concentration of the solution of the precipitator is 0.1-2.0mol/L, and the precipitator is preferably ammonia water or ammonia carbonate.
7. The method for preparing a catalyst for the synthesis of glycolic acid by the hydrolysis of methyl glycolate as claimed in claim 2, characterized in that: the group III metal precursor is mainly nitrate or isopropoxide, and the concentration of the precursor is kept between 0.1 and 0.5 mol/L.
8. The method for preparing a catalyst for the synthesis of glycolic acid by the hydrolysis of methyl glycolate as claimed in claim 2, characterized in that: the metal oxide is mainly silicon dioxide, titanium dioxide, zirconium dioxide and magnesium oxide, and the mass fraction of the metal oxide is 60-95%.
9. The use of a catalyst according to claim 1 for the hydrolysis of methyl glycolate to glycolic acid, wherein: the catalyst is used for catalyzing the hydrolysis reaction of methyl glycolate, a certain amount of catalyst is taken to react in a three-necked bottle, and the reaction conditions are as follows: the reaction temperature is 40-100 ℃, 10mmol of methyl glycolate, 50-100mmol of water and the dosage of the catalyst is 50-200 mg.
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| CN114057564A (en) * | 2021-12-09 | 2022-02-18 | 上海卓笙环保科技有限公司 | Method for hydrolyzing glycolate by taking carbonic acid system as traceless catalyst |
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| CN114057564A (en) * | 2021-12-09 | 2022-02-18 | 上海卓笙环保科技有限公司 | Method for hydrolyzing glycolate by taking carbonic acid system as traceless catalyst |
| CN114057564B (en) * | 2021-12-09 | 2023-10-03 | 上海卓笙环保科技有限公司 | Method for hydrolyzing glycollate based on carbonic acid system as traceless catalyst |
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