CN104109094B - The method of ethyl glycolate is produced by barkite - Google Patents
The method of ethyl glycolate is produced by barkite Download PDFInfo
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- CN104109094B CN104109094B CN201310130704.6A CN201310130704A CN104109094B CN 104109094 B CN104109094 B CN 104109094B CN 201310130704 A CN201310130704 A CN 201310130704A CN 104109094 B CN104109094 B CN 104109094B
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- C07—ORGANIC CHEMISTRY
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- 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
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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Abstract
The present invention relates to a kind of method of being produced ethyl glycolate by barkite, mainly solve the problem of the object product ethanol acid esters poor selectivity existed in conventional art.The present invention is by adopting with barkite and hydrogen as raw material, with the lower alcohol of 1 ~ 4 carbon for solvent, weight percentage>=10% of barkite and solvent mixture medium-height grass acid esters is 150 DEG C ~ 260 DEG C in temperature, pressure is 1.0 ~ 6.0MPa, and the weight space velocity of barkite is 0.1 ~ 1.5h
-1hydrogen and barkite mol ratio are under the condition of 20 ~ 160:1, after raw material and solvent mixture enter calandria type fixed bed reactor, under copper containing catalyst effect, reaction generates ethyl glycolate, wherein the heat-eliminating medium of calandria type fixed bed reactor is that a kind of method in barkite and solvent mixture, hydrogen or water solves this problem preferably, can be used in the industrial production of ethyl glycolate.
Description
Technical field
The present invention relates to and a kind ofly produce the method for ethyl glycolate by barkite, in particular, relate to a kind of method at calandria type fixed bed reactor dimethyl oxalate in preparation or oxalic acid diethyl ester hydrogenation production methyl glycolate or ethyl glycollate.
Background technology
Oxyacetic acid first (second) ester is the important Chemicals of a class and intermediate, is widely used in many fields such as chemical industry, medicine, agricultural chemicals, feed, fuel and spices.Mainly comprise: 1) as the fine solvent of fiber, resin and rubber; 2) further Hydrogenation ethylene glycol; 3) carbonylation propanedioic acid (list) first (second) ester; 4) ammonia solution glycine; 5) oxydehydrogenation oxoethanoic acid first (second) ester; 6) oxyacetic acid processed etc. is hydrolyzed.
At present, what the production of external ethyl glycolate mainly adopted is formaldehyde carbonylation-ester chemical combination established law, and the method is corrosion-resistant and high pressure resistant requirement is higher to equipment, disposablely has high input, and scale operation has difficulties; And domestic chloroactic acid method of also continuing to use is produced always, the method is by Mono Chloro Acetic Acid and soda lye mixing, stirs evenly.Heating on boiling water, reduction vaporization, filtering sodium-chlor, oil bath is heated to obtain paste liquid, adds methyl alcohol and the vitriol oil afterwards, and reflux to obtain methyl glycolate.Although this production technique process is simple, in production process, corrosion is heavy, pollution is large, high in cost of production problem.Therefore the eco-friendly ethyl glycolate production line of exploitation one is needed badly.
Along with the worsening shortages of petroleum resources, carry out and based on the C1 chemical industry of Sweet natural gas and coal-based feedstocks, China is had important practical significance.Correlation technique also achieves in the nineties in last century and develops fast.Wherein, CO and nitrous acid ester synthesis of oxalic ester by gaseous catalysis are the important breakthrough of C1 route synthesis of oxalate.In recent years, under the condition that the process upstream technology maturation of producing barkite is stable, the product chain further developing barkite downstream has become study hotspot and the emphasis of this catalytic field.Wherein, producing oxyacetic acid first (second) ester by oxalic acid diformazan (second) ester through hydrogenation route, and then exploitation derived product, form high-end Coal Chemical Industry product chain, is the very good technological line of prospect.US Patent No. 4602102 reports the method for a kind of prepared by dimethyl oxalate plus hydrogen for methyl glycolate, and adopt carried copper and silver catalyst, the transformation efficiency of dimethyl oxalate is about 90.2%, and the yield of methyl glycolate is 68%.Chinese patent CN200710061391.8 reports a kind of Catalysts and its preparation method of barkite hydrogenation synthesizing of glycolate methyl esters, adopt copper-silver catalyst that pickling process is prepared from, maximum the reaching of the transformation efficiency of barkite is greater than 95%, and the selectivity of ethyl glycolate is maximum reaches 84%.Chinese patent CN102001944A reports a kind of preparation method of glycolate by catalyzing oxalate under action of hydrogenation, catalyzer take Ag as main active component, under the condition of temperature of reaction 120 ~ 300 DEG C, reaction pressure 0.2 ~ 10.0MPa, the transformation efficiency > 90% of barkite, selectivity >=90% of ethyl glycolate.Chinese patent CN101954288A reports a kind of prepared by dimethyl oxalate plus hydrogen for the Catalysts and its preparation method of methyl glycolate and application, adopt the copper-based catalysts that urea decomposition-homogeneous co-precipitation is prepared from, the transformation efficiency of dimethyl oxalate is maximum reaches 94.5%, and the selectivity of methyl glycolate is maximum reaches 93.5%.
From the technological line of current report, the commercial practice about preparing ethanol by oxalate hydrogenation acid esters is explored still major part and is concentrated in the development of catalyzer, and the selectivity ratios of ethyl glycolate is lower, and has no report to adopted reactor types.And reactor produces one of nucleus equipment of ethyl glycolate industrial installation as barkite hydrogenation, its performance quality directly affects reaction effect, the utilization ratio of catalyzer and the quality of product.
As everyone knows, hydrogenation reaction is thermopositive reaction, and the reaction that barkite hydrogenation produces ethyl glycolate is no exception equally.For exothermic catalytic reaction, along with the carrying out of reaction process, the reaction heat of constantly releasing can make reaction bed temperature improve, and the inactivation of the inevitable accelerator activator of too high local temperature rise, affect the yield of reaction effect and object product.In order to improve the efficiency of reactor, need reaction heat to shift out to reduce temperature of reaction.In industrial reactor, one uses multistage laminar fixed-bed reactor, reduce temperature of reaction by injecting unstripped gas cold shock at multistage catalyst bed interlayer, this reactor, because also reducing reactant concn during unstripped gas cold shock while reduction temperature of reactor, have impact on reaction efficiency.Another kind is shell and tube reactor disclosed in patent DE2123950, unstripped gas enters from upper inlet port and is distributed in each tubulation, react with the catalyst exposure in tubulation, lateral inflow between tubulation, reaction heat is moved heat continuously by the outer boiled water of tubulation, produce steam to be gone out by side pipe, reaction gas goes out reactor by bottom escape pipe.Although, many investigators have carried out special testing research for multistage laminar fixed-bed reactor and calandria type fixed bed reactor, but this kind of research is carried out in conjunction with a certain specific reactor or a certain concrete reaction itself mostly, because condition is different, the rule that it is summed up also is difficult to be applied to other reactor.
Summary of the invention
Technical problem to be solved by this invention is the problem that there is object product ethanol acid esters poor selectivity in conventional art, provide a kind of method of being produced ethyl glycolate by barkite newly, the features such as it is high that the method has barkite transformation efficiency, and ethyl glycolate selectivity is good.
For solving the problems of the technologies described above, the present invention adopts technical scheme as follows: a kind of method of being produced ethyl glycolate by barkite, with barkite and hydrogen for raw material, with the lower alcohol of 1 ~ 4 carbon for solvent, weight percentage>=10% of barkite and solvent mixture medium-height grass acid esters, be 150 DEG C ~ 260 DEG C in temperature, pressure is 1.0 ~ 6.0MPa, and the weight space velocity of barkite is 0.1 ~ 1.5h
-1hydrogen and barkite mol ratio are under the condition of 20 ~ 160:1, after raw material and solvent mixture enter calandria type fixed bed reactor, under copper containing catalyst effect, reaction generates ethyl glycolate, wherein the heat-eliminating medium of calandria type fixed bed reactor is the one in barkite and solvent mixture, hydrogen or water, and the flow direction of heat-eliminating medium and the flow direction of raw material show the same direction or opposite directions.
In technique scheme, the operational condition of calandria type fixed bed reactor is: temperature of reaction is 180 DEG C ~ 240 DEG C, and the weight space velocity of barkite is 0.1 ~ 1.2h
-1, hydrogen and barkite mol ratio are 30 ~ 120:1, and reaction pressure is 1.5 ~ 4.0MPa, weight percentage>=10% of barkite and solvent mixture medium-height grass acid esters.The operational condition of calandria type fixed bed reactor is: temperature of reaction is 190 DEG C ~ 220 DEG C, and the weight space velocity of barkite is 0.1 ~ 0.8h
-1, hydrogen and barkite mol ratio are 40 ~ 100:1, and reaction pressure is 2.0 ~ 4.0MPa, weight percentage>=20% of barkite and solvent mixture medium-height grass acid esters.When barkite is dimethyl oxalate, solvent is methyl alcohol; When barkite is oxalic acid diethyl ester, solvent is ethanol.Copper containing catalyst with at least one in silicon oxide and aluminum oxide for carrier, main active ingredient copper is selected from metallic copper, the oxide compound of copper or its mixture, auxiliary agent is selected from least one in silver, manganese, magnesium, barium, zinc, molybdenum and titanium metal or its metal oxide, metallic copper content is 5% ~ 40% of vehicle weight, metal promoter content is 0.1 ~ 15% of vehicle weight, and carrier specific surface area is 300 ~ 600m
2/ g, catalyst particle diameter is 2 ~ 6mm.When the beds of calandria type fixed bed reactor is positioned at tubulation, heat-eliminating medium passes through from tubulation.When the beds of calandria type fixed bed reactor is positioned at outside tubulation, heat-eliminating medium passes through in tubulation.Heat-eliminating medium is preferably the one in hydrogen or water, and the flow direction of heat-eliminating medium and the flow direction of raw material are preferably in reverse direction.Calandria type fixed bed reactor is separate unit independent operation or at least 2 serial operations.
Research shows, for oxalate hydrogenation, it is typical cascade reaction, first barkite hydrogenation generates ethyl glycolate, ethyl glycolate repeated hydrogenation generating glycol, ethylene glycol excessive hydrogenation then generates ethanol, and low temperature is favourable to the reaction generating ethyl glycolate, and the reaction of high temperature to generating glycol and ethanol is favourable.Research also shows, the carrier of bigger serface is more conducive to the dispersion of catalyst activity component, and the high degree of dispersion of catalyst activity component is conducive to the reactive behavior improving barkite hydrogenation; Auxiliary agent silver, manganese, magnesium, barium, zinc and molybdenum and cooperatively interacting of active ingredient copper can make the selective hydrogenation behavior of catalyzer greatly improve simultaneously.In the present invention, on the one hand by carrying out pre-treatment to silica support, the specific surface area of suitable increase carrier, ensure that the comparatively high degree of dispersion of catalyst activity component on carrier, substantially increase the activity of catalyzer, simultaneously by the introducing of suitable auxiliary agents, substantially increase the reactivity worth that barkite hydrogenation generates ethyl glycolate, on the other hand, take into full account the heat effect of oxalate hydrogenation, by adopting heat-eliminating medium, the scheme of heat is removed to calandria type fixed bed reactor, achieve liberated heat when removing reaction in time, reduce the operation temperature rise of reactor, avoid the heat release of hydrogenation concentrations and cause the too high problem easily causing catalyzer temperature runaway and inactivation and excessive hydrogenation of local temperature rise in beds, ensure that optimal reaction temperature, optimize the operation operating mode of hydrogenation reaction, effectively protect the selective hydrogenation behavior of catalyzer, the stable period of maximized extending catalyst can be reached, and improve transformation efficiency and the object product ethanol acid esters optionally object of barkite.
Adopt technical scheme of the present invention, with dimethyl oxalate or oxalic acid diethyl ester and hydrogen for raw material, methyl alcohol or ethanol are solvent, are 180 DEG C ~ 240 DEG C in temperature of reaction, and the weight space velocity of barkite is 0.1 ~ 1.2h
-1, hydrogen and barkite mol ratio are 30 ~ 120:1, reaction pressure is 1.5 ~ 4.0MPa, weight percentage>=10% of barkite and solvent mixture medium-height grass acid esters, copper containing catalyst with at least one in silicon oxide and aluminum oxide for carrier, main active ingredient copper is selected from metallic copper, the oxide compound of copper or its mixture, auxiliary agent is selected from silver, manganese, magnesium, barium, zinc, at least one in molybdenum and titanium metal or its metal oxide, metallic copper content is 5% ~ 40% of vehicle weight, metal promoter content is 0.1 ~ 15% of vehicle weight, carrier specific surface area is 300 ~ 600m
2/ g, catalyst particle diameter is under the condition of 2 ~ 6mm, after raw material and solvent mixture enter calandria type fixed bed reactor, under copper containing catalyst effect, reaction generates ethyl glycolate, wherein the heat-eliminating medium of calandria type fixed bed reactor is the one in barkite and solvent mixture, hydrogen or water, the flow direction of heat-eliminating medium and the flow direction of raw material show the same direction or opposite directions, to be that the transformation efficiency of barkite is maximum reach 100% to its reaction result, the selectivity of ethyl glycolate is maximum reaches more than 97%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the calandria type fixed bed reactor schematic diagram that heat-eliminating medium of the present invention passes through in tubulation.
Fig. 2 is the calandria type fixed bed reactor schematic diagram that heat-eliminating medium of the present invention passes through from tubulation.
Fig. 3 is two calandria type fixed bed reactor series combination figure.
In Fig. 1,1 is little cylindrical shell, and 2 is flange, and 3 is dividing plate, 4 is stuffing box, and 5 is upper cover, and 6 is upper conduit, and 7 is upper endless tube, 8 is housing, and 9 is heat exchanging pipe, and 10 is lower endless tube, and 11 is bracing frame, 12 is overflow pipe, and 13 is house steward, and 14 is lower cover, 15 is porous gas collection plate, and 16 is catalyzer, and I1 is material inlet, O1 is product exit, and I2 is cooling medium inlet, and O2 is heat-eliminating medium outlet.
In Fig. 2,1 is upper cover, and 2 is housing, and 3 is heat exchanging pipe, and 4 is lower cover, and I1 is material inlet, and O1 is product exit, and I2 is cooling medium inlet, and O2 is heat-eliminating medium outlet.
In Fig. 3, RAI1 is the material inlet of first row tubular fixed-bed reactor RA, RAO1 is the product exit of first row tubular fixed-bed reactor RA, RAI2 is the cooling medium inlet of first row tubular fixed-bed reactor RA, RAO2 is the heat-eliminating medium outlet of first row tubular fixed-bed reactor RA, RBI1 is the material inlet of secondary series tubular fixed-bed reactor RB, RBO1 is the product exit of secondary series tubular fixed-bed reactor RB, RBI2 is the cooling medium inlet of secondary series tubular fixed-bed reactor RB, RBO2 is the heat-eliminating medium outlet of secondary series tubular fixed-bed reactor RB, I3 is the raw material of secondary series tubular fixed-bed reactor RB and the import of solvent mixture, M is mixing tank.
Fig. 1 Raw workflow is: with barkite and hydrogen for raw material, enter in calandria type fixed bed reactor through material inlet (I1) after raw material and solvent mixture preheating, with copper containing catalyst (16) contact reacts in the outer beds of tubulation, simultaneously with the heat-eliminating medium heat exchange in heat exchanging pipe (9), draw through the product exit (O1) of porous gas collection plate (15) by reactor after the reactant containing ethyl glycolate generated flows out beds, be isolated to ethyl glycolate product.Barkite and solvent mixture or hydrogen or water are introduced as the cooling medium inlet (I2) of heat-eliminating medium by reactor, each lower endless tube (10) is distributed to through house steward (13) and overflow pipe (12), then be diverted in each heat exchanging pipe (9), upwards flowing absorbs the reaction heat of the outer beds (16) of tubulation, then flow to each upper endless tube (7) on through upper conduit (6) in the little cylindrical shell (1) on dividing plate (3) top, then draw reactor through heat-eliminating medium outlet (O2).
Fig. 2 Raw workflow is: with barkite and hydrogen for raw material, enter in calandria type fixed bed reactor through material inlet (I1) after raw material and solvent mixture preheating, with the copper containing catalyst contact reacts in tubulation (3) inner catalyst bed, simultaneously with heat exchanging pipe (3) heat-eliminating medium heat exchange outward, draw through the product exit (O1) of lower cover (4) by reactor after the reactant containing ethyl glycolate generated flows out beds, be isolated to ethyl glycolate product.Hydrogen or water introduced as the cooling medium inlet (I2) of heat-eliminating medium by reactor, flowing up or down absorbs the reaction heat of tubulation inner catalyst bed, then draws reactor through heat-eliminating medium outlet (O2).
Fig. 3 Raw workflow is: with barkite and hydrogen for raw material, material inlet (RAI1) through first row tubular fixed-bed reactor RA after raw material and solvent mixture preheating enters in first row tubular fixed-bed reactor, with the copper containing catalyst contact reacts in the outer beds of tubulation, simultaneously with the heat-eliminating medium heat exchange in heat exchanging pipe, the reactant flow containing ethyl glycolate generated is drawn by the product exit (RAO1) of first row tubular fixed-bed reactor RA, is isolated to ethyl glycolate product.Hydrogen is introduced as the cooling medium inlet (RAI2) of heat-eliminating medium by first row tubular fixed-bed reactor RA, then be diverted in each heat exchanging pipe, after upwards flowing absorbs the reaction heat of the outer beds of tubulation, heat-eliminating medium outlet (RAO2) through first row tubular fixed-bed reactor RA goes out reactor RA, then the barkite introduced with the raw material of secondary series tubular fixed-bed reactor RB and the import (I3) of solvent mixture, after hydrogen and solvent mixture fully mix in mixing tank (M), enter in secondary series tubular fixed-bed reactor by the material inlet (RBI1) of secondary series tubular fixed-bed reactor RB, with the copper containing catalyst contact reacts in tubulation inner catalyst bed, simultaneously with the heat-eliminating medium heat exchange outside heat exchanging pipe, the reactant flow containing ethyl glycolate generated is drawn by the product exit (RBO1) of secondary series tubular fixed-bed reactor RB, be isolated to ethyl glycolate product.Water is introduced as the cooling medium inlet (RBI2) of heat-eliminating medium by secondary series tubular fixed-bed reactor RB, after upwards flowing absorbs the reaction heat of tubulation inner catalyst bed, heat-eliminating medium outlet (RBO2) through secondary series tubular fixed-bed reactor RB goes out reactor RB.
Below in conjunction with accompanying drawing, by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
By the flow process shown in Fig. 1, the calandria type fixed bed reactor of Hydrogenation of Dimethyl Oxalate production methyl glycolate is separate unit independent operation, with dimethyl oxalate and hydrogen for raw material, methyl alcohol is solvent, and the weight percentage of dimethyl oxalate and carbinol mixture dimethyl oxalate in preparation is 50%; Copper containing catalyst is that wherein carrier is silicon oxide, and its specific surface area is 380m according to 25% active metal copper and 5% promoter metal silver and the catalyzer prepared of 0.1% promoter metal molybdenum content
2/ g, active copper is selected from cupric nitrate, and auxiliary agent silver is selected from Silver Nitrate, and auxiliary agent molybdenum is selected from nitric acid molybdenum, and catalyst particle diameter is 3mm; Copper containing catalyst is seated in outside tubulation, dimethyl oxalate and carbinol mixture is passed through as heat-eliminating medium by tubulation, is 220 DEG C in temperature of reaction, and the weight space velocity of dimethyl oxalate is 0.5h
-1, hydrogen and dimethyl oxalate mol ratio are 60:1, and reaction pressure is under the condition of 2.8MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of methyl glycolate is 97.2%.
[embodiment 2]
By the flow process shown in Fig. 1, the calandria type fixed bed reactor of Hydrogenation of Dimethyl Oxalate production methyl glycolate is separate unit independent operation, with pure dimethyl oxalate and hydrogen for raw material; Copper containing catalyst is that wherein carrier is silicon oxide, and its specific surface area is 400m according to 30% active metal copper and 2% promoter metal silver and the catalyzer prepared of 0.5% promoter metal barium content
2/ g, active copper is selected from cupric nitrate, and auxiliary agent silver is selected from Silver Nitrate, and auxiliary agent barium is selected from nitrate of baryta, and catalyst particle diameter is 4mm; Copper containing catalyst is seated in outside tubulation, is passed through by water as heat-eliminating medium by tubulation, is 215 DEG C in temperature of reaction, and the weight space velocity of dimethyl oxalate is 0.3h
-1, hydrogen and dimethyl oxalate mol ratio are 55:1, and reaction pressure is under the condition of 3.0MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of methyl glycolate is 97.3%.
[embodiment 3]
By the flow process shown in Fig. 1, the calandria type fixed bed reactor that oxalic acid diethyl ester hydrogenation produces ethyl glycollate is separate unit independent operation, with oxalic acid diethyl ester and hydrogen for raw material, take ethanol as raw material, the weight percentage of oxalic acid diethyl ester and alcohol mixture mesoxalic acid diethyl ester is 10%; Copper containing catalyst is that wherein carrier is silicon oxide and alumina mixture, and its specific surface area is 300m according to 15% active metal copper and 15% promoter metal silver and the catalyzer prepared of 1% promoter metal titanium content
2/ g, wherein active copper is selected from cupric chloride, and auxiliary agent silver is selected from silver chloride, and auxiliary agent titanium is selected from metal titanium, and catalyst particle diameter is 2mm; Copper containing catalyst is seated in outside tubulation, is passed through by hydrogen as heat-eliminating medium by tubulation, is 190 DEG C in temperature of reaction, and the weight space velocity of oxalic acid diethyl ester is 0.6h
-1, hydrogen and oxalic acid diethyl ester mol ratio are 120:1, and reaction pressure is under the condition of 2.0MPa, and the transformation efficiency of oxalic acid diethyl ester is 99.8%, and the selectivity of ethyl glycollate is 94.5%.
[embodiment 4]
By the flow process shown in Fig. 2, the calandria type fixed bed reactor of Hydrogenation of Dimethyl Oxalate production methyl glycolate is separate unit independent operation, with dimethyl oxalate and hydrogen for raw material, methyl alcohol is solvent, and the weight percentage of dimethyl oxalate and carbinol mixture dimethyl oxalate in preparation is 20%; Copper containing catalyst is that wherein carrier is silicon oxide and alumina mixture, and its specific surface area is 450m according to 5% active metal copper and 10% promoter metal silver and the catalyzer prepared of 5% promoter metal magnesium
2/ g, active copper is selected from cupric nitrate, and auxiliary agent silver is selected from argent, and auxiliary agent zinc is selected from magnesium nitrate, and catalyst particle diameter is 6mm; Copper containing catalyst is seated in tubulation, is passed through by hydrogen as heat-eliminating medium by outside tubulation, is 240 DEG C in temperature of reaction, and the weight space velocity of dimethyl oxalate is 0.4h
-1, hydrogen and dimethyl oxalate mol ratio are 30:1, and reaction pressure is under the condition of 4.0MPa, and the transformation efficiency of dimethyl oxalate is 99.5%, and the selectivity of methyl glycolate is 94.2%.
[embodiment 5]
By the flow process shown in Fig. 2, the calandria type fixed bed reactor of Hydrogenation of Dimethyl Oxalate production methyl glycolate is separate unit independent operation, with pure dimethyl oxalate and hydrogen for raw material; Copper containing catalyst is the catalyzer prepared according to 40% active metal copper and 0.5% promoter metal Zn content, and wherein carrier is silicon oxide, and its specific surface area is 420m
2/ g, active copper is selected from the mixture of metallic copper and cupric nitrate, and auxiliary agent zinc is selected from zinc nitrate, and catalyst particle diameter is 4.5mm; Copper containing catalyst is seated in tubulation, is passed through by water as heat-eliminating medium by outside tubulation, is 210 DEG C in temperature of reaction, and the weight space velocity of dimethyl oxalate is 1.2h
-1, hydrogen and dimethyl oxalate mol ratio are 40:1, and reaction pressure is under the condition of 6.0MPa, and the transformation efficiency of dimethyl oxalate is 99.6%, and the selectivity of methyl glycolate is 95.8%.
[embodiment 6]
By the flow process shown in Fig. 2, the calandria type fixed bed reactor that oxalic acid diethyl ester hydrogenation produces ethyl glycollate is separate unit independent operation, with oxalic acid diethyl ester and hydrogen for raw material, take ethanol as raw material, the weight percentage of oxalic acid diethyl ester and alcohol mixture mesoxalic acid diethyl ester is 60%; Copper containing catalyst is the catalyzer prepared according to 30% active metal copper and the violent content of 5% promoter metal, and wherein carrier is silicon oxide, and its specific surface area is 600m
2/ g, active copper is selected from cupric nitrate, and it is violent that auxiliary agent is selected from nitric acid suddenly, and catalyst particle diameter is 3.5mm; Copper containing catalyst is seated in tubulation, is passed through by water as heat-eliminating medium by outside tubulation, is 220 DEG C in temperature of reaction, and the weight space velocity of oxalic acid diethyl ester is 0.8h
-1, hydrogen and oxalic acid diethyl ester mol ratio are 100:1, and reaction pressure is under the condition of 1.5MPa, and the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of ethyl glycollate is 95%.
[embodiment 7]
By the flow process shown in Fig. 3, the calandria type fixed bed reactor of Hydrogenation of Dimethyl Oxalate production methyl glycolate is 2 serial operations, first row tubular fixed-bed reactor with dimethyl oxalate and hydrogen for raw material, methyl alcohol is solvent, and the weight percentage of dimethyl oxalate and carbinol mixture dimethyl oxalate in preparation is 60%, copper containing catalyst in first reactor is identical with embodiment 1 with reaction conditions, copper containing catalyst is seated in outside the tubulation of the first reactor, hydrogen is passed through as heat-eliminating medium by the tubulation of the first reactor, then enter in secondary series tubular fixed-bed reactor after mixing with pure dimethyl oxalate, copper containing catalyst in second reactor is identical with embodiment 2 with reaction conditions, copper containing catalyst is seated in the tubulation of the second reactor, water is passed through as heat-eliminating medium by outside the tubulation of the second reactor, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of methyl glycolate is 97.2%.
[embodiment 8]
By the flow process shown in Fig. 3, the calandria type fixed bed reactor that oxalic acid diethyl ester hydrogenation produces ethyl glycollate is 2 serial operations, first row tubular fixed-bed reactor with oxalic acid diethyl ester and hydrogen for raw material, ethanol is solvent, and the weight percentage of oxalic acid diethyl ester and alcohol mixture mesoxalic acid diethyl ester is 40%, copper containing catalyst is seated in outside the tubulation of the first reactor, hydrogen is passed through as heat-eliminating medium by the tubulation of the first reactor, then with oxalic acid diethyl ester and ethanol, enter in secondary series tubular fixed-bed reactor after hydrogen mixture fully mixes, in second reactor, the weight percentage of oxalic acid diethyl ester and alcohol mixture mesoxalic acid diethyl ester is 80%, copper containing catalyst is seated in the tubulation of the second reactor, water is passed through as heat-eliminating medium by outside the tubulation of the second reactor, copper containing catalyst in two reactors is according to 28% active metal copper and 3% promoter metal silver and the catalyzer prepared of the violent content of 0.8% promoter metal, wherein carrier is silicon oxide, its specific surface area is 380m
2/ g, active copper is selected from cupric nitrate, and auxiliary agent silver is selected from Silver Nitrate, and it is violent that auxiliary agent is selected from nitric acid suddenly, and catalyst particle diameter is 5mm, it is 215 DEG C that the operational condition of two reactors is temperature of reaction, and the weight space velocity of oxalic acid diethyl ester is 0.6h
-1, hydrogen and oxalic acid diethyl ester mol ratio are 70:1, and reaction pressure is under the condition of 2.3MPa, and the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of ethyl glycollate is 96.3%.
[comparative example 1]
The catalyzer of Hydrogenation of Dimethyl Oxalate production methyl glycolate, reaction conditions, reaction raw materials are identical with embodiment 1, and unique difference is that its inside reactor does not arrange heat exchange.The transformation efficiency of its dimethyl oxalate is 91.3%, and the selectivity of methyl glycolate is 80.6%.
[comparative example 2]
The catalyzer of oxalic acid diethyl ester hydrogenation production ethyl glycollate, reaction conditions, reaction raw materials are identical with second reactor in embodiment 8, and unique difference is that its inside reactor does not arrange heat exchange.The transformation efficiency of its oxalic acid diethyl ester is 90.2%, and the selectivity of ethyl glycollate is 81.9%.
Claims (10)
1. produced the method for ethyl glycolate by barkite for one kind, with barkite and hydrogen for raw material, with the lower alcohol of 1 ~ 4 carbon for solvent, weight percentage>=10% of barkite and solvent mixture medium-height grass acid esters, it is 150 DEG C ~ 260 DEG C in temperature, pressure is 1.0 ~ 6.0MPa, and the weight space velocity of barkite is 0.1 ~ 1.5h
-1hydrogen and barkite mol ratio are under the condition of 20 ~ 160:1, after raw material and solvent mixture enter calandria type fixed bed reactor, under copper containing catalyst effect, reaction generates ethyl glycolate, wherein the heat-eliminating medium of calandria type fixed bed reactor is the one in barkite and solvent mixture, hydrogen or water, and the flow direction of heat-eliminating medium and the flow direction of raw material show the same direction or opposite directions.
2. method of being produced ethyl glycolate by barkite according to claim 1, it is characterized in that the operational condition of calandria type fixed bed reactor is: temperature of reaction is 180 DEG C ~ 240 DEG C, the weight space velocity of barkite is 0.1 ~ 1.2h
-1, hydrogen and barkite mol ratio are 30 ~ 120:1, and reaction pressure is 1.5 ~ 4.0MPa, weight percentage>=10% of barkite and solvent mixture medium-height grass acid esters.
3. method of being produced ethyl glycolate by barkite according to claim 2, it is characterized in that the operational condition of calandria type fixed bed reactor is: temperature of reaction is 190 DEG C ~ 220 DEG C, the weight space velocity of barkite is 0.1 ~ 0.8h
-1, hydrogen and barkite mol ratio are 40 ~ 100:1, and reaction pressure is 2.0 ~ 4.0MPa, weight percentage>=20% of barkite and solvent mixture medium-height grass acid esters.
4. method of being produced ethyl glycolate by barkite according to claim 1, it is characterized in that barkite is dimethyl oxalate, solvent is methyl alcohol.
5. method of being produced ethyl glycolate by barkite according to claim 1, when it is characterized in that barkite is oxalic acid diethyl ester, solvent is ethanol.
6. method of being produced ethyl glycolate by barkite according to claim 1, it is characterized in that copper containing catalyst with at least one in silicon oxide and aluminum oxide for carrier, main active ingredient copper is selected from metallic copper, the oxide compound of copper or its mixture, auxiliary agent is selected from least one in silver, manganese, magnesium, barium, zinc, molybdenum and titanium metal or its metal oxide, metallic copper content is 5% ~ 40% of vehicle weight, metal promoter content is 0.1 ~ 15% of vehicle weight, and carrier specific surface area is 300 ~ 600m
2/ g, catalyst particle diameter is 2 ~ 6mm.
7. method of being produced ethyl glycolate by barkite according to claim 1, it is characterized in that the beds of calandria type fixed bed reactor is positioned at tubulation, heat-eliminating medium passes through from tubulation.
8. method of being produced ethyl glycolate by barkite according to claim 1, it is characterized in that the beds of calandria type fixed bed reactor is positioned at outside tubulation, heat-eliminating medium passes through in tubulation.
9. according to claim 1ly produce the method for ethyl glycolate by barkite, it is characterized in that heat-eliminating medium is the one in hydrogen or water, the flow direction of heat-eliminating medium and the flow direction of raw material are reverse direction.
10. method of being produced ethyl glycolate by barkite according to claim 1, is characterized in that calandria type fixed bed reactor is separate unit independent operation or at least 2 serial operations.
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| CN102001944A (en) * | 2010-10-27 | 2011-04-06 | 上海华谊（集团）公司 | Method for preparing glycolate by catalyzing oxalate under action of hydrogenation |
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| CN102001944A (en) * | 2010-10-27 | 2011-04-06 | 上海华谊（集团）公司 | Method for preparing glycolate by catalyzing oxalate under action of hydrogenation |
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