CN101993349B - Method for producing glycol by using oxalic ester - Google Patents
Method for producing glycol by using oxalic ester Download PDFInfo
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- CN101993349B CN101993349B CN2009100578557A CN200910057855A CN101993349B CN 101993349 B CN101993349 B CN 101993349B CN 2009100578557 A CN2009100578557 A CN 2009100578557A CN 200910057855 A CN200910057855 A CN 200910057855A CN 101993349 B CN101993349 B CN 101993349B
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Abstract
The invention relates to a method for producing glycol by using oxalic ester, mainly solving the problems of the prior art that the radial temperature difference in a reactor is large and the selectivity of the target product glycol is lower. In the method, oxalic ester and hydrogen are used as raw materials, the mole ratio of the hydrogen to the oxalic ester is 40-200:1, fatty alcohol with 1-4 carbons is used as a solvent, the weight percent of the solvent to the oxalic ester in the raw materials is 0-0.9:1; the conditions of the method are follows: at least one of the oxalic ester, the hydrogen and the solvent is used as a cooling medium, the temperature is 160 DEG C-280 DEG C, the pressure is 1.0-6.0MPa, weight airspeed is 0.1-10h<-1> with reference to the weight of the mixture of the oxalic ester and the solvent, and the mole ratio of the hydrogen to the oxalic ester is 40-200:1; the cooling medium passes through a tube in a tube type fixed bed reactor; a catalyst bed layer is arranged outside the tube; and after being uniformly mixed together, the cooling medium and the mixture of the fresh raw materials and the solvent enter the reactor and contact a copper containing catalyst outside the tube to react to generate glycol, wherein the flowing direction of the cooling medium is identical to or opposite to the flowing direction of the mixture of the raw materials and the solvent, and the weight percentage of the oxalic ester is not less than 10%. The method disclosed in the invention better solves the problems of the prior art and can be used in the industrial production of glycol.
Description
Technical field
The present invention relates to a kind of method with preparing ethylene glycol from oxalic ester, in particular, relate to the method that a kind of calandria type fixed bed reactor mesoxalic acid dimethyl ester in inner tubulation heat exchange or oxalic acid diethyl ester hydrogenation are produced ethylene glycol.
Background technology
Ethylene glycol (EG) is a kind of important petrochemical complex basic organic material, and it can be mixed with arbitrary proportion and water, and boiling point is high, zero pour is low.Mainly for the production of trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used in addition the industries such as coating, soup, brake fluid and printing ink, solvent and medium as ammonium pertorate, for the production of special solvent glycol ether etc., purposes is very extensive.
At present, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts the operational path of oxyethane direct hydration method, namely first through the petroleum path synthesizing ethylene, reoxidizes ethylene production oxyethane, obtains EG by oxyethane on-catalytic hydration reaction at last.Production technology is monopolized by Dutch Shell, U.S. Halcon-SD and U.S. UCC three companies basically.The economic benefit of this production technique fluctuates larger owing to being subjected to the restriction of oil price.In order to overcome above-mentioned shortcoming and to reduce production costs, since 20 century 70s, begun gradually the i.e. C take matchmaker, Sweet natural gas or heavy wet goods low-cost resource as raw material of green route
1Chemical research becomes the eighties of heat subject in the world.Wherein from synthetic gas, at first by CO gas-phase catalytic coupling synthesis of oxalate, barkite again shortening is produced ethylene glycol, with many merits such as its raw material sources are extensive and cheap, Technical Economy is high, and enjoys attention.
Adopt the technique of producing ethylene glycol from hydrogenation of oxalic ester can be divided into take noble metal catalysts such as Ru as main liquid phase homogeneous hydrogenation method and take copper-based catalysts as main heterogeneous gas phase or By Liquid-phase Hydrogenation Process.Wherein, homogeneous phase liquid-phase hydrogenatin need under high pressure be carried out, and speed of reaction is slow, and product separation reclaims difficulty, there are the shortcomings such as selectivity is low in the heterogeneous liquid phase catalytic hydrogenation of loading type, has preferably transformation efficiency and selectivity and adopt loaded catalyst to carry out gas phase hydrogenation.External many companies have done research to this technology, and be oneself the barkite hydrogenation catalyst and the technique application patent.Emerging products of the remaining section of Japan beginning of the eighties, a large amount of research has been carried out in the application in hydrogenation of oxalate for preparing ethylene glycol reacts to copper base chromium-free catalyst.Clear 57-122946 wherein, clear 57-123127, clear 57-180432, clear 57-122938, clear 57-122941 has delivered about the catalyzer take copper as main body, has investigated carrier (Al
2O
3, SiO
2, La
2O
3Deng), auxiliary agent (K, Zn, Ag, Mo, Ba etc.), preparation method etc. are on the impact of catalyst activity and selectivity.The mid-80, ARCO company disclosed the Cu-Cr catalyzer that is used for barkite gas phase hydrogenation preparing ethylene glycol at US Patent No. P4677234 in 1986, and sulfur impurity, iron level in catalyzer and the raw material defined made strict regulation, requirement is below 4ppm, obtained the ethylene glycol of 95% yield under about 30atm pressure, the long running time of this catalyzer is 466h.In the same year, the emerging product of remaining section and UCC unite in the 309th～321 page of document " AppliedCatalysis " the 31st volume in 1987 and have reported the Cu/SiO that adopts cupric ammine complex and silica gel to prepare
2Catalyzer is under 215 ℃, 0.3MPa pressure, and the yield of ethylene glycol is up to 97.2%.1994 Nian Ange companies have reported oxide compound and a small amount of Al of Cu-Zn in patent USP5345005
2O
3Catalyzer, also obtained good effect.
Domestic to barkite hydrogenation research more mainly contain University Of Tianjin's carbon one Chemical Engineering Laboratory, East China University of Science and Fujian Inst. of Matter Structure, Chinese Academy of Sciences, Fujian thing structure since the just research of relevant CO catalytically synthesizing glycol of nineteen eighty-two, be that domestic progress is fast, scale greatly, one of the unit of the most fruitful research.They have reported the raw materials such as employing cupric nitrate, chromic trioxide, silicon ester, ammoniacal liquor with coprecipitation method and the standby loading type Cu-Cr catalyzer of gel-sol legal system in the 24th～27 page of document " Industrial Catalysis " 1996 4 phase of ground, be that 2.5～3.0Mpa, temperature are that 208～230 ℃, LHSV are 0.1～0.5h at pressure
-1, the gas ester is than being under 40～60 the condition, running 1134h, the oxalic acid diethyl ester average conversion is 99.8%, the average selectivity of ethylene glycol is 95.3%.University Of Tianjin adopts Cu/SiO
2Catalyzer, to 200～250 ℃, below the 3.0MPa, hydrogen ester is than 30～100, liquid hourly space velocity 0.1875～1.815h
-1Study in the scope, its optimum is oxalic acid diethyl ester transformation efficiency 95%, ethylene glycol yield about 80%.East China University of Science adopts Cu/SiO
2Catalyzer also is studied preparation of ethanediol by dimethyl oxalate hydrogenation, and top condition is that 210～220 ℃ of temperature of reaction, reaction pressure are that 2.5MPa, hydrogen ester ratio are 60, liquid hourly space velocity 0.65h
-1
The technology of reporting in above-mentioned patent or the document mainly concentrates on catalyzer and the technical study of preparing glycol by hydrogenating oxalate, has the problem of the poor stability of catalyzer, and the reactor types that adopts is had no report.And reactor is as one of nucleus equipment of producing ethylene glycol from hydrogenation of oxalic ester industrial installation, and its performance quality directly affects the utilization ratio of reaction effect, catalyzer and the quality of product.
As everyone knows, hydrogenation reaction is thermopositive reaction, and the reaction of producing ethylene glycol from hydrogenation of oxalic ester is no exception equally.For exothermic catalytic reaction, along with the carrying out of reaction process, the reaction heat of constantly emitting can make reaction bed temperature improve, and the inactivation of the inevitable accelerator activator of too high local temperature rise, affects the utilising efficiency of reaction effect and reactor.In order to improve the efficient of reactor, need to shift out to reduce temperature of reaction to reaction heat.In industrial reactor, once widely a kind of of usefulness was that the cold shock of multistage unstripped gas reduces temperature of reaction, and this reactor has also reduced reactant concn during because of the unstripped gas cold shock when reducing temperature of reactor, affected reaction efficiency.Therefore various improved forms have appearred, disclose a kind of heterogeneous synthetic improving one's methods and reactor such as Chinese patent CN1030878, but this reactor is not namely eliminated the cold shock raw material fully and indirect heat exchanger is established again in the impact of reactant concn is made device structure complicated in bed.Another kind is such as disclosed shell and tube reactor among the patent DE2123950, unstripped gas enters from the top inlet mouth and is distributed in each tubulation, with the catalyzer contact reacts in the tubulation, lateral inflow between tubulation, reaction heat is moved heat continuously by the outer boiled water of tubulation, produce steam and gone out by the side pipe, reaction gas goes out reactor by the bottom escape pipe.Although have a narrow range of temperature in this reactor, the catalyst loading coefficient is little, there is serious wall effect in the reactor catalyst bed, affects the space-time yield of catalyzer, and the difficulty that maximizes.
Summary of the invention
Technical problem to be solved by this invention is that the reactor inside diameter that exists in the conventional art is large to the temperature difference, easily cause catalyzer temperature runaway, inactivation and the low problem of purpose glycol product selectivity, a kind of new method with preparing ethylene glycol from oxalic ester is provided, the method has reactor inside diameter to having a narrow range of temperature, the barkite transformation efficiency is high, glycol selectivity is good, the characteristics such as energy efficient.
For solving the problems of the technologies described above, the present invention adopts technical scheme as follows: a kind of method with preparing ethylene glycol from oxalic ester, take barkite and hydrogen as raw material, the mol ratio of hydrogen and barkite is 40～200: 1, take the Fatty Alcohol(C12-C14 and C12-C18) of 1～4 carbon as solvent, the weight percent of solvent and raw material medium-height grass acid esters is 0～0.9: 1, at least a as heat-eliminating medium in barkite, hydrogen or the solvent, it is 160 ℃～280 ℃ in temperature, pressure is 1.0～6.0MPa, and the weight space velocity take the mixture weight of barkite and solvent as benchmark is as 0.1～10h
-1Hydrogen/ester mol ratio is under 40～200: 1 the condition, pass through in the tubulation of heat-eliminating medium in the calandria type fixed bed reactor, beds is positioned at outside the tubulation, heat-eliminating medium and fresh feed and solvent mixture enter in the reactor after evenly mixing, with the copper containing catalyst contact reacts generating glycol outside the tubulation, wherein the flow direction of the flow direction of heat-eliminating medium and raw material and solvent mixture shows the same direction or opposite directions, the weight percentage of barkite 〉=10%.
In the technique scheme, the operational condition of reactor is: temperature of reaction is 180～260 ℃, and the weight space velocity take the mixture weight of barkite and solvent as benchmark is as 0.1～6h
-1, hydrogen/ester mol ratio is 60～180: 1, and reaction pressure is 1.5～6.0MPa, and the weight percentage of barkite is 10～100%.When barkite was dimethyl oxalate, solvent was methyl alcohol.When barkite was oxalic acid diethyl ester, solvent was ethanol.Copper containing catalyst is with silicon oxide, aluminum oxide, at least a in the molecular sieve is carrier, active ingredient is selected from metallic copper, the oxide compound of copper or its mixture, auxiliary agent is selected from zinc, barium, magnesium, at least a in the oxide compound of manganese or chromium metal or its metal, take carrier as benchmark, weighing scale with elemental copper, be selected from metallic copper, the oxide compound of copper or the consumption of its mixture are that weight content is 5%～50%, preferable range is 10%～40%, weighing scale with the auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal or promoter metal is that weight content is 0.05～15%, and preferable range is 0.1%～10%.Copper containing catalyst is take silicon oxide as carrier, active ingredient is selected from the oxide compound of copper, auxiliary agent is selected from least a in the oxide compound of the oxide compound of oxide compound, barium of zinc or chromium, take carrier as benchmark, with the weighing scale of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 10%～35%, preferable range is 15%～30%, with the weighing scale of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal is that weight content is 0.1～5%, and preferable range is 0.5%～5%.
As everyone knows, hydrogenation reaction is thermopositive reaction, and the reaction of producing ethylene glycol from hydrogenation of oxalic ester is no exception equally.Studies show that in a large number, the major cause of barkite hydrogenation catalyst inactivation is catalyzer knot carbon and active ingredient grain growth sintering, and the concentrated heat release of hydrogenation process can cause the higher temperature rise of catalyzer, especially the temperature of catalyst active center may exceed catalyzer apparent tens the degree in addition more than 100 ℃, and too high local temperature rise is very fatal on the impact of catalyst life, not only can greatly aggravate catalyzer green coke process, and can greatly accelerate growing up of crystal grain, thereby the inactivation of accelerator activator, shorten stable period.Research also shows, for oxalate hydrogenation, is typical cascade reaction, at first the barkite hydrogenation generates the intermediate product ethyl glycolate, ethyl glycolate repeated hydrogenation generating glycol, the ethylene glycol excessive hydrogenation then generates by product ethanol, and high temperature is conducive to the carrying out of side reaction.In addition, all there are certain shortcoming in the multistage cold shock formula fixed-bed reactor and the shell and tube reactor that are usually used in exothermic catalytic reaction for this oxalate hydrogenation, the former is owing to also having reduced reactant concn during the unstripped gas cold shock when reducing temperature of reactor, affected reaction efficiency, thereby must affect the selectivity of transformation efficiency and the ethylene glycol of barkite, (the tubulation diameter is generally 25～50mm) and the latter is owing to tubulation is thin, catalyzer is contained in the tubulation, exist the packing factor of catalyzer little, there is serious wall effect in the reactor catalyst bed, affect the shortcoming of the space-time yield of catalyzer, thereby when being used for oxalate hydrogenation, must affect the selectivity of transformation efficiency and the ethylene glycol of barkite, and this reactor maximizes difficult.The new method with preparing ethylene glycol from oxalic ester that the present invention proposes; taken into full account the heat effect of oxalate hydrogenation; on the one hand; by heat exchanging pipe is set in reactor; logical heat-eliminating medium in the heat exchanging pipe; the scheme of the exterior catalyzer of heat exchanging pipe; not only increased the packing factor of catalyst in reactor; and realized in time removing when reaction liberated heat; reduced the operation temperature rise of reactor; avoided the heat release of hydrogenation concentrations to cause the too high problem that easily causes catalyzer temperature runaway and inactivation of local temperature rise in the beds; guaranteed optimal reaction temperature; optimize the operation operating mode of hydrogenation reaction, effectively protected the reactivity worth of catalyzer, can reach the stable period of maximized extending catalyst; and the transformation efficiency of raising barkite and the optionally purpose of purpose glycol product; on the other hand, remove reaction heat by adopting unstripped gas as heat-eliminating medium, saved investment and the energy consumption of advancing the reactor interchanger.
Adopt technical scheme of the present invention, take dimethyl oxalate or oxalic acid diethyl ester and hydrogen as raw material, methyl alcohol or ethanol are solvent, at least a in barkite, hydrogen or the solvent is heat-eliminating medium, be 180～260 ℃ in temperature of reaction, the weight space velocity take the mixture weight of barkite and solvent as benchmark is as 0.1～6h
-1Hydrogen/ester mol ratio is 60～180: 1, reaction pressure is 1.5～6.0MPa, the weight percentage of barkite is 10～100%, copper containing catalyst is take silicon oxide as carrier, active ingredient is selected from the oxide compound of copper, auxiliary agent is selected from the oxide compound of zinc, at least a in the oxide compound of barium or the oxide compound of chromium, take carrier as benchmark, weighing scale with elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 10%～35%, and with the weighing scale of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal is that weight content is under 0.1～5% the condition, the same radial section temperature difference of catalyst in reactor bed is less than 6 ℃, the transformation efficiency of barkite is greater than 98%, and the selectivity of ethylene glycol has obtained preferably technique effect greater than 90%.
Description of drawings
Fig. 1 is calandria type fixed bed reactor and reactor external equipment pipeline interface chart.
Among Fig. 1, A is material inlet, and B is the product outlet, and C is cooling medium inlet, and D is the heat-eliminating medium outlet, 1 is little cylindrical shell, and 2 is flange, and 3 is dividing plate, and 4 is stuffing box, 5 is upper cover, and 6 is upper conduit, and 7 is upper endless tube, and 8 is housing, 9 is heat exchanging pipe, and 10 is lower endless tube, and 11 is bracing frame, and 12 is overflow pipe, 13 is house steward, and 14 is lower cover, and 15 is porous gas collection plate, and 16 is catalyzer, 17,18,19 is pipeline, and M is mixing tank.
Fig. 1 Raw workflow is: contain barkite, at least a heat-eliminating medium in hydrogen or the solvent is introduced by the cooling medium inlet (C) of reactor, be distributed to each overflow pipe (12) through house steward (13), be distributed in each the arrangement pipe (9) that is connected in lower endless tube through lower endless tube (10) again, flow up or down and absorb the reaction heat of the outer beds (16) of tubulation, passing dividing plate through upper endless tube (7) and the upper conduit that is connected endless tube (6) enters in the little cylindrical shell (1), going out reactor through the heat-eliminating medium at top outlet (D) again enters in the mixing tank (M), with the fresh hydrogen after the preheating of the pipeline (17) that comes, and the fresh barkite after pipeline (18) preheating that comes and solvent mixture are mixing tank (M) in evenly after the mixing, drawn by pipeline (19), then enter in the calandria type fixed bed reactor through material inlet (A), with catalyzer (16) contact reacts in the outer beds of tubulation, simultaneously with heat exchanging pipe (9) in the cooling gas heat exchange, the reaction effluent that contains ethylene glycol that goes out beds is drawn by the product outlet (B) of reactor through porous gas collection plate (15) to the bottom, is isolated to the ethylene glycol product.
The invention will be further elaborated by embodiment below in conjunction with accompanying drawing, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Press Fig. 1, it is 2 meters that Hydrogenation of Dimethyl Oxalate is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Zn/SiO
2Catalyzer, with the weighing scale of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 35%, with the weighing scale of simple substance zinc, the consumption that is selected from the oxide compound of zinc is that weight content is 5%.Heat-eliminating medium is dimethyl oxalate and carbinol mixture.It is 160 ℃ with temperature, the dimethyl oxalate weight percentage is that 25% dimethyl oxalate and carbinol mixture are introduced by cooling medium inlet, be diverted in each heat exchanging pipe, being reverse direction with the flow direction of the outer raw material of tubulation and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation is warming up to 210 ℃, then draw reactor through the heat-eliminating medium outlet, enter in the mixer, be that 25% dimethyl oxalate and carbinol mixture evenly mix in mixing tank with fresh hydrogen after the exterior tubing preheating that comes and dimethyl oxalate weight percentage, the weight percentage of dimethyl oxalate is 25% after mixing, hydrogen and dimethyl oxalate mol ratio are 110: 1, temperature is 210 ℃, enter in the reactor through the reactor feedstocks import again, with the copper containing catalyst contact reacts outside the tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 210 ℃, and the weight space velocity take the mixture weight of dimethyl oxalate and methyl alcohol as benchmark is as 1.2h
-1, hydrogen/ester mol ratio is 110: 1, reaction pressure is 3.2MPa.Under above structural parameter and condition, by the present invention Hydrogenation of Dimethyl Oxalate being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 4 ℃, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethylene glycol is 97.7%, but energy efficient is the 11.7KJ/mol dimethyl oxalate.
[embodiment 2]
Press Fig. 1, it is 2.5 meters that Hydrogenation of Dimethyl Oxalate is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Cr/SiO
2Catalyzer, with the weighing scale of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 25%, with the weighing scale of simple substance chromium, the consumption that is selected from the oxide compound of chromium is that weight content is 10%.Heat-eliminating medium is the mixed gas that dimethyl oxalate, methyl alcohol and hydrogen form.It is 170 ℃ with temperature, the dimethyl oxalate weight percentage is that the unstripped gas that 50% dimethyl oxalate and carbinol mixture and hydrogen form is introduced by cooling medium inlet, be diverted in each heat exchanging pipe, being reverse direction with the flow direction of the outer raw material of tubulation and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation is warming up to 230 ℃, then draw reactor through the heat-eliminating medium outlet, enter in the mixer, be that 50% dimethyl oxalate and carbinol mixture evenly mix in mixing tank with fresh hydrogen after the exterior tubing preheating that comes and dimethyl oxalate weight percentage, the weight percentage of dimethyl oxalate is 50% after mixing, hydrogen and dimethyl oxalate mol ratio are 120: 1, temperature is 230 ℃, again in material inlet is introduced shell and tube reactor, with the copper containing catalyst contact reacts outside the tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 230 ℃, and the weight space velocity take the mixture weight of dimethyl oxalate and methyl alcohol as benchmark is as 0.7hr
-1, hydrogen/ester mol ratio is 120: 1, reaction pressure is 3.8MPa.Under above structural parameter and condition, by the present invention Hydrogenation of Dimethyl Oxalate being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 3.5 ℃, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethylene glycol is 96.8%, but energy efficient is the 14.78KJ/mol dimethyl oxalate.
[embodiment 3]
Press Fig. 1, it is 2.5 meters that the oxalic acid diethyl ester hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Mg/SiO
2Catalyzer, with the weighing scale of elemental copper, the consumption that is selected from the oxide compound of metallic copper and copper is that weight content is 40%, with the weighing scale of simple substance magnesium, the oxide compound consumption that is selected from magnesium is that weight content is 0.1%.Heat-eliminating medium is hydrogen.Be that 25 ℃ hydrogen is introduced by cooling medium inlet with temperature, be diverted in each heat exchanging pipe, being equidirectional with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs simultaneously the outer beds of tubulation is warming up to 260 ℃, then draw reactor through the heat-eliminating medium outlet, enter in the mixer, be that 60% oxalic acid diethyl ester and alcohol mixture evenly mix in mixing tank with fresh hydrogen after the exterior tubing preheating that comes and oxalic acid diethyl ester weight percentage, the weight percentage of oxalic acid diethyl ester is 60% after mixing, hydrogen and dimethyl oxalate mol ratio are 60: 1, temperature is 260 ℃, again in reactor is introduced in the reactor feedstocks import, with the copper containing catalyst contact reacts outside the tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 260 ℃, and the weight space velocity take the mixture weight of oxalic acid diethyl ester and ethanol as benchmark is as 0.8hr
-1, hydrogen/ester mol ratio is 60: 1, reaction pressure is 6.0MPa.Under above structural parameter and condition, by the present invention the oxalic acid diethyl ester hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 5 ℃, the transformation efficiency of oxalic acid diethyl ester is 99.8%, the selectivity of ethylene glycol is 93.1%, but energy efficient is 5.9KJ/mol hydrogen.
[embodiment 4]
Press Fig. 1, it is 3 meters that the oxalic acid diethyl ester hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Ba/SiO
2Catalyzer, with the weighing scale of elemental copper, the consumption that is selected from the oxide compound of metallic copper and copper is that weight content is 50%, with the weighing scale of simple substance barium, the consumption that is selected from barium metal is that weight content is 0.05%.Heat-eliminating medium is oxalic acid diethyl ester.Be that 80 ℃ oxalic acid diethyl ester is introduced by cooling medium inlet with temperature, be diverted in each heat exchanging pipe, being reverse direction with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs simultaneously the outer beds of tubulation is warming up to 180 ℃, then draw reactor through the heat-eliminating medium outlet, enter in the mixer, be that 100% pure oxalic acid diethyl ester evenly mixes in mixing tank with fresh hydrogen after the exterior tubing preheating that comes and oxalic acid diethyl ester weight percentage, the weight percentage of oxalic acid diethyl ester is 100% after mixing, hydrogen and oxalic acid diethyl ester mol ratio are 180: 1, temperature is 180 ℃, again in reactor is introduced in the reactor feedstocks import, with the copper containing catalyst contact reacts outside the tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 180 ℃, and the weight space velocity take oxalic acid diethyl ester as benchmark is 0.1hr
-1, hydrogen/ester mol ratio is 180: 1, reaction pressure is 4.5MPa.Under above structural parameter and condition, by the present invention the oxalic acid diethyl ester hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 6 ℃, the transformation efficiency of oxalic acid diethyl ester is 100%, the selectivity of ethylene glycol is 94.5%, but energy efficient is the 24.7KJ/mol oxalic acid diethyl ester.
[embodiment 5]
Press Fig. 1, it is 3.5 meters that Hydrogenation of Dimethyl Oxalate is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Cr/SiO
2Catalyzer, with the weighing scale of elemental copper, the consumption that is selected from the oxide compound of metallic copper and copper is that weight content is 10%, with the weighing scale of simple substance chromium, the consumption that is selected from the oxide compound of chromium is that weight content is 15%.Heat-eliminating medium is methyl alcohol.Be that 120 ℃ methyl alcohol is introduced by cooling medium inlet with temperature, be diverted in each heat exchanging pipe, being reverse direction with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs simultaneously the outer beds of tubulation is warming up to 210 ℃, then draw reactor through the heat-eliminating medium outlet, enter in the mixer, be that 100% pure dimethyl oxalate evenly mixes in mixing tank with fresh hydrogen after the exterior tubing preheating that comes and dimethyl oxalate weight percentage, the weight percentage of dimethyl oxalate is 10% after mixing, the mol ratio of hydrogen and dimethyl oxalate is 200: 1, temperature is 210 ℃, again in reactor is introduced in the reactor feedstocks import, with the copper containing catalyst contact reacts outside the tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 210 ℃, and the weight space velocity take the mixture weight of dimethyl oxalate and methyl alcohol as benchmark is as 5hr
-1, hydrogen/ester mol ratio is 200: 1, reaction pressure is 1.8MPa.Under above structural parameter and condition, by the present invention Hydrogenation of Dimethyl Oxalate being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 5 ℃, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethylene glycol is 94.2%, but energy efficient is 10.9KJ/mol methyl alcohol.
[embodiment 6]
Press Fig. 1, it is 3.5 meters that Hydrogenation of Dimethyl Oxalate is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Mn/SiO
2Catalyzer, with the weighing scale of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 25%, with the weighing scale of simple substance manganese, the consumption that is selected from the oxide compound of manganese is that weight content is 3%.Heat-eliminating medium is dimethyl oxalate.Be that 200 ℃ dimethyl oxalate is introduced by cooling medium inlet and is diverted in each heat exchanging pipe with temperature, being reverse direction with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs simultaneously the outer beds of tubulation is warming up to 280 ℃, then draw reactor through the heat-eliminating medium outlet, enter in the mixer, be that 100% pure dimethyl oxalate evenly mixes in mixing tank with fresh hydrogen after the exterior tubing preheating that comes and dimethyl oxalate weight percentage, the weight percentage of dimethyl oxalate is 100% after mixing, the mol ratio of hydrogen and dimethyl oxalate is 100: 1, temperature is 280 ℃, again in reactor is introduced in the reactor feedstocks import, with the copper containing catalyst contact reacts outside the tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 280 ℃, and the weight space velocity take dimethyl oxalate as benchmark is 0.25hr
-1, the hydrogen ester mol ratio is 100: 1, reaction pressure is 3.8MPa.Under above structural parameter and condition, by the present invention Hydrogenation of Dimethyl Oxalate being produced glycol reaction designs, the same radial section temperature difference of its catalyst in reactor bed is less than 5 ℃, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethylene glycol is 95.1%, but energy efficient is the 22.5KJ/mol dimethyl oxalate.
[embodiment 7]
Press Fig. 1, it is 3.5 meters that the oxalic acid diethyl ester hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Ca/SiO
2Catalyzer, with the weighing scale of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 32%, with the weighing scale of simple substance calcium, the consumption that is selected from the oxide compound of calcium is that weight content is 0.5%.Heat-eliminating medium is ethanol.Be that 130 ℃ ethanol is introduced by cooling medium inlet with temperature, be diverted in each heat exchanging pipe, being equidirectional with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs simultaneously the outer beds of tubulation is warming up to 220 ℃, then draw reactor through the heat-eliminating medium outlet, enter in the mixer, be that 100% pure oxalic acid diethyl ester evenly mixes in mixing tank with fresh hydrogen after the exterior tubing preheating that comes and oxalic acid diethyl ester weight percentage, the weight percentage of oxalic acid diethyl ester is 10% after mixing, hydrogen and oxalic acid diethyl ester mol ratio are 40: 1, temperature is 220 ℃, again in reactor is introduced in the reactor feedstocks import, with the copper containing catalyst contact reacts outside the tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 220 ℃, and the weight space velocity take the mixture weight of oxalic acid diethyl ester and ethanol as benchmark is as 10hr
-1, hydrogen/ester mol ratio is 40: 1, reaction pressure is 2.5MPa.Under above structural parameter and condition, by the present invention the oxalic acid diethyl ester hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 5.5 ℃, the transformation efficiency of oxalic acid diethyl ester is 99.7%, the selectivity of ethylene glycol is 93.4%, but energy efficient is 10KJ/mol ethanol.
[comparative example 1]
The structural parameter of catalyzer, condition, reaction raw materials and the fixed-bed reactor of certain Hydrogenation of Dimethyl Oxalate production ethylene glycol are identical with embodiment 1, and unique difference is that its inside reactor does not arrange heat exchanging pipe.The same cross-section radial temperature difference of its beds is less than 15 ℃, and the transformation efficiency of dimethyl oxalate is 95.8%, and the selectivity of ethylene glycol is 85.6%, not energy efficient.
[comparative example 2]
The structural parameter of catalyzer, condition, reaction raw materials and the fixed-bed reactor of certain oxalic acid diethyl ester hydrogenation production ethylene glycol are identical with embodiment 4, and unique difference is that its inside reactor does not arrange heat exchanging pipe.The same cross-section radial temperature difference of its beds is less than 18 ℃, and the transformation efficiency of oxalic acid diethyl ester is 94.6%, and the selectivity of ethylene glycol is 84.5%, not energy efficient.
Claims (6)
1. method with preparing ethylene glycol from oxalic ester, take barkite and hydrogen as raw material, the mol ratio of hydrogen and barkite is 40～200: 1, take the Fatty Alcohol(C12-C14 and C12-C18) of 1～4 carbon as solvent, the weight percent of solvent and raw material medium-height grass acid esters is 0～0.9: 1, and at least a as heat-eliminating medium in barkite, hydrogen or the solvent is 160 ℃～280 ℃ in temperature, pressure is 1.0～6.0MPa, and the weight space velocity take the mixture weight of barkite and solvent as benchmark is as 0.1～10h
-1Hydrogen/ester mol ratio is under 40～200: 1 the condition, pass through in the tubulation of heat-eliminating medium in the calandria type fixed bed reactor, beds is positioned at outside the tubulation, heat-eliminating medium and fresh feed and solvent mixture enter in the reactor after evenly mixing, with the copper containing catalyst contact reacts generating glycol outside the tubulation, wherein the flow direction of the flow direction of heat-eliminating medium and raw material and solvent mixture shows the same direction or opposite directions, the weight percentage of barkite 〉=10%.
2. the method with preparing ethylene glycol from oxalic ester according to claim 1, it is characterized in that the operational condition of reactor is: temperature of reaction is 180～260 ℃, the weight space velocity take the mixture weight of barkite and solvent as benchmark is as 0.1～6h
-1, hydrogen/ester mol ratio is 60～180: 1, and reaction pressure is 1.5～6.0MPa, and the weight percentage of barkite is 10～100%.
3. the method with preparing ethylene glycol from oxalic ester according to claim 1, when it is characterized in that described barkite is dimethyl oxalate, solvent is methyl alcohol.
4. the method with preparing ethylene glycol from oxalic ester according to claim 1, when it is characterized in that described barkite is oxalic acid diethyl ester, solvent is ethanol.
5. the method with preparing ethylene glycol from oxalic ester according to claim 1, it is characterized in that copper containing catalyst is with silicon oxide, aluminum oxide, at least a in the molecular sieve is carrier, active ingredient is selected from metallic copper, the oxide compound of copper or its mixture, auxiliary agent is selected from zinc, barium, magnesium, at least a in the oxide compound of manganese or chromium metal or its metal, take carrier as benchmark, weighing scale with elemental copper, be selected from metallic copper, the oxide compound of copper or the consumption of its mixture are that weight content is 5%～50%, with the weighing scale of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal or promoter metal is that weight content is 0.05～15%.
6. the method with preparing ethylene glycol from oxalic ester according to claim 5, it is characterized in that copper containing catalyst is take silicon oxide as carrier, active ingredient is selected from the oxide compound of copper, auxiliary agent is selected from least a in the oxide compound of the oxide compound of oxide compound, barium of zinc or chromium, take carrier as benchmark, weighing scale with elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 10%～35%, with the weighing scale of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal is that weight content is 0.1～5%.
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| CN104841339A (en) * | 2015-04-16 | 2015-08-19 | 中国五环工程有限公司 | Novel hydrogenation reactor for synthesis gas-to-ethylene glycol process |
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| CN108017511B (en) * | 2017-08-04 | 2021-01-08 | 华东理工大学 | Method for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
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| US5484576A (en) * | 1992-03-12 | 1996-01-16 | Bayer Aktiengesellschaft | Fixed bed reactors having a short catalyst bed in the direction of flow |
| CN101475441A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
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| US5484576A (en) * | 1992-03-12 | 1996-01-16 | Bayer Aktiengesellschaft | Fixed bed reactors having a short catalyst bed in the direction of flow |
| CN101475441A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
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