CN1309112A - Method for preparing alkylene diol - Google Patents
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Abstract
A process for continuously preparing alkylenediol includes reaction of alkylene oxide with CO2 in the presence of catalyst to obtain the solution containing alkylene carbonate, multi-stage hydrolysis of said solution to obtain the aqueous solution of alkylenediol while releasing CO2, distillation to obtain dewatered alkylenediol and the solution containing catalyst and providing said solution to step 1.
Description
The present invention relates to prepare the method for alkylene glycol by alkylene oxide.More specifically, relate to the method that high-level efficiency prepares alkylene glycol.
Alkylene glycol, especially ethylene glycol can be used as the raw material of synthon or resin, or as antifreezing liquid, are important industrial compounds therefore.
Prepare in the method for alkylene glycol, well-known is hydrolysis alkylene carbonate method.This class reaction is carried out in the presence of the hydrolysis reaction catalyzer usually, once proposed to use the hydrolysis reaction catalyzer, as alkaline carbonate (United States Patent (USP) 4,117,250), molybdenum compound (JP-B-55-154927) or tungsten compound (JP-B-55-154928), to improve speed of reaction.
Use the hydrolysis reaction catalyzer can quicken hydrolysis, but the degree deficiency of quickening.Satisfy industrialized speed of reaction if at high temperature react to reach, the problem of existence is the degradation of product.On the other hand, carry out if react under the lesser temps, to guarantee quality product, then speed of reaction slows down, and needing increases the productive rate that reactor volume obtains being scheduled to, or unreacted alkylene carbonate can remain in the product.
If ethylene carbonate remains in the ethylene glycol production process after the hydrolysis, ethylene carbonate and ethylene glycol form azeotropic mixture, make to separate or purify difficulty takes place, and this is very important to industrialization.
And in the alkylene carbonate hydrolysis, the molar ratio of water and alkylene carbonate is about 1.3: 1 to 5.0: 1 usually in the raw material of adding.If molar ratio is less than this scope, the problem of appearance is to carry out with reaction, and water will be consumed, and the density loss of water reduces speed of reaction, therefore, need the long period to finish reaction, and the impurity level that forms can increase.On the other hand, if the water yield that adds exceeds this scope, the amount of water obviously exceeds the amount of reaction consumes in the system, and the problem of appearance is to need a large amount of heats to come reacting by heating solution and divide dried up at purification system.
Alkylene carbonate as raw material can make by alkylene oxide and carbonic acid gas are reacted in the presence of the carbonation reaction catalyzer.Yet when this reactions steps and hydrolysing step carry out continuously, if use round-robin carbonation reaction catalyzer, carbonation catalyst is active can progressively to descend.Therefore, require a kind of method of research, do not reduce activity of such catalysts.
The object of the invention provides the method for producing alkylene glycol, and this method does not have above-mentioned problem.Particularly, the purpose of this invention is to provide a kind of method, can suppress energy consumption, reuse the carbonation reaction catalyzer by circulation, catalyst activity can variation, even using under the situation of the alkylene carbonate that alkylene oxide and carbon dioxide reaction are made, also can finish hydrolysis effectively at lesser temps and short time.
The inventor has carried out extensive studies, to solve top problem, finds to make the alkylene carbonate transformation efficiency in certain scope by water concentration in the reactive system is kept within the specific limits, can suppress energy consumption, keeps high-caliber speed of reaction.Find to have finished the present invention on the basis at this.
That is, the preparation method of alkylene glycol has reached purpose of the present invention, and this method is a continuous processing, comprise the following steps (1)-(4), wherein, hydrolysing step (2) is divided into a plurality of stages, and the water concentration that makes the alkylene carbonate transformation efficiency be at least 60% step of reaction that is hydrolyzed is 15-30% (weight):
(1) carbonation step makes alkylene oxide and carbon dioxide reaction in the presence of the carbonation reaction catalyzer, form the solution that contains the carbonic acid alkylene;
(2) hydrolysing step, the reaction soln that hydrolysing step (1) makes, while release of carbon dioxide, the aqueous solution of formation alkylene glycol;
(3) distilation steps, the distillation alkylene glycol aqueous solution, the solution that makes the alkylene glycol of dehydration at least and contain the agent of carbonating catalyzed reaction; With
(4) circulation step provides the solution that contains the carbonation reaction catalyzer to carbonation step (1).
Describe the present invention below in detail.
Among the present invention, at first, alkylene oxide and carbon dioxide gas precursor reactant form the reaction soln that contains the carbonic acid alkylene in the presence of catalyzer.Alkylene oxide should form the reaction soln that contains carbonic acid alkylene and alkylene glycol with carbon dioxide and water reaction.Can adopt known method to carry out this reaction.
The catalyzer that uses is as being alkali metal bromide or iodide, alkaline earth metal bromide or iodide, ammonium halide (tributyl-methyl phosphonium iodide ammonium) or phosphonium halide (as iodate tributyl Jia Ji Phosphonium).Wherein, preferred especially halogenation quaternary phosphine uses the halogenation quaternary phosphine that is expressed from the next usually.
In the following formula, R1-R4 represents a group independently of one another, as alkyl, alkenyl, aryl or aralkyl, can have do not participate in reacting, the substituting group of bonding.X is chlorine, bromine or iodine.
The object lesson of this class halogenation quaternary phosphine have the 2nd and the page 3 of JP-A-58-22448 described those.Wherein, particularly preferably be halogenation Si Wan Ji Phosphonium, R1-R4 wherein is C independently of one another
1-6Alkyl.Usually synthetic halogenation quaternary phosphine outside system joins system then.Yet if desired, corresponding quaternary phosphine and alkyl halide can add this reactive system, form the halogenation quaternary phosphine in this reactive system.As the carbonation reaction catalyzer, can use the halogenation quaternary phosphine separately, but if desired, can mix and use other promotor and common catalyst component.For example, the halogenation quaternary phosphine can make up with 0.01-1 mol alkali metal carbonate, might reduce by product in the carbonation step, as the formation of glycol ether, and the reaction of promotion hydrolysing step.
Carry out at 70-200 ℃ as the carbonation reaction step 1, be advisable for 100-170 ℃, 100-150 ℃ better.If temperature of reaction is low, speed of reaction can slow down.On the other hand,, can increase side reaction, because the loss that catalyst decomposes caused increases if temperature of reaction is too high.Reaction pressure is generally 5-50kg/cm
2G (0.59-5.0MPa), 10-30kg/cm
2G (1.08-3.04MPa) is advisable.Raise with reaction pressure, general alkylene oxide reaction speed can improve, and reduces the generation of by product as two aklylene glycols.Yet, under high pressure carrying out this reaction needed and use expensive reactor and other device, the cost of compression arbon dioxide gas institute energy requirement rises.
The carbon dioxide of supply response system and the molar ratio of alkylene oxide generally are 5 to the maximum, are 3 preferably to the maximum.If this molar ratio is too big, reaction can be carried out fully, but the cost of the energy of compression arbon dioxide gas increases.Even this molar ratio is less than 1, reaction still can be carried out.Yet carbon dioxide not only is used as reaction raw materials, but also is used for the stirring reaction system, in case local temperature raises.Therefore, the carbon dioxide that provides and the molar ratio of oxyethane are 0.5 to be advisable at least, and at least 1.0 is better.As described above, water should be provided in reactive system.The ratio of water and alkylene oxide can be any, but general its molar ratio is 10 to the maximum, is 5 preferably to the maximum.If this molar ratio is too big, the concentration of the alkylene glycol aqueous solution that makes by hydrolysing step subsequently reduces, and will spend a lot of money to remove and anhydrate.On the other hand, even molar ratio less than 1, when promptly providing water less than the equimolar amount with alkylene oxide, reacts and still can carry out.Yet,, provide the big water yield extremely to a certain degree favourable from the angle of control reaction temperature.
Reactor can use the reactor of any kind, as long as can provide good solution-air contact.Should use bubbling column reactor, add alkylene oxide, carbon dioxide, catalyzer and water at tower bottom, the reaction soln of formation and excess carbon dioxide gas are discharged from the top.Reaction soln is sent into next hydrolysing step, is circulated to bubbling column reactor behind the carbon dioxide of supplement consumed.This reaction is strong heat release, therefore should pass through exterior cooling system control reaction temperature, and reaction soln is discharged from cat head, by heat exchanger cooling, gets back to reactor bottom then.
The method that is used to prepare alkylene glycol and alkylene carbonate comprises by from above-mentioned carbonation step discharge section or total overall reaction solution.The solution of discharging is sent into first distilation steps, from top of tower, and distillation water outlet, alkylene glycol and a small amount of azeotropic alkylene carbonate of following, these are recycled to below with the hydrolysing step of describing (this step is used to prepare alkylene glycol).
In first distilation steps, solution keeps enough residence time in tower, makes reaction proceed to nearly all two alkylene glycol and disappears.Can think that this reaction is the carbonating of two alkylene glycol.By this step, can prevent that the entrainment of two alkylene glycol in alkylene carbonate from discharging from cat head in after-fractionating step subsequently.
The liquid that obtains at the bottom of the tower of first distilation steps is sent into the after-fractionating step.In this liquid, contain two alkylene glycol hardly.The alkylene carbonate that can obtain to purify from cat head.On the other hand, recyclable carbonic acid alkylene liquid, two alkylene glycol reaction product and the catalyzer of containing at the bottom of the tower, and they are circulated to below with the hydrolysing step of describing (this step is used to prepare alkylene glycol).
Afterwards, above the reaction soln hydrolysis that contains the carbonic acid alkylene that obtained, carbon dioxide gas forms the alkylene glycol aqueous solution simultaneously.The hydrolysis of alkylene carbonate can be represented by following formula (1).
Finish in the popular response system of hydrolysis with a step or polystep reaction, only finish this reaction by the water that adds, and can not control the concentration of water, water concentration carries out with reaction and descends, and the speed of this reaction progressively descends, and needs the long period to finish this reaction.Water concentration prevents that speed of reaction from reducing in the raw material that adds if improve, and the problem of Cun Zaiing is that a large amount of heat energy of needs are used for dividing dried up and reacting by heating solution at purification system as previously described.
Among the present invention, hydrolysing step can be divided into a plurality of stages, and the water concentration that the alkylene carbonate transformation efficiency is at least 60% step of reaction should remain on 15-30% (weight) scope.
If less than 15% (weight), as previously described, speed of reaction is tending towards descending water concentration in the step of reaction of intended conversion rate.On the other hand, even water concentration is increased to more than 30% (weight), corresponding to the not further raising of increasing amount speed of reaction of water concentration, and above-mentioned energy consumption increases, and is invalid like this.
Water concentration the method in the scope that the present invention enumerates of remaining on is for example had monitor hydrolytic process and water consumption respectively by test, and add the method for corresponding water amount continuously or intermittently, or the water yield in the periodic monitor system, and add the method for the water of requirement according to monitoring result.
The method that adds entry to system has, as the method that pumps up, and water should preheat keeping temperature of reaction constant, the supply response device, or the steam that its vapour pressure is at least reaction pressure is blown into the method for reactive system.But the method to heating does not have concrete restriction.To the selection of water feeding method, reason below considering selects the method for suitable each step of reaction more suitable.
Among the present invention, hydrolysing step should be divided into a plurality of steps, and with second with to be adjusted to post-reaction period reaction pressure separately be at most the reaction pressure of front step of reaction, as long as second and be adjusted to the reaction pressure that is lower than the front step of reaction with the reaction pressure of at least one step of reaction in the post-reaction period.Can quicken this reaction, this is desirable.Thinking that this ascribes to by system that reaction pressure is reduced to does not take place effectively to remove carbonic acid gas from system in the ebullient scope.Will with second or the reaction pressure of subsequent stage be brought down below the reaction pressure of previous stage, should stage pressure be adjusted to the 20-90% of pressure previous stage.
Be lower than 20% of pressure previous stage if predetermined step of reaction pressure is adjusted to, reaction soln seethes with excitement probably.On the other hand, if surpass 90%, the effect that reduces pressure is very little, and speed of reaction is very low most probably.
Among the present invention, separately pressure should be at least the vapour pressure of this elementary reaction solution in each step of reaction of division.If reaction pressure is lower than this vapour pressure, reaction soln seethes with excitement probably, and water concentration can reduce in the liquid phase, is used for the heat exhaustion that heating heat is used as evaporation, and this is disadvantageous from the energy consumption angle.At this, the vapour pressure of reaction soln is formed the saturation vapour pressure that calculates by the temperature of step of reaction and the reaction soln that do not comprise carbon dioxide.
Hydrolysis pressure among the present invention generally is adjusted to 0.15MPa, and 0.2-3MPa is advisable.If reaction pressure is less than 0.1MPa, as mentioned above, the boiling of the solution that reacts probably.On the other hand, if reaction pressure greater than 5MPa, be guaranteed the ability to bear etc. of pressurizeing, equipment cost increases, and this is uneconomic.
In the inventive method, hydrolysis temperature should be adjusted in 50-200 ℃ of scope.If temperature of reaction is lower than 50 ℃, speed of reaction is too low, can not try out.On the other hand, if reacting surpassing under 200 ℃ the high temperature, alkylene glycol product of poor quality.Reach the overall equilbrium preferably of speed of reaction and quality product, temperature of reaction should be 80-180 ℃ of scope, and 100-180 ℃ better.
This hydrolysis reaction is thermo-negative reaction, keep temperature of reaction to carry out this reaction, must this system of heating.Heating means generally adopt the indirect heating method, as by chuck or coil pipe such as the thermal source of high pressure steam, or electrically heated method; Or snead process, the steam that vapour pressure is at least reaction pressure is blown into reactive system.Water concentration should adopt the indirect heating method of external heat source greater than under 30% (weight) situation.Even in the system of high moisture content, be blown into steam, most of water of supply probably by and be not absorbed, efficient is low.
In the step of reaction of water concentration greater than 30% (weight), employing is effective with the snead process that steam is blown into this system in the system, because heating and water supply can be carried out simultaneously.In the step of reaction of a plurality of divisions, be at least 60% step of reaction at the alkylene carbonate transformation efficiency, water concentration remains on specific scope in the system.At the alkylene carbonate transformation efficiency less than 60% step of reaction, alkylene carbonate concentration is higher in the system, and speed of reaction is subjected to the control of alkylene carbonate concentration, and the influence of water concentration is accessory, needn't emphasize water concentration is remained on specific scope, its effect is also less.
The reactor that uses for method for hydrolysis of the present invention has, as container class reactor, multistage tower reactor or reactive distillation column.The reactor of any kind all must effectively separate the carbon dioxide that hydrolysis produces from reactive system.
In the method for the present invention, hydrolysis stage quantity is preferably 2-8 stage.If number of stages surpasses 8, equipment cost becomes main, and the problem of existence is that reaction process control is tending towards complicated.The method that reactions steps is divided into a plurality of stages generally provides a plurality of reactors corresponding to number of stages.Yet, also can use a reactor, by it being divided into a plurality of parts as separating partition.
The alkylene glycol aqueous solution that adopts the ordinary method distillation to discharge from hydrolysis reactor, alkylene glycol that obtains dewatering and the solution that contains catalyzer, the solution that contains catalyzer is supplied with the step that is generated alkylene carbonate by alkylene oxide and carbon dioxide as catalyst solution.
Discharge the carbon dioxide that hydrolysis forms from hydrolysis reactor, but also be attended by water and alkylene glycol.Among the present invention, carbon dioxide cooling forms condensed fluid, or is washed and makes the solution that contains alkylene glycol.Through being used for the cooling or the washing of condensation, make that alkylene glycol mostly is 20ppm most in the gas.For reaching the purpose that reclaims alkylene glycol, the cooling or the washing that are used for condensation under mild conditions are economically feasible.Yet even the condensed fluid of acquisition or the liquid of washing are got back to this system, the effect that suppresses the catalyst activity variation is also very little.
Contain alkylene glycol solution by what cooling or washing gas obtained, be added to from generate any position of alkylene carbonate step by alkylene oxide and carbon dioxide, to obtain to contain catalyst solution to distillation alkylene glycol aqueous solution step.Preferably it is supplied with hydrolysis reactor, or supply with Distallation systm, contain catalyst solution in the Distallation systm and obtain by aqueous glycol solution.The variation that can suppress by this way, the carbonation reaction catalyst activity that will recycle.Promptly from the hydrolysis reactor expellant gas, contain the component that suppresses the catalyst activity variation, this components dissolved is by cooling or wash in the solution that this gas obtains and recyclable, finally be circulated to the zone that generates ethylene carbonate by oxyethane and carbonic acid gas, think the variation that can suppress catalyst activity like this.Still do not know that what material is this component be.Yet, from the hydrolysis zone expellant gas, containing halogen owing to catalyzer, these halogens change liquid under above-mentioned cooling or wash conditions, therefore, think to the effect of small part inhibition catalyst activity variation owing to these halogens.
Another kind of method as the preparation alkylene glycol has a known method, in this method, and alkylene oxide and the reaction of water in the presence of carbonic acid gas.Yet this reaction relates to alkylene carbonate as intermediate product, thinks that this reaction is one embodiment of the invention, by this reaction method, obtains the alkylene glycol stage water-content is adjusted in 15-30% (weight) scope finishing reaction.And, be that the hydrolysis of remaining alkylene carbonate is effectively carried out to effect of the present invention.
The transformation efficiency of alkylene carbonate is the transformation efficiency that is converted into the alkylene carbonate of alkylene carbonate amount calculating according to whole alkylene oxides in this case.
To alkylene carbonate, be preferably the alkylene carbonate of the alkylidene group of 2-30 carbon atom as raw material in the inventive method.Wherein, preferred industrial important ethylene carbonate or Texacar PC.When the present invention was applied to have ethylene carbonate with water component distillation characteristic, its effect was good especially.
And alkylene carbonate can have the alkyl of one or more 1-12 of containing carbon atom as the substituting group on the alkylidene group.
It is about 100% that the method according to this invention, the final transformation efficiency of alkylene carbonate can reach, and especially at latter stage, the transformation efficiency of alkylene carbonate can reach about 100%.
That is, the method according to this invention is carried out the alkylene carbonate hydrolysis, can be in less volume reactor, or, can prepare alkylene glycol effectively with than short residence time(SRT).
And, even reuse, still can keep the carbonation reaction activity of such catalysts by circulation.
Fig. 1 carries out schema of the present invention.Among Fig. 1, the tower carbonation reactor of reference number 1 expression bubbling, numeral 2 expression carbonic acid gas supply pipes, numeral 3 expression supplies are as the pipeline of alkylene oxide, numeral 4 expression heat exchangers, the circulating line of numeral 5 expression reaction solns, numeral 6 expression vomit pipes, numeral 7 expression gas-liquid separators, numeral 8 expression hydrolysis devices, numeral 9 expression distillation towers, numeral 10 expression washers, numeral 11 represents gas is supplied with the pipeline of water cooler, numeral 12 expression water coolers, and the pipeline of the liquid of condensations is supplied in numeral 13 expressions.
Embodiment
Reference example is described the present invention in further detail.Yet, should be appreciated that the present invention is not subjected to the restriction of these object lessons.
According to the described flow process of Fig. 1, make ethylene glycol by oxyethane, carbon dioxide and water.
Provide carbon dioxide to bubbling column reactor 1 (internal diameter: 20 centimetres, virtual height: 200 centimetres) continuously by pipeline 2, oxyethane, water and recycling catalyst solution are without interruption by pipeline 3.Supply is respectively: carbon dioxide 140kg/hr, and oxyethane 62kg/hr, (be iodate tributyl Jia Ji Phosphonium: about 4.5kg/hr is salt of wormwood: 0.18kg/hr) about 9.0kg/hr for water 50kg/hr and recycling catalyst solution.Be reflected at 2.06MPa and carry out in 110 ℃, make the outer circulating tube 5 of partial reaction solution circulated, come control reaction temperature by comprising heat exchanger 4.
Reaction soln is sent into gas-liquid separator 7 by pipeline 6 and is carried out the solution-air separation, supplies with hydrolysis device 8 then.Hydrolysis device comprises two container class reactors that are connected in series, and controls the hydrolysising condition in each stage, and the fs is carried out under 150 ℃ at 0.55MPa, and subordinate phase is carried out under 150 ℃ at 0.25MPa.React by in each reactor, being blown into steam, make in each reactor water concentration in 15-30% (weight) scope.
As a result, the transformation efficiency that exports ethylene carbonate at the fs hydrolysis reactor is 93.0%, and the subordinate phase reactor outlet is about 100% (gas chromatographic detection limit: less than 10ppm).This moment, water concentration was respectively 18.8% and 19.2%.
At first distillation in distillation tower 9 of the aqueous glycol solution that hydrolysis device is discharged, tower top pressure is 80mmHg, column bottom temperature is 140 ℃, steam water, the solution of discharging at the bottom of the tower is supplied with the washer 10 that keeps 62mmHg pressure, evaporate most of ethylene glycol and glycol ether, the solution that contains residual unevaporated iodate tributyl Jia Ji Phosphonium catalyzer is recovered and recycled to reactor 1.
To supply with water cooler 12 by pipeline 11 from the hydrolysis device expellant gas, be cooled to water of condensation, wherein contain ethylene glycol, reclaim the aqueous solution that contains 6.2% ethylene glycol, it be supplied with the fs of hydrolysis device by pipeline 13 with 27kg/hr speed.From water cooler expellant gas temperature is 39 ℃, and glycol concentration is 4ppm.
In this manner, reaction was carried out 90 days, and the oxyethane transformation efficiency in the reactor 1 is initially 99.5%, even still be 99.4% after 90 days.
Comparative example 1
According to reacting with the mode of embodiment 1 system, difference is to have omitted and will get back to the operation of hydrolysis device by the condensed fluid that cooling forms from the hydrolysis device expellant gas.The oxyethane transformation efficiency is reduced to 98.1% after being initially 99.5%, 90 day.
Comparative example 2
Be prepared the test of ethylene glycol according to the mode with embodiment 1 system, difference is the water concentration that omits in the control latter stage hydrolysis reactor, does not therefore supply with water, and the reactor of only electricity consumption heater heats latter stage keeps its temperature of reaction.
Water concentration in the latter stage reactor is 13.7%, and ethylene carbonate total transformation efficiency in latter stage exit is 99.9%, comprises 1, the ethylene carbonate of 400ppm from the ethylene glycol that the purified solution that obtains makes.
Claims (11)
1. method for preparing alkylene glycol, this method is the method for preparing alkylene glycol continuously, it comprises following step (1)-(4), wherein hydrolysing step (2) is divided into a plurality of stages, and the water concentration that the alkylene carbonate transformation efficiency is at least in 60% the step of reaction that is hydrolyzed is a 15-30% weight:
(1) carbonation step makes alkylene oxide and carbon dioxide reaction in the presence of the carbonation reaction catalyzer, form the reaction soln that contains the carbonic acid alkylene;
(2) hydrolysing step, the prepared reaction soln of hydrolysing step (1), while release of carbon dioxide, the aqueous solution of formation alkylene glycol;
(3) distilation steps, the distillation alkylene glycol aqueous solution makes the alkylene glycol of dehydration at least and the solution that contains the carbonation reaction catalyzer; With
(4) circulation step provides the solution that contains the carbonation reaction catalyzer to carbonation step (1).
2. the method for preparing alkylene glycol as claimed in claim 1, it is characterized in that described hydrolysing step is divided into a plurality of stages, in second step of reaction with post-reaction period, reaction pressure separately is adjusted to the reaction pressure that is up to the front step of reaction, and wherein the reaction pressure of at least one step of reaction is adjusted to the pressure that is lower than the front step of reaction.
3. the method for preparing alkylene glycol as claimed in claim 1, it is characterized in that described hydrolysing step is divided into a plurality of stages, second step of reaction and be adjusted to the 20-90% of front step of reaction pressure with the pressure of at least one reactions steps in the post-reaction period.
4. the method for preparing alkylene glycol as claimed in claim 1 is characterized in that in a plurality of hydrolysis stages of described division that separately reaction pressure is in the 0.1-5MPa scope.
5. preparation alkylene glycol method as claimed in claim 1 is characterized in that in a plurality of hydrolysis stages of described division that separately temperature of reaction is 50-200 ℃ of scope.
6. the method for preparing alkylene glycol as claimed in claim 1 is characterized in that described alkylene carbonate is ethylene carbonate or Texacar PC.
7. the method for preparing alkylene glycol as claimed in claim 1 is characterized in that using quaternary phosphine halogenide as the carbonation reaction catalyzer.
8. the method for preparing alkylene glycol as claimed in claim 7, the gas that it is characterized in that containing the carbon dioxide that discharges from each stage of a plurality of hydrolysis stages of dividing is cooled and condensation, or wash with washings, make the alkylene glycol in the gas mostly be 20ppm most, acquisition contains alkylene glycol solution, with the arbitrary step in these solution supplying step (1)-(4).
9. the method for preparing alkylene glycol as claimed in claim 7 is characterized in that the water supply carbonation step, makes to generate alkylene carbonate and alkylene glycol.
10. the method for preparing alkylene glycol as claimed in claim 8, it is characterized in that will be by cooling and condensed gas, or with the solution supplying step (2) or (3) that contain alkylene glycol of washings washing gas acquisition.
11. the method for preparing alkylene glycol and alkylene carbonate as claimed in claim 1, it is characterized in that the reaction soln that step (1) makes is partly or entirely sent into first distilation steps, from cat head distillation water outlet, alkylene glycol and the azeotropic alkylene carbonate of following, they are recycled to hydrolysing step (2), to send into the after-fractionating step by the liquid that obtains at the bottom of the tower simultaneously, obtain the alkylene carbonate of purification from after-fractionating step cat head, reclaim at the bottom of its tower and contain the carbonic acid alkylene, the liquid of reaction product two alkylene glycol and catalyzer, and be recycled to hydrolysing step (2).
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| CN102791663A (en) * | 2010-03-12 | 2012-11-21 | Hrd有限公司 | Method of making alkylene glycols |
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| CN101578253B (en) * | 2006-12-04 | 2012-12-05 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN101910097B (en) * | 2007-12-06 | 2013-09-18 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN102036940B (en) * | 2008-04-10 | 2013-11-13 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN102177119A (en) * | 2008-10-09 | 2011-09-07 | 国际壳牌研究有限公司 | Process for the recovery of monoethylene glycol |
| CN102177119B (en) * | 2008-10-09 | 2013-09-25 | 国际壳牌研究有限公司 | Process for the recovery of monoethylene glycol |
| CN102791663A (en) * | 2010-03-12 | 2012-11-21 | Hrd有限公司 | Method of making alkylene glycols |
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