CN107445828A - The method of synthesizing glyoxalic acid ester - Google Patents
The method of synthesizing glyoxalic acid ester Download PDFInfo
- Publication number
- CN107445828A CN107445828A CN201610367259.9A CN201610367259A CN107445828A CN 107445828 A CN107445828 A CN 107445828A CN 201610367259 A CN201610367259 A CN 201610367259A CN 107445828 A CN107445828 A CN 107445828A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- fluid
- acid ester
- reaction
- glyoxalic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Abstract
A kind of the problem of the present invention relates to method of synthesizing glyoxalic acid ester, mainly solves prior art and reaction temperature height be present, and glyoxylic ester is selectively low.The present invention preferably solves the problem by using the technical scheme including making nitrogen-containing oxide fluid, oxygen-bearing fluid, fluid containing ethyl glycolate contact the reactions steps for generating glyoxylic ester, in the industrial production that glyoxylic ester processed is aoxidized available for ethyl glycolate.
Description
Technical field
The present invention relates to a kind of method of synthesizing glyoxalic acid ester.
Background technology
Glyoxylic ester has the chemical property of aldehyde and ester concurrently, and a variety of reactions can occur, particularly hydrolyze
Glyoxalic acid can be prepared.And glyoxalic acid be synthetic perfume, medicine, food, varnish raw material, dyestuff,
The organic intermediates such as plastic additive, available for production oral penicillin, vanillic aldehyde, mandelic acid and
Allantoin etc., so both at home and abroad to the consumption figure of glyoxalic acid also always into the trend of rising.
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.Industrially most
Conventional has acid by electrolytic reduction of oxalic method, glyoxal nitric acid oxidation method, maleic acid (acid anhydride) ozonization method
Deng.Current domestic glyoxalic acid industry run into two it is larger the problem of：First, it is high-volume, high-quality
The glyoxalic acid of amount is insufficient, prevents the price advantage of product downstream from giving full play to, serious
It has impact on the market development of glyoxalic acid and its downstream product；Secondly, the country is substantially all uses second
Dialdehyde method produces glyoxalic acid.And the fluctuation of International Crude Oil, the price of glyoxal is influenceed, finally
Influence glyoxalic acid price.
China has abundant coal, natural gas resource, and petroleum resources are insufficient, so opening up non-
The method of petroleum path, there is its own strategic significance in China.In the 1970s, by world's stone
The influence of oily crisis, various countries start to carry out the largely C1 based on natural gas and coal-based feedstocks one after another
Chemical research, correlation technique also achieve quick development in the nineties in last century, are especially studying
Great breakthrough, thing followed meeting are achieved in terms of producing ethylene glycol as raw material using coal or natural gas
Substantial amounts of process byproducts ethyl glycolate is produced, so exploitation aoxidizes glyoxylic ester processed with ethyl glycolate
Non oil-based route there is very high competitiveness.
But the method at present using ethyl glycolate as raw material oxidative synthesis glyoxylic ester is substantially gas
Phase oxidation is reacted, and the reaction temperature is higher, it is necessary to which 200~400 DEG C could obtain higher ethanol
Acid esters conversion ratio.Not only observable index is larger for higher reaction temperature, and product easily gathers under high temperature
Close, also easily oxidation reaction is excessively produced great amount of carbon dioxide and water, cause glyoxylic ester yield
It is relatively low.Such as it using ethyl glycolate is raw material at 100~600 DEG C that document US4340748, which is disclosed a kind of,
Under the conditions of catalytic gas phase oxidation carried out to it with oxygen-containing gas obtain the method for glyoxylic ester, liquid phase production
The yield of glyoxylic ester is below 88.3% in thing, and the yield of glyoxylic ester only has under the conditions of some
43.5%, and the reaction temperature in embodiment is both greater than 200 DEG C.
The content of the invention
The technical problems to be solved by the invention are that prior art has reaction temperature height, glyoxylic ester
A kind of the problem of selectivity is low, there is provided method of new synthesizing glyoxalic acid ester.This method has reaction
The characteristics of temperature is low, and glyoxylic ester is selectively high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：One kind synthesis acetaldehyde
The method of acid esters, including make nitrogen-containing oxide fluid, oxygen-bearing fluid, the contact of fluid containing ethyl glycolate
Generate the reactions steps of glyoxylic ester.
In above-mentioned technical proposal, reaction temperature is 50~180 DEG C, and reaction pressure is 0~2MPa；It is excellent
Selection of land, reaction temperature are 70~150 DEG C, and reaction pressure is 0~1.0MPa.
In above-mentioned technical proposal, the nitrogen-containing oxide fluid includes NO, N2O3Or NO2In extremely
Few one kind.
In above-mentioned technical proposal, it is preferable that NO volume contents are more than in the nitrogen-containing oxide fluid
50%.
In above-mentioned technical proposal, the oxygen-bearing fluid is oxygen, air or oxygen and indifferent gas
The mixture of body；Oxygen content is more than 20 volume % in the oxygen-bearing fluid.
In above-mentioned technical proposal, oxygen and second in the fluid containing ethyl glycolate in the oxygen-bearing fluid
The mol ratio of carboxylic ester is (0.6~10):1；Nitrogen oxides contains with described in the nitrogen oxides fluid
The mol ratio of oxygen is (4~50) in oxygen fluid:1；Weight of the fluid containing ethyl glycolate to catalyst
It is 0.1~10 hour to measure air speed-1。
In above-mentioned technical proposal, it is preferable that the reaction is carried out in the presence of a catalyst, described
Catalyst is aluminum oxide.
In above-mentioned technical proposal, by weight percentage, the catalyst also includes 0.0005~1%
P.
In above-mentioned technical proposal, the glyoxylic ester is glyoxalic acid methylester or glyoxylic acid ethyl ester.
In the inventive method the preparation method of phosphorus-containing alumina catalyst be to be known in the art,
Generally：Mixed after concentrated phosphoric acid is diluted with water with aluminum oxide, under the conditions of 50~90 DEG C stirring 2~
24 hours, after 80~120 DEG C of drying 400~550 DEG C of roastings produce the catalyst within 4~8 hours.
The inventive method generates the route of glyoxylic ester using nitrogen oxides, oxygen, ethyl glycolate reaction,
Compared with the technology path directly reacted using oxygen and ethyl glycolate under catalyst action, due to
The inventive method is added including NO, N in reaction system2O3Or NO2At least one of nitrogen
Oxide, NO volume contents in nitrogen-containing oxide fluid are controlled to be more than 50%, such nitric oxide
It is easy to continue to be oxidized to nitrogen dioxide, dinitrogen tetroxide in oxygen-enriched environment.From electrode potential
Understand, they all have very strong oxidability, can under the conditions of comparatively gentle Oxidation of Alcohol it is sour
Alcoholic extract hydroxyl group in ester.Meanwhile control NO volume contents in nitrogen-containing oxide fluid to be more than 50%,
Hydroxyl over oxidation can be avoided, obtains the selectivity of higher glyoxylic ester.And aluminium oxide catalyst,
The catalyst of P element is particularly with the addition of, its acid activity position is also beneficial to improve turning for ethyl glycolate
Rate.Using the inventive method, under relatively low reaction temperature (50~180 DEG C), it is ensured that
Ethyl glycolate conversion ratio reaches 95%, and the selectivity of glyoxylic ester achieves preferable skill to 94%
Art effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
6g aluminium oxide catalysts are weighed in fixed bed reactors, using NO and air and glycolic
Methyl esters is raw material, and wherein NO is 6 with contained oxygen molar ratio in air, oxygen and ethanol in air
Sour methyl esters mol ratio is 0.8, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature, 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 1.
【Embodiment 2】
Press【Embodiment 1】Reaction condition, simply change catalyst be the oxidation containing 0.0005%P
Al catalysts.Aluminium oxide catalysts of the 6g containing 0.0005%P is weighed in fixed bed reactors,
Use NO with air and methyl glycollate for raw material, wherein NO and contained oxygen molar ratio in air
For 6, oxygen and methyl glycollate mol ratio are 0.8 in air, in 80 DEG C of reaction temperature, reaction pressure
Power 0.2MPa, methyl glycollate mass space velocity 1h-1Under the conditions of with catalyst haptoreaction, after reaction
Product condenses, and gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 1.
【Embodiment 3】
Press【Embodiment 1】Reaction condition, simply change catalyst be the aluminum oxide containing 0.05%P
Catalyst.Aluminium oxide catalysts of the 6g containing 0.01%P is weighed in fixed bed reactors, is used
NO is raw material with air and methyl glycollate, and wherein NO is 6 with contained oxygen molar ratio in air,
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, produced after reaction
Thing condenses, and gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 1.
【Embodiment 4】
Press【Embodiment 1】Reaction condition, simply change catalyst be the aluminum oxide containing 1%P urge
Agent.Aluminium oxide catalysts of the 6g containing 1%P is weighed in fixed bed reactors, using NO
It is raw material with air and methyl glycollate, wherein NO is 6 with contained oxygen molar ratio in air, empty
Oxygen and methyl glycollate mol ratio are 0.8 in gas, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 5】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using containing
40%NO and 60%NO2Oxides of nitrogen gas and air and methyl glycollate be raw material, wherein nitrogen
Oxide is 6 with contained oxygen molar ratio in air, and oxygen and methyl glycollate mol ratio are in air
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 1.
【Embodiment 6】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using containing
80%NO, 15%NO2And 5%N2O3Oxides of nitrogen gas is raw material with air and methyl glycollate,
Wherein nitrogen oxides and contained oxygen molar ratio in air are 6, and oxygen and methyl glycollate rub in air
You are than being 0.8, 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 separation, liquid phase is taken
Sample is analyzed.Reaction result is shown in Table 1.
【Embodiment 7】
It is that raw material enters in the fixed bed reactors equipped with filler by NO, air and methyl glycollate,
Wherein NO is 6 with contained oxygen molar ratio in air, oxygen and methyl glycollate mol ratio in air
For 4, in 150 DEG C, reaction pressure 2MPa of reaction temperature, methyl glycollate mass space velocity 0.1h-1
Under the conditions of react, after reaction product condense, gas-liquid separation, sampling analysis is done to liquid phase.Reaction knot
Fruit is shown in Table 1.
【Embodiment 8】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO gas
Body is raw material, wherein NO and oxygen with oxygen, nitrogen mixed gas and methyl glycollate containing 15% oxygen
Mol ratio is 6, and oxygen and methyl glycollate mol ratio are 0.8 in gaseous mixture, 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 separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 1.
【Embodiment 9】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.6, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 10】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 2, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 11】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 3, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 12】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.5, in 100 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 13】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.8, in 50 DEG C, reaction pressure 1.5MPa of reaction temperature,
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 1.
【Embodiment 14】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.8, in 180 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 15】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.8, in 80 DEG C, reaction pressure 0MPa of reaction temperature,
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 1.
【Embodiment 16】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.8, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
Methyl glycollate mass space velocity 0.1h-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 1.
【Embodiment 17】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO
It is raw material with air and methyl glycollate, wherein NO is 6 with contained oxygen molar ratio in air, empty
Oxygen and methyl glycollate mol ratio are 0.8 in gas, in 100 DEG C of reaction temperature, reaction pressure
0.2MPa, methyl glycollate mass space velocity 3h-1Under the conditions of with catalyst haptoreaction, produced after reaction
Thing condenses, and gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in Table 1.
【Embodiment 18】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.8, in 120 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 19】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.8, in 150 DEG C, reaction pressure 0.2MPa of reaction temperature,
Methyl glycollate mass space velocity 10h-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 1.
【Embodiment 20】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 4 with contained oxygen molar ratio in air, air
Middle oxygen and methyl glycollate mol ratio is 0.8, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 21】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 15 with contained oxygen molar ratio in air, empty
Oxygen and methyl glycollate mol ratio are 0.8 in gas, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 22】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 30 with contained oxygen molar ratio in air, empty
Oxygen and methyl glycollate mol ratio are 0.8 in gas, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 23】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and methyl glycollate are raw material, and wherein NO is 50 with contained oxygen molar ratio in air, empty
Oxygen and methyl glycollate mol ratio are 0.8 in gas, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Embodiment 24】
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using NO with
Air and ethyl glycolate are raw material, and wherein NO is 6 with contained oxygen molar ratio in air, air
Middle oxygen and ethyl glycolate mol ratio is 0.8, in 80 DEG C, reaction pressure 0.2MPa of reaction temperature,
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 1.
【Comparative example 1】
Press【Embodiment 3】Reaction condition, simply do not use nitrogen oxides directly to use air oxidation.
Aluminium oxide catalysts of the 6g containing 0.05%P is weighed in fixed bed reactors, using air and second
Alkyd methyl esters is raw material, and oxygen and methyl glycollate mol ratio are 0.8 wherein in air, in reaction temperature
80 DEG C, reaction pressure 0.2MPa of degree, methyl glycollate mass space velocity 1h-1Under the conditions of connect with catalyst
Reaction is touched, product condenses after reaction, gas-liquid separation, sampling analysis is done to liquid phase.Reaction result is shown in
Table 1.
Table 1
| Embodiment | Reaction temperature | Ethyl glycolate conversion ratio, % | Glyoxylic ester selectivity, % |
| Embodiment 1 | 80 | 91.1 | 90.9 |
| Embodiment 2 | 80 | 95.8 | 90.7 |
| Embodiment 3 | 80 | 95.1 | 93.9 |
| Embodiment 4 | 80 | 94.9 | 93.3 |
| Embodiment 5 | 80 | 92.2 | 90.5 |
| Embodiment 6 | 80 | 94.3 | 93.2 |
| Embodiment 7 | 150 | 65.1 | 92.7 |
| Embodiment 8 | 80 | 91.1 | 91.1 |
| Embodiment 9 | 80 | 94.2 | 94.5 |
| Embodiment 10 | 80 | 97.8 | 89.3 |
| Embodiment 11 | 80 | 98.1 | 88.9 |
| Embodiment 12 | 100 | 94.2 | 94.2 |
| Embodiment 13 | 50 | 90.3 | 93.5 |
| Embodiment 14 | 180 | 99.1 | 87.9 |
| Embodiment 15 | 80 | 96.1 | 92.9 |
| Embodiment 16 | 80 | 98.2 | 88.6 |
| Embodiment 17 | 100 | 94.6 | 94.8 |
| Embodiment 18 | 120 | 93.8 | 94.0 |
| Embodiment 19 | 150 | 94.8 | 92.7 |
| Embodiment 20 | 80 | 96.2 | 93.6 |
| Embodiment 21 | 80 | 97.2 | 91.2 |
| Embodiment 22 | 80 | 98.1 | 89.9 |
| Embodiment 23 | 80 | 98.4 | 90.2 |
| Embodiment 24 | 80 | 96.2 | 93.0 |
| Comparative example 1 | 80 | 15.1 | 87.0 |
Claims (10)
1. a kind of method of synthesizing glyoxalic acid ester, including make nitrogen-containing oxide fluid, oxygen-bearing fluid,
The reactions steps of the contact generation glyoxylic ester of fluid containing ethyl glycolate.
2. the method for synthesizing glyoxalic acid ester according to claim 1, it is characterised in that reaction temperature
Spend for 50~180 DEG C, reaction pressure is 0~2MPa.
3. the method for synthesizing glyoxalic acid ester according to claim 2, it is characterised in that reaction temperature
Spend for 70~150 DEG C, reaction pressure is 0.2~1.5MPa.
4. the method for synthesizing glyoxalic acid ester according to claim 1, it is characterised in that described to contain
Nitrogen oxides fluid includes NO, N2O3Or NO2In one kind at least.
5. the method for synthesizing glyoxalic acid ester according to claim 4, it is characterised in that described to contain
NO volume contents are more than 50% in nitrogen oxides fluid.
6. the method for synthesizing glyoxalic acid ester according to claim 1, it is characterised in that described to contain
Oxygen content is more than 20 volume % in oxygen fluid.
7. the method for synthesizing glyoxalic acid ester according to claim 1, it is characterised in that described to contain
In oxygen fluid in oxygen and the fluid containing ethyl glycolate ethyl glycolate mol ratio for (0.6~
10):1；The mol ratio of nitrogen oxides and oxygen in the oxygen-bearing fluid is in the nitrogen oxides fluid
(4~50):1；The fluid containing ethyl glycolate is 0.1~10 hour to the weight space velocity of catalyst-1。
8. the method for synthesizing glyoxalic acid ester according to claim 1, it is characterised in that described anti-
It should carry out in the presence of a catalyst, the catalyst is aluminum oxide.
9. the method for synthesizing glyoxalic acid ester according to claim 8, it is characterised in that with weight
Percentages, the catalyst also include 0.0005~1% P.
10. the method for synthesizing glyoxalic acid ester according to claim 1, it is characterised in that the second
Aldehydic acid ester is glyoxalic acid methylester or glyoxylic acid ethyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610367259.9A CN107445828B (en) | 2016-05-30 | 2016-05-30 | Method for synthesizing glyoxylic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610367259.9A CN107445828B (en) | 2016-05-30 | 2016-05-30 | Method for synthesizing glyoxylic acid esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107445828A true CN107445828A (en) | 2017-12-08 |
| CN107445828B CN107445828B (en) | 2020-08-07 |
Family
ID=60484750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610367259.9A Active CN107445828B (en) | 2016-05-30 | 2016-05-30 | Method for synthesizing glyoxylic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107445828B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105328A (en) * | 2021-04-06 | 2021-07-13 | 上海卓笙环保科技有限公司 | Production method for preparing methyl glyoxylate by selective catalysis of methyl glycolate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340748A (en) * | 1979-02-08 | 1982-07-20 | Hoechst Aktiengesellschaft | Process for the manufacture of glyoxylic acid esters |
-
2016
- 2016-05-30 CN CN201610367259.9A patent/CN107445828B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340748A (en) * | 1979-02-08 | 1982-07-20 | Hoechst Aktiengesellschaft | Process for the manufacture of glyoxylic acid esters |
Non-Patent Citations (1)
| Title |
|---|
| NAIMI-JAMAL M. R. ET AL.: "Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions", 《CHEMSUSCHEM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105328A (en) * | 2021-04-06 | 2021-07-13 | 上海卓笙环保科技有限公司 | Production method for preparing methyl glyoxylate by selective catalysis of methyl glycolate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107445828B (en) | 2020-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107445827A (en) | The method of ethyl glycolate oxidative dehydrogenation glyoxylic ester | |
| CN101475472B (en) | Method for preparing oxalate by coupling reaction of CO in gaseous phase | |
| Gérardy et al. | Sustaining the Transition from a petrobased to a Biobased Chemical Industry with Flow Chemistry | |
| JP6100972B2 (en) | Method for producing acrylic acid from glycerol | |
| CN107445830A (en) | The method that ethyl glycolate oxidative dehydrogenation produces glyoxylic ester | |
| CN104926657B (en) | The method of oxalate gas phase hydrogenation synthesizing alcohol acid esters | |
| JP2012512236A (en) | Method for preparing acrolein from glycerol or glycerin | |
| CN109111343B (en) | Method for preparing benzyl alcohol and homologues through catalytic conversion of low-carbon alcohol and used catalyst | |
| CN107445831B (en) | Process for producing glyoxylic acid esters | |
| CN102989459B (en) | Catalyst for preparing epsilon-caprolactone by oxidizing cyclohexanone/oxygen under aldehyde-assisted oxidizing action | |
| CN107445832A (en) | The method of ethyl glycolate oxidation generation glyoxylic ester | |
| CN107141211B (en) | Preparation method of benzaldehyde | |
| CN107445833B (en) | Method for synthesizing glyoxylic ester by oxidizing glycolate | |
| KR101622236B1 (en) | Heterogeneous Catalyst for Production of Acrylic Acid From Allyl Alcohol, and A Method for Preparation of Acrylic Acid From Allyl Alcohol Using Thereof | |
| CN101838198A (en) | Method for preparing carboxylic ester | |
| CN107445828A (en) | The method of synthesizing glyoxalic acid ester | |
| CN108117489A (en) | A kind of method that ester is prepared by crotonaldehyde and formaldehyde | |
| CN107445839A (en) | The synthetic method of glyoxylic ester | |
| CN107445838A (en) | The oxidation synthesis method of glyoxylic ester | |
| CN113651786B (en) | Method for synthesizing 6-hydroxy-2-ethyl-2H-pyrone- [3] by catalyzing oxidation of alpha-furopropanol and product thereof | |
| CN111217704B (en) | Method for preparing butyl butyrate by directly catalyzing and converting n-butyraldehyde | |
| CN107445834A (en) | The method for producing glyoxylic ester | |
| KR20160041248A (en) | Heterogeneous Catalyst for Production of 3-hydroxypropionic acid From Allyl Alcohol, and A Method for Preparation of 3-hydroxypropionic acid From Allyl Alcohol Using Thereof | |
| CN101161649B (en) | Method for synthesizing lactone compound by catalytic oxidation of cyclone | |
| CN108117472A (en) | It is a kind of that the method containing benzene ring compound is prepared by pinacol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |