CN113198492A - Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof - Google Patents
Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof Download PDFInfo
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- CN113198492A CN113198492A CN202110516390.8A CN202110516390A CN113198492A CN 113198492 A CN113198492 A CN 113198492A CN 202110516390 A CN202110516390 A CN 202110516390A CN 113198492 A CN113198492 A CN 113198492A
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- lactate
- pyruvate
- indium
- zinc
- photocatalytic
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- 238000000034 method Methods 0.000 title claims abstract description 37
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 title claims abstract description 36
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 claims abstract description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 28
- 239000011701 zinc Substances 0.000 claims description 16
- 229940116333 ethyl lactate Drugs 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 2
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 2
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 claims description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical group C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 2
- 229940057867 methyl lactate Drugs 0.000 claims description 2
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 229940076788 pyruvate Drugs 0.000 description 21
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 10
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 10
- 229940117360 ethyl pyruvate Drugs 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229940107700 pyruvic acid Drugs 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000911 decarboxylating effect Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910000343 potassium bisulfate 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
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/20—Sulfiding
-
- 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
-
- 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
- C07C67/313—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 doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing pyruvate by photocatalytic lactate oxidation and a method thereof, the method takes a sulfur indium zinc compound as a photocatalyst, takes oxygen or air as an oxygen source, and realizes the purpose of catalyzing lactate to prepare pyruvate by a photocatalytic method for the first time under the illumination condition, the reaction condition is mild, the method can be carried out at room temperature, the method has high selectivity, the selectivity of the pyruvate can reach more than 90 percent, and the purpose of preparing the pyruvate by catalyzing the lactate oxidation with high selectivity is realized.
Description
Technical Field
The invention belongs to the technical field of acid ester preparation, and particularly relates to a catalyst for preparing pyruvate through photocatalytic oxidation of lactate and a method thereof.
Background
Pyruvic acid and its ester have wide application in pesticide, food, perfume, biological preparation and other industries, and are important chemical products. At present, the production of pyruvic acid and esters thereof is mainly completed by using tartaric acid as a raw material and excessive potassium bisulfate as a decarboxylating agent through a dehydration and decarboxylation process. The production process has low atom economy, high production cost and serious environmental pollution. The search for a green pyruvic acid (ester) synthesis process has important economic and environmental values.
Lactic acid and its esters are an important class of bio-based chemicals, obtainable by conversion of biomass (sugars, cellulose, etc.). The chemical structures of lactic acid (ester) and pyruvic acid (ester) are similar. The method for preparing pyruvic acid (ester) by converting lactic acid (ester) by using the oxidation technology is a biomass conversion route with high atom economy and good market prospect.
The catalytic oxidation method is an important oxidation technology and can realize the oxidation of lactate to prepare pyruvate. Molecular oxygen is taken as an oxidant, Ag is taken as an active component, and pyruvate can be prepared by catalyzing lactate to be oxidized (US-4229590; Chin. J. Catal. 1998, 19, 428-. However, the pyruvate yield of the process is low and the reaction needs to be carried out>At a temperature of 400 ℃. By using MoO3-TiO2The catalyst can lower the reaction temperature to 200 ℃, but the pyruvate yield is still low (Green chem.2017, 19, 3014-3022).
Pyruvate is thermally unstable and can decompose at higher reaction temperatures, which is a major cause of its low yield. Lowering the reaction temperature helps to increase its yield. Chinese patent document CN 103570532B uses alcohols or aromatic hydrocarbons as solvent and H2O2Is an oxidant, TS-1 molecular sieve is a catalyst, and the yield of pyruvate can reach 79 percent under the condition of 70 ℃. Chinese patent documentUnder the solvent-free condition, using hydrogen to donate CN 107930687B2O2Is oxidant and TS-1 is catalyst, the yield of pyruvate can reach 95%. However, the above process is accompanied by a large amount of H2O2The use of (2) increases the safety risk of the pyruvate production process and causes the production cost to increase. Therefore, under mild conditions, the green and efficient catalytic conversion of lactate to pyruvate is of great significance.
Disclosure of Invention
The invention provides a catalyst for preparing pyruvate by photocatalytic oxidation of lactate, which solves the problems of low yield of pyruvate, safety risk in pyruvate production process, high cost and the like in the prior art.
In order to solve the technical problem, the catalyst for preparing pyruvate through photocatalytic lactate oxidation is a sulfur indium zinc compound, and the molar ratio of zinc to indium in the sulfur indium zinc compound is 1: 2-2: 1.
Preferably: the preparation method of the sulfur indium zinc compound comprises the following steps: adding a zinc source, an indium source and thioacetamide into a flask in sequence according to the molar ratio of zinc to indium, adding water to dissolve, heating the solution to 60-90 ℃, keeping for 3-10 hours, then carrying out ultrasonic treatment for 0.2-2 hours, centrifuging, washing, and carrying out vacuum drying for 3-10 hours at 40-70 ℃.
Preferably: the zinc source is one or more of zinc sulfate, zinc nitrate, zinc acetate and zinc chloride; the indium source is one or more of indium sulfate, indium nitrate, indium acetate and indium chloride.
The invention also provides a method for preparing pyruvate by photocatalytic lactate oxidation, which takes the sulfur indium zinc compound as a photocatalyst and oxygen or air as an oxygen source to catalyze lactate oxidation to prepare pyruvate with high selectivity under the illumination condition.
Preferably: the lactate is one or more of methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferably: the process can be carried out without solvent or in acetonitrile or toluene.
Preferably: in the method, the wavelength of the light source is 250 nm-800 nm.
Preferably: in the method, the weight ratio of the catalyst to the reaction substrate is 0.1-10.
Preferably: the partial pressure of the oxygen is 0.05-2.0 MPa, and the optimal partial pressure of the oxygen is 0.1-1.5 MPa; in the method, the reaction temperature is room temperature, the reaction time is 0.5-15 hours, and the optimized optimal reaction time is 3-7 hours.
Has the advantages that:
1. the method for preparing pyruvate by catalyzing lactate is realized for the first time by a photocatalysis method, the reaction condition is mild, and the method can be carried out at room temperature.
2. The method has high selectivity, and the selectivity of pyruvate can reach more than 90%.
Detailed Description
The essential features and remarkable effects of the present invention can be embodied in the following examples, which are not intended to limit the scope of the present invention in any way. The invention is not limited to the embodiments described above, but rather, various modifications and changes may be made by those skilled in the art without departing from the scope of the invention.
Example 1
A catalyst for preparing pyruvate through photocatalytic lactate oxidation is a sulfur indium zinc compound, and the molar ratio of zinc to indium in the sulfur indium zinc compound is 1: 2-2: 1.
The preparation method of the sulfur indium zinc compound comprises the following steps: adding a zinc source, an indium source and thioacetamide into a flask in sequence according to the molar ratio of zinc to indium, adding water to dissolve, heating the solution to 60-90 ℃, keeping for 3-10 hours, and then carrying out ultrasonic treatment for 0.2-2 hours, wherein the ultrasonic power is as follows: 400W, centrifuging, washing, and vacuum drying at 40-70 ℃ for 3-10 hours.
The zinc source is one or more of zinc sulfate, zinc nitrate, zinc acetate and zinc chloride; the indium source is one or more of indium sulfate, indium nitrate, indium acetate and indium chloride. The specific parameters are shown in Table 1.
This example uses Zn (CH)3COO)2•2H2O and InCl3•4H2O is used as raw material, and other zinc source and indium source can be adopted.
Example 2
A method for preparing pyruvate by photocatalytic lactate oxidation comprises the steps of respectively using a zinc-indium molar ratio of 1:2 (ZnIn)2S4）、1:1（Zn2In2S5）、3:2（Zn3In2S6）、4:2（Zn4In2S7) The sulfur indium zinc compound is used as a catalyst to catalyze the ethyl lactate to oxidize and prepare the ethyl pyruvate, and the specific experimental process is described as follows:
0.1 g of catalyst, 0.1181 g of ethyl lactate and 5 ml of acetonitrile were weighed into a reaction kettle. Oxygen gas was charged to 0.1 MPa, the xenon lamp light source (current 15A, wavelength of 400nm-780nm (added with ultraviolet filter) was turned on at room temperature, stirring was continued for 5 hours, and the product was analyzed by gas chromatography after the reaction was completed, with the results shown in Table 2.
As can be seen from the table, the sulfur indium zinc compound as a photocatalyst shows excellent catalytic performance in the reaction of catalyzing ethyl lactate to oxidize to prepare ethyl pyruvate, and the selectivity of the catalysts with different zinc indium molar ratios to ethyl pyruvate is more than 90%.
Example 3
With Zn3In2S6The catalyst is used for catalyzing ethyl lactate to oxidize and prepare ethyl pyruvate, and the specific experiment is as follows:
the description is as follows: a certain amount of catalyst and ethyl lactate were weighed, as well as 5 ml of acetonitrile, into the reaction kettle. Charging oxygen to a certain pressure, turning on xenon lamp light source (current 15A, wavelength of xenon lamp light source: 400nm-780nm (adding ultraviolet filter)) at room temperature, stirring and maintaining for a certain time. After the reaction, the product was analyzed by gas chromatography.
The amounts of catalyst and ethyl lactate added, the oxygen pressure, the reaction time and the corresponding reaction results are shown in table 3.
Example 4
0.1 g of catalyst, 0.1181 g of ethyl lactate and 5 ml of toluene were weighed into a reaction kettle. Charging oxygen to 0.5 MPa, turning on xenon lamp light source (current 15A, wavelength of xenon lamp light source: 400nm-780nm (adding ultraviolet filter)) at room temperature, stirring and maintaining for 6 h. After the reaction, the product was analyzed by gas chromatography.
The conversion rate of ethyl lactate and the yield of ethyl pyruvate are respectively 78% and 73%, and the selectivity of ethyl pyruvate is 96%. Therefore, the method can be used for preparing the ethyl pyruvate with high selectivity by catalyzing the oxidation of the ethyl lactate by using the toluene as the solvent.
Example 5
0.1 g of catalyst and 0.5905 g of ethyl lactate were weighed into a reaction kettle. Charging oxygen to 0.5 MPa, turning on xenon lamp light source (current 15A, wavelength of xenon lamp light source: 400nm-780nm (adding ultraviolet filter)) at room temperature, stirring and maintaining for 6 h. After the reaction, the product was analyzed by gas chromatography.
The conversion rate of ethyl lactate and the yield of ethyl pyruvate are 44% and 40%, respectively, and the selectivity of ethyl pyruvate is 93%. Therefore, the method can be used for preparing the ethyl pyruvate with high selectivity by catalyzing the oxidation of the ethyl lactate under the solvent-free condition.
Although embodiments of the present invention have been described above, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims.
Claims (9)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082152A (en) * | 2023-02-17 | 2023-05-09 | 江苏师范大学 | A kind of photocatalytic oxidation ethyl lactate prepares the method for ethyl pyruvate |
| CN116217393A (en) * | 2022-12-05 | 2023-06-06 | 天津理工大学 | A kind of photocatalytic ethyl lactate prepares the method for ethyl pyruvate |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000017230A (en) * | 1998-07-02 | 2000-01-18 | Showa Denko Kk | Coating composition containing photocatalyst and method for forming coating film |
| CN102218333A (en) * | 2011-01-07 | 2011-10-19 | 大连海事大学 | A method for preparing ZnIn2S4 visible light catalyst at low temperature |
| CN104276951A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for using water phase to catalytically oxidize lactates for preparing pyruvates |
| CN104860824A (en) * | 2014-02-24 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method for preparing pyruvate through catalyzing oxygen to oxidize lactate |
| CN104860825A (en) * | 2014-02-24 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method for preparing pyruvate through catalytic conversion of lactic acid |
| CN107930687A (en) * | 2017-11-06 | 2018-04-20 | 郑州大学 | The method of modifying of TS 1 and its application in solvent-free catalysis lactate prepares pyruvate |
| WO2019197992A1 (en) * | 2018-04-09 | 2019-10-17 | King Abdullah University Of Science And Technology | Bacteria-based catalysts and method of making |
| CN110743573A (en) * | 2018-07-23 | 2020-02-04 | 中国科学院大连化学物理研究所 | Method for photocatalytic carbon dioxide reduction |
| CN112094190A (en) * | 2020-09-28 | 2020-12-18 | 江南大学 | Method for preparing ester by photocatalytic oxidation esterification of glycerol |
-
2021
- 2021-05-12 CN CN202110516390.8A patent/CN113198492B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000017230A (en) * | 1998-07-02 | 2000-01-18 | Showa Denko Kk | Coating composition containing photocatalyst and method for forming coating film |
| CN102218333A (en) * | 2011-01-07 | 2011-10-19 | 大连海事大学 | A method for preparing ZnIn2S4 visible light catalyst at low temperature |
| CN104276951A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for using water phase to catalytically oxidize lactates for preparing pyruvates |
| CN104860824A (en) * | 2014-02-24 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method for preparing pyruvate through catalyzing oxygen to oxidize lactate |
| CN104860825A (en) * | 2014-02-24 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method for preparing pyruvate through catalytic conversion of lactic acid |
| CN107930687A (en) * | 2017-11-06 | 2018-04-20 | 郑州大学 | The method of modifying of TS 1 and its application in solvent-free catalysis lactate prepares pyruvate |
| WO2019197992A1 (en) * | 2018-04-09 | 2019-10-17 | King Abdullah University Of Science And Technology | Bacteria-based catalysts and method of making |
| CN110743573A (en) * | 2018-07-23 | 2020-02-04 | 中国科学院大连化学物理研究所 | Method for photocatalytic carbon dioxide reduction |
| CN112094190A (en) * | 2020-09-28 | 2020-12-18 | 江南大学 | Method for preparing ester by photocatalytic oxidation esterification of glycerol |
Non-Patent Citations (4)
| Title |
|---|
| PIERRE CUENDET ET.AL: "Direct Photoconversion of Pyruvate to Lactate in Aqueous TiO2 Dispersions", 《THE JOURNAL OF CHEMICAL PHYSICS》 * |
| ZHIXIN CHEN ET.AL: "Low-Temperature and Template-Free Synthesis of ZnIn2S4 Microspheres", 《INORGANIC CHEMISTRY》 * |
| 安家君等: "可见光催化剂ZnIn_2S_4改性研究进展", 《水处理技术》 * |
| 曹鑫等: "超大比表面积硫铟锌的低温水浴合成及光催化性能研究", 《湖北理工学院学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116217393A (en) * | 2022-12-05 | 2023-06-06 | 天津理工大学 | A kind of photocatalytic ethyl lactate prepares the method for ethyl pyruvate |
| CN116082152A (en) * | 2023-02-17 | 2023-05-09 | 江苏师范大学 | A kind of photocatalytic oxidation ethyl lactate prepares the method for ethyl pyruvate |
| CN116082152B (en) * | 2023-02-17 | 2024-11-29 | 江苏师范大学 | A method for preparing ethyl pyruvate by photocatalytic oxidation of ethyl lactate |
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