CN108325532A - Catalyst in the building-up process of methyl glycollate and preparation method thereof, application - Google Patents
Catalyst in the building-up process of methyl glycollate and preparation method thereof, application Download PDFInfo
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- B01J23/83—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 rare earths or actinides
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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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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Abstract
The invention discloses catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, applications.The present invention is to be pre-processed first to silica supports, utilizes " air bag retardance " principle, carrier outer layer is made to pass through process part desiliconization alkanisation; with partial hydrophilicity; and inside is protected not processed, holding hydrophobicity by air bag, impregnates active component with aqueous solvent to prepare egg shell shape catalyst.Compared with coprecipitation and preparation catalyst, eggshell layer structure catalyst prepared by the present invention, the active site of high degree of dispersion is formed in catalyst coating, not only inhibit dimethyl oxalate deep hydrogenation, improve methyl glycollate selectivity, and catalytic inner duct deposited carbon effect is reduced, improve catalyst stabilization performance.In addition, catalyst egg shell structurre reduces catalyst activity component load capacity, catalyst cost is reduced.
Description
Technical field
The present invention relates to a kind of ester through hydrogenation catalyst preparation and application fields, and in particular to a kind of prepared by dimethyl oxalate plus hydrogen
The method for preparing catalyst of standby methyl glycollate and application.
Background technology
Methyl glycollate(HOCH2COOCH3, MG)Also known as hydroxy methyl acetate, because containing α-in its molecular structure simultaneously
H, hydroxyl and ester group and simultaneously with the chemical property of alcohol and ester, methyl glycollate can occur catalytic hydrogenation synthesis second two
It is sweet that alcohol, hydrolysis generate glycolic, oxidation reaction generates glyoxalic acid methylester, carbonylation prepares dimethyl malenate, ammonolysis system
Propylhomoserin.As a kind of important chemical intermediate, methyl glycollate is widely used in chemical industry, feed, pesticide, medicine, dyestuff
With the multiple fields such as fragrance.Wherein methyl glycollate hydrolysis prepares glycolic, and then can be closed by way of autohemagglutination or copolymerization
At the aliphatic polyester series high molecular material that can be decomposed completely, there is great Development volue and wide as a kind of environment-friendly materials
Market prospects.
Currently, the production method of domestic methyl glycollate mainly uses chloroactic acid method, monoxone is mixed with sodium hydroxide
Hydrolysis occurs and generates glycolic, second can be obtained by esterification by removing the ethyl alcohol acid crude that the sodium chloride of generation obtains
Alkyd methyl esters.Not only production technology is long for this method, high energy consumption, and production is seriously polluted, and waste water is difficult to handle, and produces glycolic
Methyl esters it is of high cost.The typical structural characteristics of " few gas rich in coal and poor in oil " are presented in China's energy resource structure, and grass is synthesized through synthesis gas by coal
Then Hydrogenation has carried out industrialized production to dimethyl phthalate for ethylene glycol.And prepared by dimethyl oxalate plus hydrogen is for methyl glycollate phase
It is more economical for, environmentally friendly and be more suitable for actual industrial production.This method is big with domestic dimethyl oxalate commercial plant
Large-scale production construction, production cost will be greatly lowered, and the prospect of marketing is optimistic.
The reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollate is as follows:
As can be seen from the above equation, Hydrogenation of Dimethyl Oxalate generates methyl glycollate, and methyl glycollate is further hydrogenated to second two
Alcohol and ethyl alcohol.Selectivity of the methyl glycollate in Hydrogenation of Dimethyl Oxalate reaction is improved, needs to avoid deep hydrogenation reaction
Occur.From the point of view of the document reported at present, Hydrogenation of Dimethyl Oxalate reacts mainly with copper-based and argentum-based catalyzer, copper-based catalysts
Hydrogenation activity is high, and product is the dominant catalyst of coal-ethylene glycol device based on ethylene glycol and ethyl alcohol;Although argentum-based catalyzer
Methyl glycollate high selectivity, but poor activity, and argentum-based catalyzer manufacturing cost height is not suitable for commercial plant application.This
Outside, product ethanol acid methyl esters is easy carbon distribution in Hydrogenation of Dimethyl Oxalate reaction and blocking duct makes catalyst inactivation.Patent
JP135895 reports a kind of prepared by dimethyl oxalate plus hydrogen for methyl glycollate copper-based catalysts, and the catalyst choice is relatively low.
Chinese patent(CN 103785408)A kind of copper Si catalyst of various metals modification prepared by coprecipitation is reported in oxalic acid
Excellent selectivity is showed in the reaction of dimethyl ester preparation of ethanol through hydrogenation acid methyl esters, but stability waits to investigate.Therefore, in this field
There is still a need for develop the good catalyst of a kind of height at low cost, active, high selectivity, stability.
From the point of view of existing literature, in prepared by dimethyl oxalate plus hydrogen in the reaction of methyl glycollate, either co-precipitation is gone back
It is catalyst prepared by infusion process, belongs to uniformity catalyst, Active components distribution is in entire caltalyst phase.This makes
Being in the active component of duct deep inside reduces reagentia, not only reduces active component utilization rate, increases catalyst
Cost, and target product methyl glycollate is more prone to carbon distribution in duct and leads to catalyst inactivation.Egg shell shape is catalyzed
Agent not only improves catalyst activity component utilization rate, can also inhibit the further hydrogenation reaction of methyl glycollate to improve selection
Property, while the methyl glycollate generated in catalyst shell is easier to spread and prevent carbon distribution from improving catalyst stability.
Invention content
The problems in for the above-mentioned prior art, it is an object of the invention to provide this one kind is of low cost, high stability,
High activity, highly selective hydrogenation catalyst preparation method, and reacted for methyl glycollate applied to prepared by dimethyl oxalate plus hydrogen
In.
The present invention is to be pre-processed first to silica supports, utilizes " air bag retardance " principle, makes carrier outer layer at
Part desiliconization alkanisation is managed, there is partial hydrophilicity, and inside is protected not processed, holding hydrophobicity by air bag, is soaked with aqueous solvent
Stain active component is to prepare egg shell shape catalyst.
The technical scheme is that:
A kind of prepared by dimethyl oxalate plus hydrogen for methyl glycollate catalyst, using Cu as active component, Pt, Au, Pd, Ru, Zn,
One or more of Mn, Mo, Al, Ni, Co, La are used as auxiliary agent, wherein the mass fraction of active component is 1%-40%, auxiliary agent
Mass fraction be 0%-30%, remaining is carrier silicas.
The preparation method of above-mentioned catalyst specifically includes following steps:
1)Silica supports are placed at 100-130 DEG C in the toluene solution of dimethyldichlorosilane and are heated to reflux 1-100
Hour, preferably 12-48 hours, wherein dimethyldichlorosilane mass fraction was 10%-50%, preferably 20%-40%.
2)After drying, with ethanol water impregnation of silica carrier 1-100 hours of certain proportion ammonium fluoride, wherein second
The ratio of alcohol and water is 1:100-100:1, the mass fraction of ammonium fluoride is 1-30%.
3)It is 10-24 hours dry under the conditions of 60-120 DEG C after filtering.
4)By step 3)The carrier silicas gone after silanization treatment is impregnated in maceration extract 8-36 hours, then in
60-120 DEG C dries 8-24 hours, is roasted 2-36 hours for 200-650 DEG C in Muffle furnace, wherein the maceration extract is activearm
Point and the solution that is formed with the water as solvent of auxiliary agent soluble salt, heating rate is 0.2-3 DEG C/min when roasting.
The active component and promoter soluble salt is copper nitrate, chloroplatinic acid, gold chloride, palladium nitrate, ruthenium trichloride, nitre
Sour zinc, manganese nitrate, nitric acid molybdenum, aluminum nitrate, nickel nitrate, cobalt nitrate, lanthanum borate.
The silica of the catalyst carrier is in macroporous silica, mesoporous silicon oxide and mesoporous silica
It is one or more.
The application in the building-up process of methyl glycollate of above-mentioned catalyst:
The Catalyst packing is in continuous fixed bed reactors, and the catalyst is before the use in hydrogen and indifferent gas
It is restored in the gaseous mixture of body, the content of hydrogen is 1-100%, preferably 30-100%, and reducing condition is:Reduction pressure is 0.1-
9.0MPa, gaseous mixture volume space velocity are 30-5000h-1, preferably 300-3000 h-1, reduction temperature is 100-400 DEG C, preferably
160-350 DEG C, the rate that the reduction activation temperature is risen to by room temperature be with 0.1-5 DEG C/min, preferably 0.1-2.5 DEG C/
min;Reaction condition is:Reaction temperature be 130-320 DEG C, preferably 180-250 DEG C, reaction pressure 0.2-8.0MPa, preferably
For 0.5-3.5MPa, dimethyl oxalate liquid liquid hourly space velocity (LHSV) is 0.05-10.0h-1, preferably 0.2-3.0 h-1, hydrogen and oxalic acid
The molar ratio of dimethyl ester is 5:1-360:1, preferably 10:1-200:1.
The present invention can be catalyzed prepared by dimethyl oxalate plus hydrogen for methyl glycollate, and the catalyst for reacting required is urged for egg shell shape
Agent, of low cost, stability, catalytic activity, high selectivity.Wherein, under certain condition, catalysis dimethyl oxalate conversion ratio can
92.8%, methyl glycollate selectivity is stablized 1000 hours or more up to 91.4%, has prospects for commercial application.
Specific implementation mode
Embodiment 1
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 10 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g copper nitrates and
In the aqueous solution of 0.1169g zinc nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-1%Zn-10-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 0.5h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 65.7%, and methyl glycollate is selectively 87.3%.
Embodiment 2
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 10 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g copper nitrates and
In the aqueous solution of 0.117g lanthanum nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying exists
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-1.5%La-10-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 1.0 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 55.6%, and methyl glycollate is selectively 89.2%.
Embodiment 3
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 10 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g copper nitrates and
In the aqueous solution of 0.195g cobalt nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying exists
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-1.5%Co-10-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 0.5 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 95.2%, and methyl glycollate is selectively 78.5%.
Embodiment 4
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 10 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g copper nitrates and
In the aqueous solution of 0.117g nickel nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying exists
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-1.5%Ni-10-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 0.7 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 88.6%, and methyl glycollate is selectively 83.7%.
Embodiment 5
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 10 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g manganese nitrates and
In the aqueous solution of 0.167g zinc nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying exists
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-0.86%Mn-10-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 0.5 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 76.3%, and methyl glycollate is selectively 89.2%.
Embodiment 6
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 5 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g copper nitrates and
In the aqueous solution of 0.167g manganese nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying exists
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-0.86%Mn-5-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 1.0 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 69.5%, and methyl glycollate is selectively 91.3%.
Embodiment 7
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 15 hours, wherein ethyl alcohol and water
Ratio be 1:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g copper nitrates and
In the aqueous solution of 0.167g manganese nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying exists
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-0.86%Mn-15-1/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 1.0 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 75.1%, and methyl glycollate is selectively 88.2%.
Embodiment 8
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 20 hours, wherein ethyl alcohol and water
Ratio be 1:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g copper nitrates and
In the aqueous solution of 0.2338g zinc nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-2%Zn-20-1/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 0.8 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 48.3%, and methyl glycollate is selectively 84.3%.
Embodiment 9
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 15 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 0.739g copper nitrates and
In the aqueous solution of 0.2338g zinc nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 10%Cu-2%Zn-15-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 1.0 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 38.2%, and methyl glycollate is selectively 87.8%.
Embodiment 10
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 10 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Above-mentioned pretreated silica 2.5g is weighed, by its incipient impregnation in containing 0.739g copper nitrates,
In the aqueous solution of 0.2338g zinc nitrates and 0.0395g aluminum nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.
Catalyst after drying roasts 4 hours in Muffle furnace at 400 DEG C.Group in gained catalyst is divided into 10%Cu-2%Zn-1%
Al-10-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
2.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 1.0 h-1, hydrogen ester
Than being 50:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas-chromatography
Analysis, dimethyl oxalate conversion ratio are 58.5%, and methyl glycollate is selectively 88.6%.
Embodiment 11
5.0g silica is weighed, flow back in dimethyldichlorosilane toluene solution 24 hours, wherein dimethyl two are placed it in
Chlorosilane mass fraction is 20%, and temperature is 90-100 DEG C;Washing is 24 hours dry under the conditions of 130 DEG C after filtering.
Treated silica is placed in the ethanol water of ammonium fluoride and impregnates 10 hours, wherein ethyl alcohol and water
Ratio be 2:1, the mass fraction of ammonium fluoride is 20%;It is 20 hours dry under the conditions of 120 DEG C after washing.
Weigh above-mentioned pretreated silica 2.5g, by its incipient impregnation in containing 1.109g copper nitrates and
In the aqueous solution of 0.2338g zinc nitrates, dip time is 48 hours, is dried 24 hours in 90 DEG C of baking ovens.Catalyst after drying
It is roasted 4 hours at 400 DEG C in Muffle furnace.Group in gained catalyst is divided into 15%Cu-2%Zn-10-2/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, reduction treatment is carried out.Reduction temperature is heated up from room temperature with 2 DEG C/min
To 300 DEG C, reduction pressure is 0.2MPa, hydrogen gas space velocity 150h-1, the recovery time is 6 hours.Temperature is reduced to 200 DEG C, pressure
3.0MPa is risen to, constant-flux pump squeezes into the methanol solution of dimethyl oxalate, and the liquid hourly space velocity (LHSV) of dimethyl oxalate is 1.0 h-1, hydrogen ester
Than being 150:1. the mass fraction of its dimethyl oxalate in preparation methanol solution dimethyl oxalate in preparation is 15%.Reaction product is through gas phase color
Spectrum analysis, dimethyl oxalate conversion ratio are 92.8%, and methyl glycollate is selectively 91.4%.
To sum up, compared with coprecipitation and preparation catalyst, eggshell layer structure catalyst prepared by the present invention,
Catalyst coating forms the active site of high degree of dispersion, not only inhibits dimethyl oxalate deep hydrogenation, improves methyl glycollate
Selectivity, and catalytic inner duct deposited carbon effect is reduced, improve catalyst stabilization performance.In addition, catalyst eggshell layer knot
Structure reduces catalyst activity component load capacity, reduces catalyst cost.The catalyst of the present invention has synthetic method simple, honest and clean
Valence is easy to get, and catalyst high selectivity in Hydrogenation of Dimethyl Oxalate reaction, stability is good, environmental-friendly feature.
Above example is used only as illustrating present disclosure, and in addition to this, the present invention also has other embodiment.But it is all
The technical solution formed using equivalent replacement or equivalent deformation mode is all fallen in protection scope of the present invention.
Claims (7)
1. a kind of prepared by dimethyl oxalate plus hydrogen that is used for is for the catalyst during methyl glycollate, it is characterised in that:It is to live with Cu
Property component, Pt, Au, Pd, Ru, Zn, Mn, Mo, Al, Ni, Co, one or more of La be used as auxiliary agent, wherein active component
Mass fraction be 1%-40%, the mass fraction of auxiliary agent is 0%-30%, remaining is carrier silicas.
2. the method for preparing catalyst described in claim 1, it is characterised in that this method specifically includes following steps:
Step 1)Silica supports are placed at 100-130 DEG C in the toluene solution of dimethyldichlorosilane and are heated to reflux 1-
100 hours, wherein dimethyldichlorosilane mass fraction was 10%-50%;
Step 2)After drying, with ethanol water impregnation of silica carrier 1-100 hours of certain proportion ammonium fluoride, wherein second
The ratio of alcohol and water is 1:100-100:1, the mass fraction of ammonium fluoride is 1-30%;
Step 3)It is 10-24 hours dry under the conditions of 60-120 DEG C after filtering;
Step 4)By step 3)Sample is impregnated in maceration extract 8-36 hours, and it is small that 8-24 is then dried in 60-120 DEG C of baking oven
When, it is roasted 2-36 hours for 200-650 DEG C in Muffle furnace, wherein the maceration extract is for active component and auxiliary agent and as solvent
The solution that is formed of water, heating rate is 0.2-3 DEG C/min when roasting.
3. according to the method described in claim 2, it is characterized in that:Step 1)Described in be heated to reflux the time be 12-48 it is small
When;The dimethyldichlorosilane mass fraction is 20%-40%.
4. according to the method described in claim 2, it is characterized in that:In step 4)In, the active component is copper nitrate, institute
The auxiliary agent stated is soluble-salt, including chloroplatinic acid, gold chloride, palladium nitrate, ruthenium trichloride, zinc nitrate, manganese nitrate, nitric acid molybdenum, nitre
Sour aluminium, nickel nitrate, cobalt nitrate or lanthanum borate.
5. according to the method described in claim 2, it is characterized in that:The silica supports are selected from macroporous silica, are situated between
It is one or more in hole silica and mesoporous silica.
6. the catalyst that the method according to claim 11 obtains is in prepared by dimethyl oxalate plus hydrogen for answering in methyl glycollate
With, which is characterized in that by the Catalyst packing in continuous fixed bed reactors, the catalyst is before the use in hydrogen
It is restored in the gaseous mixture of inert gas, the content of hydrogen is 1-100%, and reducing condition is:Reduction pressure is 0.1-9.0MPa,
Gaseous mixture volume space velocity is 30-5000h-1, reduction temperature is 100-400 DEG C, and the rate that reduction temperature is risen to by room temperature is 0.1-5
℃/min;Reaction condition is:Reaction temperature is 130-320 DEG C, reaction pressure 0.2-8.0MPa, when dimethyl oxalate liquid liquid
Air speed is 0.05-10.0h-1, the molar ratio of hydrogen and dimethyl oxalate is 5:1-360:1.
7. application according to claim 6, it is characterised in that:The content of the hydrogen is 30-100%;Reducing condition is:
Gaseous mixture volume space velocity is 300-3000 h-1;Reduction temperature is 160-350 DEG C;The rate that reduction temperature is risen to by room temperature is
0.1-2.5℃/min;Reaction condition is:Reaction temperature is 180-250 DEG C, reaction pressure 0.5-3.5MPa;Dimethyl oxalate
Liquid liquid hourly space velocity (LHSV) is 0.2-3.0 h-1, the molar ratio of hydrogen and dimethyl oxalate is 10:1-200:1.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110856817A (en) * | 2018-08-22 | 2020-03-03 | 上海浦景化工技术股份有限公司 | Catalyst for producing methyl glycolate and preparation method and application thereof |
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CN112536041A (en) * | 2019-09-20 | 2021-03-23 | 中石化南京化工研究院有限公司 | Catalyst for preparing methyl isobutyl carbinol and preparation method thereof |
CN112642441A (en) * | 2020-12-10 | 2021-04-13 | 西安凯立新材料股份有限公司 | Catalyst for preparing 1,2, 4-butanetriol through catalytic hydrogenation and preparation method and application thereof |
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 |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101954288A (en) * | 2010-09-27 | 2011-01-26 | 上海华谊(集团)公司 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
CN106582652A (en) * | 2015-10-16 | 2017-04-26 | 上海华谊能源化工有限公司 | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof |
CN106807371A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | Hydrogenolysis of glycerin prepares egg-shell catalyst and its preparation and the application of 1,3- propane diols |
CN107586254A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院大连化学物理研究所 | A kind of method of oxalic ester hydrogenation synthesizing of ethylene glycol |
CN107694572A (en) * | 2017-09-19 | 2018-02-16 | 河南能源化工集团研究院有限公司 | A kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol catalyst |
-
2018
- 2018-03-13 CN CN201810205018.3A patent/CN108325532B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101954288A (en) * | 2010-09-27 | 2011-01-26 | 上海华谊(集团)公司 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
CN106582652A (en) * | 2015-10-16 | 2017-04-26 | 上海华谊能源化工有限公司 | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof |
CN106807371A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | Hydrogenolysis of glycerin prepares egg-shell catalyst and its preparation and the application of 1,3- propane diols |
CN107586254A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院大连化学物理研究所 | A kind of method of oxalic ester hydrogenation synthesizing of ethylene glycol |
CN107694572A (en) * | 2017-09-19 | 2018-02-16 | 河南能源化工集团研究院有限公司 | A kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol catalyst |
Non-Patent Citations (1)
Title |
---|
BAOWEI WANG ET AL.: "Synthesis of methyl glycolate by hydrogenation of dimethyl oxalate over Cu-Ag/SiO2 catalyst", 《JOURNAL OF NATURAL GAS CHEMISTRY》 * |
Cited By (12)
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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 |
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