CN107445830A - The method that ethyl glycolate oxidative dehydrogenation produces glyoxylic ester - Google Patents
The method that ethyl glycolate oxidative dehydrogenation produces glyoxylic ester Download PDFInfo
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- CN107445830A CN107445830A CN201610367942.2A CN201610367942A CN107445830A CN 107445830 A CN107445830 A CN 107445830A CN 201610367942 A CN201610367942 A CN 201610367942A CN 107445830 A CN107445830 A CN 107445830A
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- ethyl glycolate
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- 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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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The present invention relates to a kind of ethyl glycolate oxidative dehydrogenation to produce glyoxylic ester method, and it is low mainly to solve the problems, such as that prior art has glyoxylic ester yield.The present invention is by using including making nitrogen oxides, oxygen-containing gas and ethyl glycolate contact the reactions steps of generation glyoxylic ester in the presence of a catalyst；The catalyst is in terms of parts by weight, including following component：A) mixture of 0.3~20 part of molybdenum and vanadium；B) 0.05~15 part is selected from least one of copper, palladium, manganese, nickel, cerium, bismuth, potassium, lanthanum, magnesium, tin, iron, calcium or cobalt；C) technical scheme of 65~99.8 parts of carriers preferably solves the problem, in the industrial production available for ethyl glycolate oxidative dehydrogenation glyoxylic ester.
Description
Technical field
The present invention relates to a kind of method of ethyl glycolate oxidative dehydrogenation production glyoxylic ester.
Background technology
Glyoxylic ester has the chemical property of aldehyde and ester concurrently, and a variety of reactions can occur, and particularly hydrolysis can prepare glyoxalic acid.
And glyoxalic acid is the organic intermediates such as synthetic perfume, medicine, food, varnish raw material, dyestuff, plastic additive, available for producing
Oral penicillin, vanillic aldehyde, mandelic acid and allantoin etc., so both at home and abroad to the consumption figure of glyoxalic acid also becoming into rising always
Gesture.
Process for production of glyoxalic acid is different by initiation material, and it is as many as several to there are about ten at present.Industrial the most frequently used have oxalic acid
Electrolytic reduction, glyoxal nitric acid oxidation method, maleic acid (acid anhydride) ozonization method etc..Current domestic glyoxalic acid industry run into two compared with
The problem of big：First, it is high-volume, the glyoxalic acid insufficient supply of high quality, prevents the price advantage of product downstream from abundant
Play, the serious market development that have impact on glyoxalic acid and its downstream product；Secondly, it is domestic substantially all using glyoxal method
Produce glyoxalic acid.And the fluctuation of International Crude Oil, the price of glyoxal is influenceed, it is final to influence glyoxalic acid price.
China has abundant coal, natural gas resource, and petroleum resources are insufficient, so opening up the side of Non oil-based route
Method, there is its own strategic significance in China.In the 1970s, being influenceed by world oil crisis, various countries start to carry out one after another
Largely the C1 chemical research based on natural gas and coal-based feedstocks, correlation technique also achieve quickly in the nineties in last century
Development, especially achieve great breakthrough, thing followed meeting in terms of research produces ethylene glycol using coal or natural gas as raw material
Substantial amounts of process byproducts ethyl glycolate is produced, so the Non oil-based route that exploitation aoxidizes glyoxylic ester processed with ethyl glycolate has
Very high competitiveness.
But it is that the first order in whole oxidation reaction process is anti-by the reaction of ethyl glycolate oxidation synthesis glyoxylate ester
Should, if continuing to walk downward can make glyoxalic acid methylester be further oxidized to acid, further aoxidize, can produce substantial amounts of a large amount of
Carbon dioxide and water, the two reactions can all cause the reduction of glyoxylic ester yield；And due to this oxidation reaction need 200~
400 DEG C could obtain higher ethyl glycolate conversion ratio, also easily make oxidation reaction excessive under this condition, so having to
The yield for improving glyoxylic ester using higher catalyst is reacted stair oxidation.But just both at home and abroad at present to such reaction
Report that the yield of glyoxylic ester is not high.For example, document US4340748 disclose it is a kind of using ethyl glycolate as raw material 100~
Catalytic gas phase oxidation is carried out to it with oxygen-containing gas under the conditions of 600 DEG C, preferably 200~400 DEG C and obtains the method for glyoxylic ester, but
It is that catalyst used in this method is relatively low to the yield of glyoxylic ester, below 90%.
The content of the invention
The technical problems to be solved by the invention are that prior art has ethyl glycolate oxidative dehydrogenation glyoxylic ester yield
A kind of the problem of low, there is provided method of new ethyl glycolate oxidative dehydrogenation production glyoxylic ester.This method has glyoxylic ester receipts
The characteristics of rate is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of ethyl glycolate oxidative dehydrogenation second
The method of aldehydic acid ester, including nitrogen oxides, oxygen-containing gas and ethyl glycolate is contacted generation glyoxylic ester in the presence of a catalyst
Reactions steps；The catalyst is in terms of parts by weight, including following component：
A) mixture of 0.3~20 part of molybdenum and vanadium；
B) 0.05~15 part is selected from least one of copper, palladium, manganese, nickel, cerium, bismuth, potassium, lanthanum, magnesium, tin, iron, calcium or cobalt；
C) 65~99.65 parts of carriers.
In above-mentioned technical proposal, in terms of parts by weight, component a) dosage is 0.5~15 part, and component b) dosage is 0.1
~7 parts, component c) dosage is 78~99.4 parts.
In above-mentioned technical proposal, the component b) is selected from least one of palladium, manganese, nickel, cerium, potassium, lanthanum, iron or cobalt.
In above-mentioned technical proposal, the carrier is in silica, aluminum oxide, zirconium oxide, titanium oxide or Si-Al molecular sieve
At least one.The silicoaluminophosphate molecular is screened from least one of SBA15, MCM-41, ZSM-5.Preferably, the carrier choosing
At least one of self-alumina, zirconium oxide or titanium oxide.It is highly preferred that the carrier is selected from aluminum oxide, zirconium oxide or titanium oxide
In at least two.
In above-mentioned technical proposal, in the mixture of molybdenum and vanadium, the mol ratio of molybdenum and vanadium is 0.1~10.
In above-mentioned technical proposal, reaction condition is：50~180 DEG C of reaction temperature, reaction pressure -0.09~1.5MPa.It is excellent
The reaction condition is selected to be：70~150 DEG C, 0~1.0MPa of reaction pressure of reaction temperature,
In above-mentioned technical proposal, the nitrogen oxides includes NO, N2O3Or NO2In one kind at least.
In above-mentioned technical proposal, NO volumn concentrations are more than 50% in the nitrogen oxides.
In above-mentioned technical proposal, the mol ratio of oxygen and ethyl glycolate is (0.6~10) in the oxygen-bearing fluid:1；Nitrogen oxygen
Compound and the mol ratio of oxygen in oxygen-bearing fluid are (4~50):1；The weight space velocity of the ethyl glycolate is 0.1~10 hour-1。
In above-mentioned technical proposal, the glyoxylic ester is glyoxalic acid methylester or glyoxylic acid ethyl ester.
The preparation method of catalyst described in the inventive method is as follows：
1) by active constituent a) soluble-salt wiring solution-forming I；
2) carrier c) is added to solution I, stirs 2~10 hours, obtain slurry II；
3) by auxiliary agent b) soluble-salt wiring solution-forming III；
4) under stirring, solution III is slowly added dropwise to slurry II, stirred 1~5 hour；
5) placed 12~24 hours under the conditions of 100~200 DEG C of the slurry that step 4) obtains；
6) after the mixture cooling that obtains above-mentioned steps, filtering, washing, drying, 200~400 DEG C of roastings, compression molding
After produce the synthesizing glyoxalic acid ester catalyst.
The reaction of ethyl glycolate oxidative dehydrogenation glyoxylic ester is primarily present two difficult points.First, easily send out at high temperature
Raw over oxidation generation acid either further aoxidizes, and can produce substantial amounts of carbon dioxide and water, influences glyoxylic ester receipts
Rate.Another is exactly that whether feed ethanol acid methyl esters or glyoxalic acid methylester are not very stable, easily generation polymerizations etc.
Reaction influences the yield of glyoxylic ester.Nitrogen oxides, oxygen, ethyl glycolate reaction generation glyoxylic ester are used in the process of the present invention
Route, compared with the technology path directly reacted under catalyst action using oxygen and ethyl glycolate, due to present invention side
Method is added including NO, N in reaction system2O3Or NO2At least one of nitrogen oxides, control nitrogen-containing oxide fluid in
NO volume contents are more than 50%, and such nitric oxide is easy to continue to be oxidized to nitrogen dioxide, four oxidations in oxygen-enriched environment
Phenodiazine.It was found from electrode potential, they all have very strong oxidability, can under the conditions of comparatively gentle Oxidation of Alcohol acid esters
In alcoholic extract hydroxyl group.Meanwhile control NO volume contents in nitrogen-containing oxide fluid to be more than 50%, hydroxyl over oxidation can be avoided, is obtained
Take the selectivity of higher glyoxylic ester.Catalyst used in the present invention has complex metal, has higher
Catalysis oxidation ability, be advantageous to improve the conversion ratio of ethyl glycolate.Using the inventive method, relatively low reaction temperature (50~
180 DEG C) under, just the yield of glyoxylic ester can be made to reach 92%, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
100ml is prepared containing molybdenum 12.5%, the ammonium molybdate of vanadium 3.4% and ammonium metavanadate aqueous solution I, adds 84g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then the iron nitrate solution of 100ml iron content 4% is slowly added dropwise under stirring
Slurry is poured into 500ml autoclave, places 15 hours under the conditions of 180 DEG C of control, then cool down by slurry II, stirring after 2 hours
Filtering, is washed with deionized, and 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA1, takes catalyst
Sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, uses NO and air and methyl glycollate as raw material, wherein NO and
Contained oxygen molar ratio is 6 in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in 80 DEG C of reaction temperature, reaction
Pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, product condenses after reaction, gas-liquid point
From doing sampling analysis to liquid phase.Reaction result is shown in Table 2.
【Embodiment 2】
100ml is prepared containing molybdenum 6.3%, the ammonium molybdate of vanadium 3.4 and ammonium metavanadate aqueous solution I, adds 90g Zirconia carriers,
Stirring 5 hours, obtains slurry II；Then the iron nitrate solution of 100ml iron content 4% is slowly added dropwise to slurry under stirring
II, 500ml autoclave is poured into slurry after 2 hours in stirring, places 15 hours under the conditions of 180 DEG C of control, then cold filtration,
It is washed with deionized, 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA2, takes catalyst sample
Do X- fluorescence (XRF) characterization test and determine that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 3】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 100ml containing 0.25% molybdenum and 0.2 vanadium are prepared, adds 97g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then the iron nitrate solution of 100ml iron content 4% is slowly added dropwise under stirring
Slurry is poured into 500ml autoclave, places 15 hours under the conditions of 180 DEG C of control, then cool down by slurry II, stirring after 2 hours
Filtering, is washed with deionized, and 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA3, takes catalyst
Sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 4】
Ammonium molybdate and the metavanadic acid aqueous solution I of the 100ml containing 22.5% molybdenum and 1.4% vanadium are prepared, adds 76g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then the iron nitrate solution of 100ml iron content 4% is slowly added dropwise under stirring
Slurry is poured into 500ml autoclave, places 15 hours under the conditions of 180 DEG C of control, then cool down by slurry II, stirring after 2 hours
Filtering, is washed with deionized, and 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA4, takes catalyst
Sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 5】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 100ml containing 0.63% molybdenum and 063% vanadium are prepared, adds 92g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then 100ml nickeliferous 9.5% nickel nitrate solution is slowly added dropwise under stirring
Enter slurry II, slurry is poured into 500ml autoclave, placed 15 hours under the conditions of 200 DEG C of control, Ran Houleng by stirring after 5 hours
But filter, be washed with deionized, 120 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA5, takes catalysis
Agent sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 6】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 100ml containing molybdenum 12.5% and vanadium 4.4% are prepared, adds 84g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then copper nitrate solutions of the 100ml containing 4% bronze medal is slowly added dropwise under stirring
Slurry is poured into 500ml autoclave, places 24 hours under the conditions of 180 DEG C of control, then cool down by slurry II, stirring after 2 hours
Filtering, is washed with deionized, and 100 DEG C of drying, 400 DEG C are calcined 4 hours, then compression molding obtains catalyst CA6, takes catalyst
Sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 7】
Ammonium molybdates and ammonium metavanadate aqueous solution I of the 100ml containing molybdenum 8.8% and containing vanadium 3.2 are prepared, adds 90g titanium oxide
Carrier, stir 5 hours, obtain slurry II；Then chlorine palladium acid solutions of the 100ml containing palladium 0.14% is slowly dripped under stirring
Slurry II is added, 500ml autoclave is poured into slurry after 5 hours in stirring, places 15 hours under the conditions of 100 DEG C of control, then
Cold filtration, it is washed with deionized, 120 DEG C of drying, 200 DEG C are calcined 4 hours, then compression molding obtains catalyst CA7, takes and urges
Agent sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 8】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 200ml containing molybdenum 1.9% and vanadium 10% are prepared, 78g zirconium oxides is added and carries
Body, stir 5 hours, obtain slurry II；Then manganese nitrate solutions of the 100ml containing manganese 4% is slowly added dropwise under stirring
Slurry is poured into 500ml autoclave, places 15 hours under the conditions of 200 DEG C of control, then cool down by slurry II, stirring after 5 hours
Filtering, is washed with deionized, and 120 DEG C of drying, 300 DEG C are calcined 4 hours, then compression molding obtains catalyst CA8, takes catalyst
Sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 9】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 100ml containing 18.75% molybdenum and 1.4% vanadium are prepared, adds 83g silica
Carrier, stir 5 hours, obtain slurry II；Then nickel nitrate solutions of the 100ml containing 0.7% nickel is slowly dripped under stirring
Slurry II is added, 500ml autoclave is poured into slurry after 5 hours in stirring, places 15 hours under the conditions of 200 DEG C of control, then
Cold filtration, it is washed with deionized, 120 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA9, takes and urges
Agent sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 10】
Prepare 100ml and contain 1.3% molybdenum and the ammonium molybdate of 0.7% vanadium and the aqueous solution I of ammonium metavanadate, add 97g SBA15
Molecular sieve carrier, stir 5 hours, obtain slurry II；Then by the molten of cerous nitrates of the 100ml containing 2.7% cerium under stirring
Liquid is slowly added dropwise to slurry II, and 500ml autoclave is poured into slurry after 5 hours in stirring, and it is small to place 15 under the conditions of 200 DEG C of control
When, then cold filtration, is washed with deionized, and 120 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst
CA10, take catalyst sample to do X- fluorescence (XRF) characterization test and determine that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 11】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 100ml containing 12.5% molybdenum and 3.4% vanadium are prepared, adds 88g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then the bismuth nitrate solution of 100ml bismuth-containings 0.13% is slowly added dropwise under stirring
Enter slurry II, slurry is poured into 500ml autoclave, placed 15 hours under the conditions of 200 DEG C of control, Ran Houleng by stirring after 5 hours
But filter, be washed with deionized, 120 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA11, takes and urges
Agent sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 12】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 100ml containing 12.5% molybdenum and 2.3% vanadium are prepared, adds 87g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then potassium nitrate solutions of the 100ml containing potassium 1.3% is slowly added dropwise under stirring
Enter slurry II, slurry is poured into 500ml autoclave, placed 15 hours under the conditions of 200 DEG C of control, Ran Houleng by stirring after 5 hours
But filter, be washed with deionized, 120 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA12, takes and urges
Agent sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 13】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 100ml containing 12.5 molybdenums and 1.7% vanadium are prepared, adds 89g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then lanthanum nitrate hexahydrates of the 100ml containing 0.27% lanthanum is slowly added dropwise under stirring
Enter slurry II, slurry is poured into 500ml autoclave, placed 24 hours under the conditions of 180 DEG C of control, Ran Houleng by stirring after 2 hours
But filter, be washed with deionized, 100 DEG C of drying, 400 DEG C are calcined 4 hours, then compression molding obtains catalyst CA13, takes and urges
Agent sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 14】
Ammonium molybdate and ammonium metavanadate aqueous solution I of the 100ml containing 12.5% molybdenum and 3.4% vanadium are prepared, adds 87g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then magnesium nitrate solutions of the 100ml containing magnesium 0.7% is slowly added dropwise under stirring
Enter slurry II, slurry is poured into 500ml autoclave, placed 15 hours under the conditions of 200 DEG C of control, Ran Houleng by stirring after 5 hours
But filter, be washed with deionized, 120 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA14, takes and urges
Agent sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 15】
100ml is prepared containing molybdenum 12.5%, the ammonium molybdate of vanadium 3.4% and ammonium metavanadate aqueous solution I, add 71g aluminum oxide and
15g titanium dioxide carriers, stir 5 hours, obtain slurry II；Then it is under stirring that 100ml stanniferous 1.4% stannic chloride is molten
Liquid is slowly added dropwise to slurry II, and 500ml autoclave is poured into slurry after 2 hours in stirring, and it is small to place 15 under the conditions of 180 DEG C of control
When, then cold filtration, is washed with deionized, and 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst
CA1, take catalyst sample to do X- fluorescence (XRF) characterization test and determine that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 16】
100ml is prepared containing molybdenum 12.5%, the ammonium molybdate of vanadium 3.4% and ammonium metavanadate aqueous solution I, add 44g aluminum oxide and
42g titanium dioxide carriers, stir 5 hours, obtain slurry II；Then it is under stirring that the calcium nitrate of 100ml calcics 1.4% is molten
Liquid is slowly added dropwise to slurry II, and 500ml autoclave is poured into slurry after 2 hours in stirring, and it is small to place 15 under the conditions of 180 DEG C of control
When, then cold filtration, is washed with deionized, and 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst
CA1, take catalyst sample to do X- fluorescence (XRF) characterization test and determine that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 17】
100ml is prepared containing molybdenum 12.5%, the ammonium molybdate of vanadium 3.4% and ammonium metavanadate aqueous solution I, add 42g aluminum oxide and
44g titanium dioxide carriers, stir 5 hours, obtain slurry II；Then it is under stirring that cobalt acetates of the 100ml containing cobalt 2.7% is molten
Liquid is slowly added dropwise to slurry II, and 500ml autoclave is poured into slurry after 2 hours in stirring, and it is small to place 15 under the conditions of 180 DEG C of control
When, then cold filtration, is washed with deionized, and 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst
CA1, take catalyst sample to do X- fluorescence (XRF) characterization test and determine that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 18】
100ml is prepared containing molybdenum 12.5%, the ammonium molybdate of vanadium 3.4% and ammonium metavanadate aqueous solution I, adds 83g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then by copper nitrate and nitric acid of the 100ml containing 4% bronze medal and 1.3% potassium under stirring
Potassium solution is slowly added dropwise to slurry II, and slurry is poured into 500ml autoclave, placed under the conditions of 180 DEG C of control by stirring after 2 hours
15 hours, then cold filtration, was washed with deionized, and 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding is urged
Agent CA1, take catalyst sample to do X- fluorescence (XRF) characterization test and determine that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 19】
100ml is prepared containing molybdenum 12.5%, the ammonium molybdate of vanadium 3.4% and ammonium metavanadate aqueous solution I, adds 71g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then the iron nitrate solution of 100ml iron content 20% is slowly added dropwise under stirring
Slurry is poured into 500ml autoclave, places 15 hours under the conditions of 180 DEG C of control, then cool down by slurry II, stirring after 2 hours
Filtering, is washed with deionized, and 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA1, takes catalyst
Sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 20】
100ml is prepared containing molybdenum 12.5%, the ammonium molybdate of vanadium 3.4% and ammonium metavanadate aqueous solution I, adds 87g carrying aluminas
Body, stir 5 hours, obtain slurry II；Then the iron nitrate solution of 100ml iron content 0.07% is slowly added dropwise under stirring
Enter slurry II, slurry is poured into 500ml autoclave, placed 15 hours under the conditions of 180 DEG C of control, Ran Houleng by stirring after 2 hours
But filter, be washed with deionized, 100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CA1, takes catalysis
Agent sample does X- fluorescence (XRF) characterization test and determines that catalytic component is shown in Table 1.
6g catalyst is weighed in fixed bed reactors, is pressed【Embodiment 1】Conditioned response, reaction result is shown in Table 2.
【Embodiment 21】
6g CA2 catalyst is weighed in fixed bed reactors, using containing 40%NO and 60%NO2Nitrogen oxides gas
Body and air and methyl glycollate be raw material, and wherein nitrogen oxides and contained oxygen molar ratio in air are 6, in air oxygen with
Methyl glycollate mol ratio is 0.8, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature, methyl glycollate mass space velocity 1h-1Condition
Lower and catalyst haptoreaction, product condenses after reaction, gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 22】
6g CA2 catalyst is weighed in fixed bed reactors, using containing 80%NO, 15%NO2And 5%N2O3Nitrogen oxidation
Thing gas is raw material with air and methyl glycollate, and wherein nitrogen oxides and contained oxygen molar ratio in air are 6, oxygen in air
Gas and methyl glycollate mol ratio are 0.8, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature, methyl glycollate mass space velocity 1h-1
Under the conditions of with catalyst haptoreaction, after reaction product condense, gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table
2。
【Embodiment 23】
6g CA2 catalyst is weighed in fixed bed reactors, is mixed using gas containing NO and oxygen, nitrogen containing 15% oxygen
It is raw material to close gas and methyl glycollate, and wherein NO is 6 with oxygen molar ratio, and oxygen and methyl glycollate mol ratio are in gaseous mixture
0.8, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature, methyl glycollate mass space velocity 1h-1Under the conditions of contacted with catalyst instead
Should, product condenses after reaction, gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 24】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.6 in air, in reaction temperature 80
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 25】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Contained oxygen molar ratio is 6 in middle NO and air, and oxygen and methyl glycollate mol ratio are 2 in air, in 80 DEG C of reaction temperature,
Reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense, gas
Liquid is separated, and sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 26】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Contained oxygen molar ratio is 6 in middle NO and air, and oxygen and methyl glycollate mol ratio are 3 in air, in 80 DEG C of reaction temperature,
Reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense, gas
Liquid is separated, and sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 27】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.5 in air, in reaction temperature 100
DEG C, reaction pressure 1MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense, gas
Liquid is separated, and sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 28】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 50
DEG C, reaction pressure 1.5MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 29】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 180
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 30】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 80
DEG C, reaction pressure 0MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense, gas
Liquid is separated, and sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 31】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 80
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 0.1h-1Under the conditions of with catalyst haptoreaction, product is cold after reaction
It is solidifying, gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 32】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 100
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 3h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 33】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 120
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 7h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 34】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 150
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 10h-1Under the conditions of with catalyst haptoreaction, product is cold after reaction
It is solidifying, gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 35】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 4 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 80
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 36】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 15 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 80
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 37】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 30 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 80
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 38】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and methyl glycollate for raw material, its
Middle NO is 50 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are 0.8 in air, in reaction temperature 80
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Embodiment 39】
6g CA2 catalyst is weighed in fixed bed reactors, uses NO with air and ethyl glycolate for raw material, its
Middle NO is 6 with contained oxygen molar ratio in air, and oxygen and ethyl glycolate mol ratio are 0.8 in air, in reaction temperature 80
DEG C, reaction pressure 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense,
Gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 2.
【Comparative example 1】
6g CA2 catalyst is weighed in fixed bed reactors, using air and methyl glycollate, its is hollow for raw material
Oxygen and methyl glycollate mol ratio are 0.8 in gas, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature, methyl glycollate quality
Air speed 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense, gas-liquid separation, sampling analysis is done to liquid phase.Reaction knot
Fruit is shown in Table 2.
【Comparative example 2】
Ammonium molybdate aqueous solutions I of the 100ml containing molybdenum 12.5% is prepared, adds 87g alumina supports, stirs 5 hours, is starched
Material II；Then the iron nitrate solution of 100ml iron content 4% is slowly added dropwise to slurry II under stirring, will after stirring 2 hours
Slurry pours into 500ml autoclave, is placed 15 hours under the conditions of 180 DEG C of control, and then cold filtration, is washed with deionized,
100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CB2, takes catalyst sample to make X- fluorescence (XRF) table
Sign test determines that catalytic component is shown in Table 1.
6g inertia ceramic rings are weighed in fixed bed reactors, use NO with air and methyl glycollate for raw material, its is hollow
Oxygen and methyl glycollate mol ratio are 0.8 in gas, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature, methyl glycollate quality
Air speed 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense, gas-liquid separation, sampling analysis is done to liquid phase.Reaction knot
Fruit is shown in Table 2.
【Comparative example 3】
The metavanadic acid aqueous solution I of the 100ml containing vanadium 3.4% is prepared, adds 94g alumina supports, stirs 5 hours, is starched
Material II；Then the iron nitrate solution of 100ml iron content 4% is slowly added dropwise to slurry II under stirring, will after stirring 2 hours
Slurry pours into 500ml autoclave, is placed 15 hours under the conditions of 180 DEG C of control, and then cold filtration, is washed with deionized,
100 DEG C of drying, 250 DEG C are calcined 4 hours, then compression molding obtains catalyst CB3, takes catalyst sample to make X- fluorescence (XRF) table
Sign test determines that catalytic component is shown in Table 1.
6g inertia ceramic rings are weighed in fixed bed reactors, use NO with air and methyl glycollate for raw material, its is hollow
Oxygen and methyl glycollate mol ratio are 0.8 in gas, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature, methyl glycollate quality
Air speed 1h-1Under the conditions of with catalyst haptoreaction, after reaction product condense, gas-liquid separation, sampling analysis is done to liquid phase.Reaction knot
Fruit is shown in Table 2.Table 1
Table 2
| Embodiment | Reaction temperature | Ethyl glycolate conversion ratio, % | Glyoxylic ester yield, % |
| Embodiment 1 | 80 | 97.1 | 90.41 |
| Embodiment 2 | 80 | 97.8 | 90.68 |
| Embodiment 3 | 80 | 94.5 | 87.81 |
| Embodiment 4 | 80 | 97.1 | 87.29 |
| Embodiment 5 | 80 | 97.1 | 90.32 |
| Embodiment 6 | 80 | 94.2 | 85.05 |
| Embodiment 7 | 80 | 97.1 | 90.41 |
| Embodiment 8 | 80 | 99.2 | 90.72 |
| Embodiment 9 | 80 | 97.1 | 84.54 |
| Embodiment 10 | 80 | 95.1 | 86.60 |
| Embodiment 11 | 80 | 93.3 | 83.78 |
| Embodiment 12 | 80 | 98.1 | 89.24 |
| Embodiment 13 | 80 | 97.5 | 89.45 |
| Embodiment 14 | 80 | 92.4 | 83.06 |
| Embodiment 15 | 80 | 93.1 | 83.51 |
| Embodiment 16 | 80 | 92.8 | 84.51 |
| Embodiment 17 | 80 | 98.1 | 92.01 |
| Embodiment 18 | 80 | 97.2 | 91.34 |
| Embodiment 19 | 80 | 97.5 | 86.79 |
| Embodiment 20 | 80 | 94.3 | 86.70 |
| Embodiment 21 | 80 | 92.98 | 85.37 |
| Embodiment 22 | 80 | 95.95 | 90.26 |
| Embodiment 23 | 80 | 92.41 | 84.92 |
| Embodiment 24 | 80 | 94.95 | 90.37 |
| Embodiment 25 | 80 | 98.54 | 89.49 |
| Embodiment 26 | 80 | 98.78 | 89.44 |
| Embodiment 27 | 100 | 94.97 | 90.62 |
| Embodiment 28 | 50 | 91.54 | 85.65 |
| Embodiment 29 | 180 | 99.15 | 88.49 |
| Embodiment 30 | 80 | 97.47 | 91.25 |
| Embodiment 31 | 80 | 99.48 | 88.38 |
| Embodiment 32 | 100 | 95.03 | 91.30 |
| Embodiment 33 | 120 | 95.12 | 89.90 |
| Embodiment 34 | 150 | 95.04 | 89.39 |
| Embodiment 35 | 80 | 96.98 | 91.39 |
| Embodiment 36 | 80 | 98.21 | 90.84 |
| Embodiment 37 | 80 | 98.87 | 90.57 |
| Embodiment 38 | 80 | 99.14 | 90.42 |
| Embodiment 39 | 80 | 96.87 | 90.76 |
| Comparative example 1 | 80 | 20.3 | 16.74 |
| Comparative example 2 | 80 | 87.6 | 81.22 |
| Comparative example 3 | 80 | 90.3 | 75.19 |
Claims (13)
1. a kind of method of ethyl glycolate oxidative dehydrogenation production glyoxylic ester, including make nitrogen oxides, oxygen-containing gas and glycolic
The reactions steps of ester contact generation glyoxylic ester；The catalyst is in terms of parts by weight, including following component：
A) mixture of 0.3~20 part of molybdenum and vanadium；
B) 0.05~15 part is selected from least one of copper, palladium, manganese, nickel, cerium, bismuth, potassium, lanthanum, magnesium, tin, iron, calcium or cobalt；
C) 65~99.65 parts of carriers.
2. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 1, it is characterised in that with parts by weight
Number meter, component a) dosage is 0.5~15 part, and component b) dosage is 0.1~7 part, and component c) dosage is 78~99.4 parts.
3. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 1, it is characterised in that the component
B) selected from least one of palladium, manganese, nickel, cerium, potassium, lanthanum, iron or cobalt.
4. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 1, it is characterised in that the carrier
Selected from least one of silica, aluminum oxide, zirconium oxide, titanium oxide or Si-Al molecular sieve.
5. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 4, it is characterised in that the carrier
Selected from least one of aluminum oxide, zirconium oxide or titanium oxide.
6. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 4, it is characterised in that the carrier
At least two in aluminum oxide, zirconium oxide or titanium oxide.
7. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 1, it is characterised in that molybdenum and vanadium
In mixture, the mol ratio of molybdenum and vanadium is 0.1~1.
8. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 1, it is characterised in that reaction condition
Including：50~180 DEG C of reaction temperature, 0~1.5MPa of reaction pressure.
9. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 8, it is characterised in that reaction condition
Including：70~150 DEG C of reaction temperature, 0~1.0MPa of reaction pressure.
10. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 1, it is characterised in that the nitrogen
Oxide includes NO, N2O3Or NO2In one kind at least.
11. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 10, it is characterised in that the nitrogen
NO volumn concentrations are more than 50% in oxide.
12. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 10, it is characterised in that oxygen-containing stream
The mol ratio of oxygen and ethyl glycolate is (0.6~10) in body:1；The mol ratio of nitrogen oxides and oxygen in oxygen-bearing fluid is (4
~50):1；The weight space velocity of the ethyl glycolate is 0.1~10 hour-1。
13. the method for ethyl glycolate oxidative dehydrogenation production glyoxylic ester according to claim 10, it is characterised in that the second
Aldehydic acid ester is glyoxalic acid methylester or glyoxylic acid ethyl ester.
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| CN114591170B (en) * | 2020-12-07 | 2023-06-06 | 中国科学院大连化学物理研究所 | Method for preparing glyoxylate by oxidizing glycolate |
| CN114591170A (en) * | 2020-12-07 | 2022-06-07 | 中国科学院大连化学物理研究所 | Method for preparing glyoxylic acid ester by oxidizing glycolic acid ester |
| CN115368237A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | <xnotran></xnotran> |
| CN114308010A (en) * | 2021-12-23 | 2022-04-12 | 江苏金聚合金材料有限公司 | Preparation and application of titanium dioxide loaded molybdenum trioxide and vanadium pentoxide catalyst |
| CN114308010B (en) * | 2021-12-23 | 2023-11-03 | 江苏金聚合金材料有限公司 | Preparation and application of titanium dioxide loaded molybdenum trioxide and vanadium pentoxide catalyst |
| CN114656360A (en) * | 2022-03-03 | 2022-06-24 | 常州大学 | Method for preparing glyoxylic acid methyl ester/glyoxylic acid by continuously oxidizing methyl glycolate |
| CN114656360B (en) * | 2022-03-03 | 2024-03-29 | 常州大学 | Method for preparing methyl glyoxylate/glyoxylate by utilizing continuous oxidation of methyl glycolate |
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