CN1192941A - Method for recovering catalyst for preparing binary alcohol - Google Patents
Method for recovering catalyst for preparing binary alcohol Download PDFInfo
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- CN1192941A CN1192941A CN98101330A CN98101330A CN1192941A CN 1192941 A CN1192941 A CN 1192941A CN 98101330 A CN98101330 A CN 98101330A CN 98101330 A CN98101330 A CN 98101330A CN 1192941 A CN1192941 A CN 1192941A
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Abstract
The method for recovering catalyst used in preparation of dihydroxy alcohol by means of reaction of epoxidized compound and water which are mixed together is characterized by that an organic solvent which does not produce chemical reaction with catalyst and polydihydroxy alcohol, and at the same time can dissolve polydihydroxy alcohol, but does not dissolve or slightly dissolve catalyst is added to make washing, and the cleaned solid catalyst can be repeatedly used. After having been distalled to remove polydihydroxy alcohol said organic solvent can be repeatedly utilized, and at the same time the polydihydroxy alcohol can be used as by-product, and recovered.
Description
The present invention relates to a kind of recovery method of catalyst, specifically, is the recovery method that a kind of epoxide and water hybrid reaction prepare the catalyst of dihydroxylic alcohols.
Epoxide among the present invention can be oxirane, expoxy propane etc.With regard to oxirane, the production of present industrial ethylene glycol does not add legal the making of pressure (hydraulic) water of catalyst with oxirane.The legal reaction of pressure (hydraulic) water is carried out under 150～220 ℃ and 1.0～2.5mPa condition usually.After about 30 minutes of oxirane and the water hybrid reaction, the oxirane conversion ratio can reach 100%.The selectivity of glycol product depends primarily on water than (mixed proportion of water and oxirane), and existing industrial level is that the water ratio is 10 (wt.), and the selectivity of ethylene glycol can reach 90%.Because reaction will be removed a large amount of moisture content after finishing, the process energy consumption is very big.Therefore, some developed countries of the world have generally begun the research of catalysis hydration process.Wherein the research of homogeneous catalysis hydration method early, effect is better, realizes on existing commercial plant also the easiliest.U.S. Pat 4,760,200 propose to carry out the method that homogeneous catalysis hydration method is reacted with sodium molybdate as catalyst, reduce at 1～5 o'clock at the water ratio, and the selectivity of ethylene glycol is still more than 90%.The key of homogeneous catalysis hydration method reaction is the recovery circulation of catalyst, but above-mentioned patent is not exactly mentioned the recovery circulatory problems of catalyst.
Clear 56-90029 of Japan Patent and 56-92228 propose at CO
2Exist down, carry out hydration reaction as catalyst with potassium molybdate or KI.The result is 1～5 o'clock in the mol ratio of oxirane and water, and the selectivity that reaction generates ethylene glycol can reach 95%.This patent is thought and can be realized continued operation at industrially scalable, and done industrialized design.Its recovery circulatory problems to catalyst is to adopt the way of distillation to solve.Moisture content in the mixture and ethylene glycol will be separated the mixture that distillation leftover promptly is made up of a large amount of polyethylene glycol and catalyst after promptly will reacting by distillation.Because polyethylene glycol viscosity is very big, flowability is relatively poor, therefore this mixture is difficult to the purpose that direct Returning reactor reaches recycling catalyst.To this, the solution that this patent proposes is that water content is higher than 0.1% (wt.) in this concentrated solution of maintenance, overcomes the mobile relatively poor problem that polyethylene glycol viscosity is brought greatly like this, makes polyethylene glycols and catalyst get back to reactor together smoothly.But according to the principle of hydration reaction, the increase of polyethyleneglycol content will cause the chance of oxirane generation side reaction to increase greatly in the reactor, thereby the overall selectivity of ethylene glycol is descended.Therefore the recovery endless form of this catalyst still can not be dealt with problems preferably.
Europe EP297647 discloses a kind of process route that adopts ethylene carbonate.Its technical process is: in the condition that has catalyst to exist, first step oxirane generates the intermediate product ethylene carbonate with carbon dioxide reaction earlier, and the second step ethylene carbonate generates ethylene glycol with the water reaction again.This technology also is to adopt the way of distillation to the separation of product ethylene glycol, and promptly moisture content, ethylene carbonate and the ethylene glycol that will react in the mixture of back with the way of distillation is separated, and vinasse is exactly polyethylene glycol and mixture of catalysts.The recovery method of its catalyst is to add acylating agent in above-mentioned vinasse, and the reaction of acylating agent and polyethylene glycol generates water-soluble ester class, thus with solid-state catalyst separation.But because chemical reaction has taken place for the acylating agent and the polyethylene glycol that add, so this part polyethylene glycol and acylating agent all can not reclaim again and use; Secondly, because the limitation of the acylation reaction that molecular balance determined itself must add excessive acylating agent; Moreover a small amount of chelate can take place in acylating agent and catalyst, and simultaneously because catalyst is water miscible, and acylation reaction can generate water, and this all can cause the loss of catalyst.
Purpose of the present invention is exactly to overcome above-mentioned prior art to adopt the way of distillation to reclaim the shortcoming of catalyst, has proposed a kind of with poly-dihydric alcohol and catalyst separation and reclaim the new method of catalyst.The method of recovery catalyst of the present invention has solved the separation problem of poly-dihydric alcohol, the loss problem of catalyst, economy problems of use chemical raw material or the like, the industrialization thereby the method that makes the hydration of epoxide homogeneous catalysis prepare dihydroxylic alcohols can be marched toward.
The present invention proposes the recovery method that a kind of epoxide and water hybrid reaction prepare the catalyst of binary alcohol, comprise with the way of distillation and isolate glycol products and water in epoxide and the reactant aqueous solution afterproduct, then distillation leftover is handled.The recovery method of catalyst of the present invention is achieved in that
For in distillation leftover, containing a large amount of catalyst and poly-dihydric alcohol, adopt to add the method that organic solvent carries out carrying out washing treatment; This organic solvent not with catalyst and poly-dihydric alcohol generation chemical reaction, this organic solvent can dissolve poly-dihydric alcohol and insoluble or slightly soluble catalyst simultaneously; Solid catalyst behind washing, purifying is re-used in the preparation dihydroxylic alcohols; The organic solvent that is dissolved with poly-dihydric alcohol reuses after distillation removes poly-dihydric alcohol, poly-dihydric alcohol reclaims as byproduct simultaneously.
Catalyst of the present invention can be selected from molybdate, tungstates, vanadate, carbonate, halogen; Wherein preferred especially following compounds: sodium molybdate, potassium molybdate, sodium tungstate, potassium tungstate.
It is 1～8 hydrocarbon, alcohol, ether, amine, ketone, simple aromatic compound that the solvent that recovery catalyst of the present invention is used is selected from carbon number; Wherein preferred solvent is selected from acetone, monoethanolamine, diethanol amine, methyl alcohol, ethanol, glycerine, pentane, phenol, pyridine, furfural; The solvent that best recovery catalyst is used is selected from methyl alcohol, ethanol, acetone.
The consumption of the solvent that recovery catalyst of the present invention is used is 2-40 a times of poly-dihydric alcohol weight in the residue; The consumption of the solvent that preferred recovery catalyst is used is 2-30 a times of poly-dihydric alcohol weight in the residue.
Epoxide of the present invention can be one of following epoxide: oxirane, expoxy propane, phenyl ethylene oxide etc.
Catalyst recovery process of the present invention can be carried out by twice above same sampling technology of repeated using.
With regard to oxirane, the recovery method of catalyst of the present invention specifically can be realized like this:
Oxirane enters tubular reactor after the aqueous solution of catalyst and carries out hydration reaction with containing, and the product after the hydration reaction is ethylene glycol, water, polyethylene glycol and mixture of catalysts.This mixture is after separated goes out product ethylene glycol, water or continues to isolate diethylene glycol, triethylene glycol, TEG, adding organic solvent in the bottoms that contain polyethylene glycol and catalyst of remainder washs, this organic solvent can dissolve polyethylene glycol and catalyst-solvent not, and this organic solvent not with polyethylene glycol and catalyst generation chemical reaction.Catalyst after washing returns reactor and goes to reuse, and the organic solvent that is dissolved with polyethylene glycol reclaims solvent and polyethylene glycol respectively through simple distillation.
The used water and the mol ratio of oxirane are preferably 1～5 in the above-mentioned course of reaction.
Above-mentioned catalyst is preferably from following compounds: sodium molybdate, potassium molybdate, sodium tungstate, potassium tungstate.
The solvent that above-mentioned recovery catalyst is used is methyl alcohol, ethanol, acetone preferably.The consumption of this solvent is 2-30 a times of ethylene glycol weight ratio.
Can add other gases or solvent and carry out to promote reaction in above-mentioned reaction, described gas or solvent are carbon dioxide or glycol dimethyl ether.
Above-mentioned catalyst recovery process can be carried out by twice above same sampling technology of repeated using.
Adopt method of the present invention, solved poly-dihydric alcohol separation problem in the recycling use of catalyst; Solved the loss problem of catalyst, made a step rate of recovery of catalyst be not less than 94%, reclaimed through multistep, the overall recovery of catalyst is then higher; The present invention can also make the water consumption in the epoxide hydration produce diatomic alcohol process descend, be that the water ratio can reduce to 5～1 by 10; The employed solvent of catalyst recovery then can be realized recycling substantially; The selectivity of dihydroxylic alcohols is constant when reclaiming the catalyst repeated use that obtains simultaneously.In sum, method of the present invention has reduced the energy consumption of the consumption and the separation process of chemical raw material, and product dihydroxylic alcohols production cost is reduced greatly; Adopt method of the present invention that existing commercial plant be need not too big change in addition, just can make the production capacity of existing apparatus improve several times.Therefore, method of the present invention has solved the recovery circulatory problems of catalyst in the homogeneous catalysis hydro-combination process well, has eliminated the homogeneous catalysis method and has realized an industrialized obstacle.
Embodiment:
The used raw material of embodiment of the invention hydrating process is an oxirane, and catalyst is a sodium molybdate.Oxirane and purity are respectively through measuring pump metering after to mix at 1: 2 greater than the aqueous solution of 99.5% sodium molybdate by weight, enter internal diameter 10mm then, the stainless steel tubular type reactor of long 1200mm, the control reaction temperature is 140 ℃, pressure is 2.0MPa, and reaction time is 45 minutes.Product enters basin after cooling.
Again above-mentioned product being sent into rectifying column separates with the way of distillation.By multiple-effect evaporation moisture content being separated, then ethylene glycol is separated (sample 1) through reduction vaporization again, also can further be that 2,3,4 polyethylene glycol is that diethylene glycol, triethylene glycol, TEG are separated (sample 2) together with the degree of polymerization.The mixture that distillation leftover promptly is made up of a large amount of polyethylene glycol and catalyst.
Organic content chromatograph (GB/T 14571.2-93) before and after the reaction, the chromatography result, the conversion ratio of oxirane is 100%, the selectivity of ethylene glycol is 90.5%; The catalyst sodium molybdate is analyzed (Q/HG 11-162-82) embodiment 1～3 with chemical method
The solvent that embodiment 1～3 selects for use is followed successively by methyl alcohol, ethanol and acetone.The bottoms of selecting for use are respectively moisture content when having steamed substantially (sample 1), and ethylene glycol, diethylene glycol, triethylene glycol, (sample 2) two kinds of samples when TEG has all steamed substantially.
Wherein 10 times of absolute ethyl alcohols to its weight of sample 1 usefulness are that solvent washs, and leave standstill and obtain water white catalyst crystal after 24 hours, and its catalyst recovery yield only is 65%.Therefore the presentation of results of sample 1, if further be not that 2,3,4 polyethylene glycol is that diethylene glycol, triethylene glycol, TEG are also separated with the degree of polymerization, the recovering effect of catalyst is not good.
Sample 2 (being embodiment 1～3) is handled with three kinds of solvents respectively, its method and the results are shown in following table 1, table 2:
The clean result of the following three kinds of solvents of table 1 room temperature
Table 2 changes the result after the solvent wash condition
| Separation method | Cold filtration | Hot extracting | Hot extracting |
| The extracting time (hr) | ?????6 | ?????6 | ?????6 |
| Reclaim the purity of catalyst, (%) | ????97.24 | ????99.24 | ????99.41 |
| Catalyst recovery yield (%) | ????95.33 | ????94.19 | ????96.92 |
Cold filtration in the table is meant to add methyl alcohol and mix the back and leaves standstill in 4 ℃, filters then and obtains catalyst solid, carries out analytical calculation after the drying.
Hot extracting in the table is to carry out in cable-styled extractor.The filtration paper cylinder of spooling with solvent washing is dried the back weighing earlier, is weighed into the bottoms of a certain amount of (accurately to 0.0002g) again, and this filtration paper cylinder is put into extractor.Solvent splashes in the extractor after solvent evaporation rising condensation again during heating in the distilling flask of bottom, flows down voluntarily when solvent liquid level rises to the bend pipe highest point, so circulation.Reflux behind the maintenance 6hr, take out filtration paper cylinder, dry, weigh.In the tube promptly is the catalyst that is recovered to.
Sample 2 is the presentation of results of embodiment 1～3, is that diethylene glycol, triethylene glycol, TEG also separate at the polyethylene glycol that further is 2,3,4 with the degree of polymerization, the recovering effect remarkable improvement of catalyst, and catalyst recovery yield has reached more than 94%.
The catalyst that the foregoing description 1～3 is recovered to uses by the experiment condition of catalyzing epoxyethane hydration part again, and its result is, oxirane conversion ratio 100%.Glycol selectivity 89.8%.
Claims (10)
1. the recovery method of the used catalyst of epoxide and water hybrid reaction produce diatomic alcohol comprises with the way of distillation and isolates glycol products and water in epoxide and the reactant aqueous solution afterproduct, it is characterized in that:
For catalyst that in distillation leftover, contains and poly-dihydric alcohol, adopt to add the method that organic solvent washs; This organic solvent not with catalyst and poly-dihydric alcohol generation chemical reaction, this organic solvent can dissolve poly-dihydric alcohol and insoluble or slightly soluble catalyst simultaneously; Solid catalyst behind washing, purifying is re-used in the preparation dihydroxylic alcohols; The organic solvent that is dissolved with poly-dihydric alcohol reuses after distillation removes poly-dihydric alcohol, poly-dihydric alcohol reclaims as byproduct simultaneously.
2. the recovery method of catalyst according to claim 1 is characterized in that, described catalyst is selected from molybdate, tungstates, vanadate, carbonate, halogen.
3. the recovery method of catalyst according to claim 1 is characterized in that, the catalyst of described recovery is selected from sodium molybdate, potassium molybdate, sodium tungstate, potassium tungstate.
4. the recovery method of catalyst according to claim 1 is characterized in that, the solvent that described recovery catalyst is used is selected from alcohol, ether, amine, ketone, hydrocarbon, the simple aromatic compound that carbon number is 1-8.
5. the recovery method of catalyst according to claim 1 is characterized in that, the solvent that described recovery catalyst is used is selected from acetone, monoethanolamine, diethanol amine, methyl alcohol, ethanol, glycerine, pentane, phenol, pyridine, furfural.
6. the recovery method of catalyst according to claim 1 is characterized in that, the solvent that described recovery catalyst is used is selected from methyl alcohol, ethanol, acetone.
7. the recovery method of catalyst according to claim 1 is characterized in that, the consumption of the solvent that described recovery catalyst is used is 2-40 a times of poly-dihydric alcohol weight in the residue.
8. the recovery method of catalyst according to claim 1 is characterized in that, the consumption of the solvent that described recovery catalyst is used is 2-30 a times of poly-dihydric alcohol weight in the residue.
9. the recovery method of catalyst according to claim 1 is characterized in that, described epoxide is a kind of in oxirane, expoxy propane or the phenyl ethylene oxide.
10. according to the recovery method of the described catalyst of one of claim 1～9, it is characterized in that twice above same sampling technology of described catalyst recovery process repeated using carries out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98101330A CN1101258C (en) | 1998-04-08 | 1998-04-08 | Method for recovering catalyst for preparing binary alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98101330A CN1101258C (en) | 1998-04-08 | 1998-04-08 | Method for recovering catalyst for preparing binary alcohol |
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| Publication Number | Publication Date |
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| CN1192941A true CN1192941A (en) | 1998-09-16 |
| CN1101258C CN1101258C (en) | 2003-02-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98101330A Expired - Fee Related CN1101258C (en) | 1998-04-08 | 1998-04-08 | Method for recovering catalyst for preparing binary alcohol |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1026696C (en) * | 1989-06-02 | 1994-11-23 | 岳阳石油化工总厂研究院 | Method of recovering epoxy chloropropane and toluene |
| CN1062738A (en) * | 1990-12-26 | 1992-07-15 | 天津商学院 | The method of purification of polyoxyethylene glycol |
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Granted publication date: 20030212 Termination date: 20100408 |