CN109574834A - The production method of glyoxylic ester - Google Patents
The production method of glyoxylic ester Download PDFInfo
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- CN109574834A CN109574834A CN201710904401.3A CN201710904401A CN109574834A CN 109574834 A CN109574834 A CN 109574834A CN 201710904401 A CN201710904401 A CN 201710904401A CN 109574834 A CN109574834 A CN 109574834A
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- 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
The present invention relates to a kind of production methods of glyoxylic ester.The step of the method includes ethyl glycolates and oxygen-containing gas under the conditions of oxidative dehydrogenation by the reactor at least one section catalyst bed；The catalyst bed has the mixture of inert filler and catalyst；In the mixture, the weight ratio of inert filler and catalyst is (0.01~2): 1.This method can be used in the industrial production of glyoxylic ester.
Description
Technical field
The present invention relates to a kind of production methods of glyoxylic ester.
Background technique
Glyoxylic ester has the chemical property of aldehyde and ester concurrently, and a variety of reactions can occur, and especially hydrolysis can prepare glyoxalic acid.
And glyoxalic acid is the organic intermediate of synthetic perfume, medicine, food, varnish raw material, dyestuff, plastic additive, can be used 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 at rising always
Gesture.
Domestic and international glyoxalic acid preparation method specifically includes that oxidation of glyoxal, acid by electrolytic reduction of oxalic method, dichloro with raw material point
Acetic acid or dibromoacetic acid Hydrolyze method, maleic anhydride Ozonation, glycolic enzymatic oxidation method, in addition there are ethylene oxies
Change method and acetaldehyde oxidation etc..Wherein, oxidation of glyoxal is the main production process of current glyoxalic acid, but the main of this method is asked
Topic have glyoxalic acid yield is low, environmental pollution weight, equipment corrosion are fast, reaction condition acutely and product separation difficulty etc..In above-mentioned second
In the various production technologies of aldehydic acid, cost of material height and product isolation technics complexity are main bottlenecks.Currently, domestic glyoxalic acid is raw
Production technology generally relatively falls behind, and especially product impurity content is high, limits its scope of application, to severely impact
The market development of glyoxalic acid and its downstream product, thus improve oxoacetic acid product quality, reduce production cost, find it is suitable
Vanguard technology has important practical significance.
Coal-ethylene glycol technique obtains fast development in recent years, and domestic industry production technology is increasingly mature at present, number
A coal-ethylene glycol commercialized devices have been gone into operation or just in the Large scale construction stage, consequent can generate a large amount of technique pair
Product ethanol acid esters.The development and utilization of methyl glycollate rationally efficiently make good use of second also increasingly by the attention of researchers
Alkyd methyl esters is of great significance to coal-ethylene glycol process efficiency and reduction glyoxalic acid production cost is improved, thus develops with second
Carboxylic ester catalysis oxidation glyoxylic ester, then the process route that glyoxalic acid is made through catalyzing hydrolysis is very necessary and with market
Competitiveness.
It is well known that methyl glycollate is in the presence of a catalyst, generating glyoxalic acid methylester by oxidative dehydrogenation is one
Exothermal reaction process generates CO as the complete oxidation that side reaction or subsequent reactions occur acts on2And water, it can also release big
The heat of amount.Thus to inhibit worthless subsequent reactions, the yield of purpose product is improved, heat must be enable preferably timely
It removes.But the patent and document published are concentrated mainly on the catalyst of methyl glycollate catalysis oxidation production glyoxalic acid methylester
In terms of technique research and development, very few and low there are glyoxalic acid methylester yield obvious shortcoming is reported used type of reactor,
It still needs to be further improved and develops.And reactor is as methyl glycollate catalysis oxidation production glyoxalic acid methylester industrial production dress
One of core equipment set, its performance quality directly affect the quality of reaction effect, the utilization rate of catalyst and product.Cause
And the needs of glyoxalic acid methylester technology and production development are produced according to glyoxalic acid methylester catalytic gas phase oxidation, these technologies have
Further development and improved space.
Document US4340748 discloses a kind of using ethyl glycolate as raw material, oxygen-containing gas under the conditions of 100~600 DEG C
The method that catalytic gas phase oxidation obtains glyoxylic ester is carried out to it, the yield of glyoxylic ester is up to 88.3% in liquid product,
The yield of glyoxylic ester only has 43.5% under the conditions of some.
Document CN85101409A discloses a kind of method for preparing hydrated glyoxylate as raw material using gaseous state ethyl glycolate,
Using tubular reactor, catalyst support has at least been done sternly by a cylindrical type monomer composition, and to the arrangement mode of monomer
Lattice limit, and the yield of glyoxylic ester is up to 82.1% in liquid product.
Summary of the invention
The present invention relates to a kind of production methods of glyoxylic ester.
Specifically, the present invention relates to a kind of production method of glyoxylic ester, including ethyl glycolate and oxygen-containing gas are in oxygen
The step of passing through the reactor at least one section catalyst bed under the conditions of fluidized dehydrogenation；The catalyst bed is filled out with inertia
The mixture of material and catalyst；In the mixture, the weight ratio of inert filler and catalyst is (0.01~2): 1.
According to an aspect of the present invention, the reactor is calandria type fixed bed reactor.
According to an aspect of the present invention, in the mixture, the weight ratio of inert filler and catalyst be (0.01~
1.8): 1, preferably (0.01~1.5): 1.
According to an aspect of the present invention, the ethyl glycolate has general formula HO-CH2-COOR；Wherein, R is alkyl, excellent
It is selected as the linear chain or branched chain aliphatic alkyl of 1~8 carbon atom, the linear or branched alkyl group of more preferably 1~5 carbon atom,
Most preferably methyl or ethyl.
According to an aspect of the present invention, in terms of volume parts, in the oxygen-containing gas, the content of air is 0~100
Part, O2Content be 1~20 part, N2Content be 80~99 parts.
According to an aspect of the present invention, the oxidative dehydrogenation condition includes: oxygen and ethyl glycolate molar ratio is 0.6:1
~3:1, the weight space velocity of ethyl glycolate are 0.05~2.0 hour-1, reaction temperature be 200~400 DEG C, reaction pressure be 0~
1.0MPa；Preferably include: oxygen is 0.6:1~2:1 with ethyl glycolate molar ratio, and the weight space velocity of ethyl glycolate is 0.1~1.5
Hour-1, reaction temperature is 220~350 DEG C, and reaction pressure is 0~0.8MPa；It include: more preferably oxygen and ethyl glycolate mole
Than being 0.1~1.0 hour for the weight space velocity of 0.6:1~1.5:1, ethyl glycolate-1, reaction temperature is 220~320 DEG C, reaction
Pressure is 0~0.5MPa.
According to an aspect of the present invention, based on parts by weight, the catalyst includes: 2~20 parts by vanadium and silver-colored group
At at least one of group active component, 0~10 part of at least one of the group being made of molybdenum, copper, bismuth, magnesium and sodium help
Agent, at least one of 10~90 parts of groups being made of aluminium oxide and silica carrier.
According to an aspect of the present invention, the inert filler in the group being made of inert alumina and porcelain ball extremely
Few one kind.
According to an aspect of the present invention, the reactor has n catalyst bed, and n is the integer between 2 to 6.
According to an aspect of the present invention, inert filler is identical as the weight ratio of catalyst in n catalyst bed.
According to an aspect of the present invention, autoreactor entrance is to exporting, in n catalyst bed, inert filler with urge
The weight ratio of agent gradually decreases.
According to an aspect of the present invention, autoreactor entrance plays meter, and inert filler accounts for mixed in first catalyst bed
The 40~70% of object total weight are closed, catalyst content accounts for the 30~60% of total weight of the mixture；In later each catalyst bed,
Inert filler content successively reduces 10~40%, and catalyst content successively increases 10~40%.
It should be noted that n-th section of heretofore described catalyst bed, be all based on for reactor inlet
N sections of catalyst beds.
The present inventor the study found that in oxygen and ethyl glycolate catalytic reaction process, the excessive oxidation of glyoxylic ester and
Decomposition be cause react purpose product glyoxylic ester yield it is low the main reason for, and the excessive oxidation of glyoxylic ester and decompose with instead
The temperature for answering device bed is closely related, the excessive oxidation of the higher glyoxylic ester of temperature and to decompose probability higher.Thus, for
For ethyl glycolate catalytic oxidative dehydrogenation glyoxylic ester, control reaction hot(test)-spot temperature, for preventing glyoxylic ester excessive oxidation
And decomposition, the yield for improving purpose product are very important.Ethyl glycolate is in the presence of a catalyst, raw by oxidative dehydrogenation
It is a strong exothermal reaction process at glyoxylic ester, as the complete oxidation that side reaction or subsequent reactions occur acts on, generates CO2
And water, it can also release a large amount of heat.Thus to inhibit worthless subsequent reactions, the yield of purpose product is improved, must be made
Heat can be removed preferably in time.And dynamics research shows the reaction rate of ethyl glycolate catalytic dehydrogenation glyoxylic ester
Related to the distribution density of the active component of catalyst, the distribution of the active component of unit carrier specific surface is higher, reaction speed
Rate is faster, and local temperature rise is higher, and therefore, it is steady how to control reaction process, prevents local temperature rise excessively high, and then avoid glyoxalic acid
The excessive oxidation of ester and decomposition are the key problem in technology for improving purpose product yield.Although current calandria type fixed bed reactor is logical
Supercooling medium can remove a large amount of reaction heat to a certain extent, but be still unavoidable from since inducer reactant is dense
Degree is higher, and the temperature rise of upper section catalyst bed is higher in tubulation, and in catalyst bed upper section, there are hot spots to reaction effect and to urge
The unfavorable disadvantage of agent.It is used inert material and catalyst mixed packing in the present invention in calandria type fixed bed reactor
Mode not only can effectively reduce the concentration of Active components distribution in unit volume reactor catalyst bed, effectively avoid part
Reaction rate is too fast, meanwhile, the introducing of inert filler also functions to the effect of heat carrier, can effectively accelerated heat transmit, dispersion heat
Amount, avoids local temperature rise excessively high and causes ethyl glycolate catalytic oxidation rate too fast.Thus technical solution of the present invention is effective
It is too fast to avoid reaction rate, concentrates heat release, cooling medium has little time to remove a large amount of reaction heat in time and lead to local temperature rise
Excessively high disadvantage guarantees the conversion ratio and purpose of raw material to ensure that the performance of catalyst action and the utilization rate of catalyst
The yield of product glyoxylic ester.In the present invention, the mode that loads in mixture of inert filler and catalyst can in calandria type fixed bed reactor
To be loaded in many ways, can to load in mixture ratio big for inert filler and catalyst at reactor inlet section, then along urging
Agent bed gradually reduces, and entirely bed can also uniformly load in mixture.Using technical solution of the present invention, the yield of glyoxylic ester is most
It is big by reachable 90% or more, achieve preferable technical effect.
The present invention will be further described below by way of examples, it should be noted however that protection model of the invention
It encloses and is not limited to these specific embodiments, but be determined by the appended claims.Meanwhile it needing to illustrate
, in the context of the present specification disclosed two or more aspects (or embodiment) can any combination each other, by
This and the technical solution that is formed belongs to a part of this specification original disclosure, while also falling into protection scope of the present invention
Within.
Specific embodiment
[embodiment 1]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Oxygen-containing gas is air.The molar ratio of oxygen and methyl glycollate into reactor is 3:1, methyl glycollate
Weight space velocity be 2.0h-1, reaction temperature is 350 DEG C, pressure 1.0MPa.
Catalyst is using aluminium oxide as carrier, and using vanadium as active component, using sodium as auxiliary agent, the parts by weight of vanadium are 10 parts, sodium
Parts by weight be 2 parts, the parts by weight of carrier are 88 parts.
It include three sections of catalyst beds in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 2:1, inert alumina and catalyst are loaded in mixture than for 0.65:1 in second segment catalyst bed, in third section catalyst bed
Inert alumina and catalyst are loaded in mixture than for 0.01:1.
In the above conditions, the yield of glyoxalic acid methylester is 84.5%.
[embodiment 2]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Oxygen-containing gas is air.The molar ratio of oxygen and methyl glycollate into reactor is 2:1, methyl glycollate
Weight space velocity be 1.0h-1, reaction temperature is 260 DEG C, pressure 0.6MPa.
Catalyst is the same as [embodiment 1].
It include three sections of catalyst beds in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 1.8:1, inert alumina and catalyst is loaded in mixture than for 0.6:1, third section catalyst bed in second segment catalyst bed
Interior inert alumina and catalyst are loaded in mixture than for 0.02:1.
In the above conditions, the yield of glyoxalic acid methylester is 89.3%.
[embodiment 3]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Oxygen-containing gas is the mixture of oxygen and nitrogen, and in terms of volume parts, oxygen content is 1 part, nitrogen content 99
Part.The molar ratio of oxygen and methyl glycollate into reactor is 2:1, and the weight space velocity of methyl glycollate is 1.2h-1, reaction
Temperature is 300 DEG C, pressure 0.8MPa.
Catalyst is using silica as carrier, and using vanadium as active component, using molybdenum as auxiliary agent, the parts by weight of vanadium are 5 parts, molybdenum
Parts by weight are 10 parts, and the parts by weight of carrier are 85 parts.
It include two-stage catalytic agent bed in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 1.5:1, inert alumina and catalyst is loaded in mixture than for 0.35:1 in second segment catalyst bed.
In the above conditions, the yield of glyoxalic acid methylester is 87.6%.
[embodiment 4]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Used catalyst and process conditions are identical as [embodiment 3].
It include three sections of catalyst beds in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 1.45:1, inert alumina and catalyst is loaded in mixture than for 0.6:1, third section catalyst bed in second segment catalyst bed
Interior inert alumina and catalyst are loaded in mixture than for 0.01:1.
In the above conditions, the yield of glyoxalic acid methylester is 88.5%.
[embodiment 5]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Oxygen-containing gas is the mixture of oxygen and nitrogen, and in terms of volume parts, oxygen content is 15 parts, and nitrogen content is
85 parts.The molar ratio of oxygen and methyl glycollate into reactor is 1.5:1, and the weight space velocity of methyl glycollate is 0.6h-1,
Reaction temperature is 250 DEG C, and pressure is normal pressure.
Catalyst is using aluminium oxide as carrier, and with vanadium, silver for active component, the parts by weight of vanadium are 2 parts, silver-colored parts by weight
It is 6 parts, the parts by weight of carrier are 92 parts.
It include three sections of catalyst beds in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 1.4:1, inert alumina and catalyst is loaded in mixture than for 0.55:1, third section catalyst bed in second segment catalyst bed
Interior inert alumina and catalyst are loaded in mixture than for 0.01:1.
In the above conditions, the yield of glyoxalic acid methylester is 89.8%.
[embodiment 6]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Used catalyst and process conditions are identical as [embodiment 5].
It include two sections of catalyst beds in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 1:1, inert alumina and catalyst is loaded in mixture than for 0.35:1 in second segment catalyst bed.
In the above conditions, the yield of glyoxalic acid methylester is 89.5%.
[embodiment 7]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Oxygen-containing gas is air.The molar ratio of oxygen and methyl glycollate into reactor is 1:1, methyl glycollate
Weight space velocity be 0.05h-1, reaction temperature is 220 DEG C, pressure 0.5MPa.
Catalyst is using silica as carrier, and with vanadium, silver for active component, using copper, magnesium as auxiliary agent, the parts by weight of vanadium are
5 parts, silver-colored parts by weight are 3.5 parts, and the parts by weight of copper are 3 parts, and the parts by weight of magnesium are 1.5 parts, the parts by weight of carrier
It is 87 parts.
It include two sections of catalyst beds in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 0.8:1, inert alumina and catalyst is loaded in mixture than for 0.25:1 in second segment catalyst bed.
In the above conditions, the yield of glyoxalic acid methylester is 90.2%.
[embodiment 8]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Used catalyst and process conditions are identical as [embodiment 7].
Include one section of catalyst bed in tubulation, inert alumina and catalyst are loaded in mixture than being 0.7 in catalyst bed:
1。
In the above conditions, the yield of glyoxalic acid methylester is 89.4%.
[embodiment 9]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Oxygen-containing gas is the mixture of oxygen and nitrogen, and in terms of volume parts, oxygen content is 20 parts, and nitrogen content is
80 parts.The molar ratio of oxygen and methyl glycollate into reactor is 0.6:1, and the weight space velocity of methyl glycollate is 0.15h-1, reaction temperature is 240 DEG C, pressure 0.3MPa.
Catalyst is using aluminium oxide as carrier, and using silver as active component, using molybdenum as auxiliary agent, silver-colored parts by weight are 20 parts, molybdenum
Parts by weight be 0.25 part, remaining is carrier.
It include two-stage catalytic agent bed in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 0.8:1, porcelain ball and catalyst is loaded in mixture than for 0.2:1 in second segment catalyst bed.
In the above conditions, the yield of glyoxalic acid methylester is 90.3%.
[embodiment 10]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Oxygen-containing gas is the mixture of oxygen and nitrogen, and in terms of volume parts, oxygen content is 20 parts, and nitrogen content is
80 parts.The molar ratio of oxygen and methyl glycollate into reactor is 1.2:1, and the weight space velocity of methyl glycollate is 0.3h-1,
Reaction temperature is 250 DEG C, pressure 0.4MPa.
Catalyst is using silica as carrier, and using silver as active component, using bismuth as auxiliary agent, silver-colored parts by weight are 10 parts, bismuth
Parts by weight be 2 parts, the parts by weight of carrier are 88 parts.
It include four sections of catalyst beds in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 1:1, inert alumina and catalyst is loaded in mixture than for 0.35:1, third section catalyst bed is lazy in second segment catalyst bed
Property aluminium oxide and catalyst are loaded in mixture than for 0.15:1, the 4th section of catalyst bed inert alumina and catalyst load in mixture than for
0.01:1。
In the above conditions, the yield of glyoxalic acid methylester is 90.5%.
[embodiment 11]
Methyl glycollate catalyst oxidation reactor is tubulation fixed bed reactors, and tubulation apparatus with catalyst inside, tubulation is outside cold
But medium.Oxygen-containing gas is the mixture of oxygen and nitrogen, and in terms of volume parts, oxygen content is 20 parts, nitrogen content 80
Part.The molar ratio of oxygen and methyl glycollate into reactor is 0.8:1, and the weight space velocity of methyl glycollate is 0.2h-1, instead
Answering temperature is 230 DEG C, pressure 0.4MPa.
It include four sections of catalyst beds in tubulation, catalyst is to carry with silica in first segment and second segment catalyst bed
Body, using vanadium as active component, using molybdenum as auxiliary agent, the parts by weight of vanadium are 6 parts, and the parts by weight of molybdenum are 2.5 parts, the weight of carrier
Number is 91.5 parts；Catalyst is using silica as carrier in third section and the 4th section of catalyst bed, using silver as active component, with
Bismuth is auxiliary agent, and silver-colored parts by weight are 12 parts, and the parts by weight of bismuth are 1 part, and the parts by weight of carrier are 87 parts.
Porcelain ball and catalyst are loaded in mixture than for 1.2:1 in first segment catalyst bed, porcelain ball in second segment catalyst bed
With loading in mixture than for 0.6:1 for catalyst, porcelain ball and catalyst are loaded in mixture than for 0.35:1 in third section catalyst bed, and the 4th section
Porcelain ball and catalyst loads in mixture than for 0.01:1 in catalyst bed.
In the above conditions, the yield of glyoxalic acid methylester is 91%.
[embodiment 12]
Methyl glycollate catalyst oxidation reactor is calandria type fixed bed reactor, and tubulation apparatus with catalyst inside is outside tubulation
Cooling medium.Oxygen-containing gas is the mixture of oxygen and nitrogen, and in terms of volume parts, oxygen content is 22 parts, and nitrogen content is
78 parts.The molar ratio of oxygen and methyl glycollate into reactor is 1:1, and the weight space velocity of methyl glycollate is 0.12h-1,
Reaction temperature is 240 DEG C, pressure 0.35MPa.
Catalyst is using silica as carrier, and using silver as active component, using bismuth as auxiliary agent, silver-colored parts by weight are 11 parts, bismuth
Parts by weight be 1 part, the parts by weight of carrier are 88 parts.
It include six sections of catalyst beds in tubulation, inert alumina and catalyst loads in mixture ratio in first segment catalyst bed
For 1.6:1, inert alumina and catalyst is loaded in mixture than for 1:1, third section catalyst bed is lazy in second segment catalyst bed
Property aluminium oxide and catalyst are loaded in mixture than for 0.65:1, the 4th section of catalyst bed inert alumina and catalyst load in mixture than for
0.4:1, inert alumina and catalyst loads in mixture than for 0.2:1, the 6th section of catalyst bed is lazy in the 5th section of catalyst bed
Property aluminium oxide and catalyst are loaded in mixture than for 0.01:1.
In the above conditions, the yield of glyoxalic acid methylester is 91.2%.
[comparative example 1]
According to [embodiment 2] identical condition and reaction raw materials, only loading catalyst in reactor tubulation does not use inertia
Fillers dilute, the yield of glyoxalic acid methylester are 79.5%.
[embodiment 13]
It include three sections of catalyst beds, first segment catalysis in tubulation according to [embodiment 5] identical condition and reaction raw materials
Inert alumina and catalyst loads in mixture inert alumina and catalysis in second segment catalyst bed than for 1.2:1 in agent bed
Agent is loaded in mixture than for 0.6:1, and third section catalyst bed inert alumina and catalyst are loaded in mixture than for 1:1.
In the above conditions, the yield of glyoxalic acid methylester is 83.3%.
[comparative example 2]
According to [embodiment 10] identical condition and reaction raw materials, only loading catalyst in reactor tubulation is not used lazy
Property fillers dilute, the yield of glyoxalic acid methylester is 83.6%.
[embodiment 14]
It include four sections of catalyst beds in tubulation, first segment is urged according to [embodiment 10] identical condition and reaction raw materials
Inert alumina and catalyst loads in mixture inert alumina and catalysis in second segment catalyst bed than for 1:1 in agent bed
Agent is loaded in mixture than for 0.35:1, and third section catalyst bed inert alumina and catalyst are loaded in mixture than for 0.6:1, the 4th section is urged
Agent bed inert alumina and catalyst are loaded in mixture than for 0.1:1.In the above conditions, the yield of glyoxalic acid methylester is
84.9%.
Claims (12)
1. a kind of production method of glyoxylic ester, including ethyl glycolate and oxygen-containing gas pass through under the conditions of oxidative dehydrogenation with extremely
The step of reactor of few one section of catalyst bed；The catalyst bed has the mixture of inert filler and catalyst；Institute
It states in mixture, the weight ratio of inert filler and catalyst is (0.01~2): 1.
2. the production method of glyoxylic ester according to claim 1, which is characterized in that the reactor is calandria type fixed bed
Reactor.
3. the production method of glyoxylic ester according to claim 1, which is characterized in that in the mixture, inert filler with
The weight ratio of catalyst is (0.01~1.8): 1, preferably (0.01~1.5): 1.
4. the production method of glyoxylic ester according to claim 1, which is characterized in that the ethyl glycolate has general formula HO-
CH2-COOR；Wherein, R is alkyl, the linear chain or branched chain aliphatic alkyl of preferably 1~8 carbon atom, more preferably 1~5
The linear or branched alkyl group of carbon atom, most preferably methyl or ethyl.
5. the production method of glyoxylic ester according to claim 1, which is characterized in that described oxygenous in terms of volume parts
In body, the content of air is 0~100 part, O2Content be 1~20 part, N2Content be 80~99 parts.
6. the production method of glyoxylic ester according to claim 1, which is characterized in that the oxidative dehydrogenation condition includes: oxygen
Gas and ethyl glycolate molar ratio are 0.6:1~3:1, and the weight space velocity of ethyl glycolate is 0.05~2.0 hour-1, reaction temperature is
200~400 DEG C, reaction pressure is 0~1.0MPa；
Preferably include: oxygen is 0.6:1~2:1 with ethyl glycolate molar ratio, and the weight space velocity of ethyl glycolate is 0.1~1.5 small
When-1, reaction temperature is 220~350 DEG C, and reaction pressure is 0~0.8MPa；
It more preferably include: oxygen and ethyl glycolate molar ratio is 0.6:1~1.5:1, the weight space velocity of ethyl glycolate is 0.1~
1.0 hour-1, reaction temperature is 220~320 DEG C, and reaction pressure is 0~0.5MPa.
7. the production method of glyoxylic ester according to claim 1, which is characterized in that based on parts by weight, the catalyst
Include: 2~20 parts by least one of vanadium and the group that forms of silver active component, 0~10 part by molybdenum, copper, bismuth, magnesium and sodium
At least one of group of composition auxiliary agent, at least one of 10~90 parts of groups being made of aluminium oxide and silica carrier.
8. the production method of glyoxylic ester according to claim 1, which is characterized in that the inert filler is selected from by inertia oxygen
Change at least one of the group of aluminium and porcelain ball composition.
9. the production method of glyoxylic ester according to claim 1, which is characterized in that the reactor has n catalyst
Bed, n are the integer between 2 to 6.
10. the production method of glyoxylic ester according to claim 9, which is characterized in that inert filler in n catalyst bed
It is identical as the weight ratio of catalyst.
11. the production method of glyoxylic ester according to claim 9, which is characterized in that for autoreactor entrance to exporting, n is a
In catalyst bed, the weight ratio of inert filler and catalyst is gradually decreased.
12. the production method of glyoxylic ester according to claim 11, which is characterized in that autoreactor entrance, which rises, to be counted, and first
Inert filler accounts for the 40~70% of total weight of the mixture in a catalyst bed, catalyst content account for total weight of the mixture 30~
60%；In later each catalyst bed, inert filler content successively reduces 10~40%, and catalyst content successively increases 10~
40%.
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Cited By (4)
| 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 |
| 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 |
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| CN115672337A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing glyoxylic ester and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| CN115368237A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | <xnotran></xnotran> |
| CN115672337A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing glyoxylic ester and preparation method and application thereof |
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