CN102971450B - The manufacture method of alkyl glycidyl ether - Google Patents
The manufacture method of alkyl glycidyl ether Download PDFInfo
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- CN102971450B CN102971450B CN201180029328.0A CN201180029328A CN102971450B CN 102971450 B CN102971450 B CN 102971450B CN 201180029328 A CN201180029328 A CN 201180029328A CN 102971450 B CN102971450 B CN 102971450B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
Abstract
The present invention relates to the manufacture method of alkyl glycidyl ether, wherein, to be made up of non-homogeneous phase system (oil phase/water phase) and containing concentration be the chloropharin ether of more than 5 % by weight, the composition (A) of water and eletrolytes to be directed in the electrodialysis with Bipolar Membrane and to apply electric current, thus utilize the effect of the OH-produced by Bipolar Membrane to be transformed to alkyl glycidyl ether by the chloropharin ether in the composition (A) containing chloropharin ether, and the Cl-simultaneously given birth to by by-product is as HCL(hydrochloric acid) carry out Separation and Recovery.
Description
Technical field
The present invention relates to the manufacture method of alkyl glycidyl ether, specifically relate to use the manufacture method of the alkyl glycidyl ether of the electrodialysis with Bipolar Membrane.
Background technology
In the past, alkyl glycidyl ether is by the presence of acid catalyst, make after alcohol and Epicholorohydrin be obtained by reacting chloropharin ether (chlorohydrinether) compound, use the alkaline agent (calcium hydroxide etc.) of more than chloropharin ether and equivalent to manufacture according to making it shown in following reaction formula to carry out ring-closure reaction and obtain.
(in formula, R represent from raw alcohol removing 1 hydroxyl after residue.）
But, when use alkaline agent carries out ring-closure reaction, the metal-salt that a large amount of by-product life is obtained by alkaline agent.Therefore, these metal-salts etc. will be removed as object, be necessary to carry out washing etc. treatment process, and occur not only needing a large amount of water resourcess, and also produce the problem containing metal-salt and organic waste water, thus seek its solution.
On the other hand, in JP-A2001-240594, describe and chloropharin ether compound is reacted with alkaline agent being dissolved under the state in hydrophilic organic solvent, isolate an alkali metal salt of solid phase from resultant of reaction after, from liquid phase, reclaim the method for organic solvent and glycidyl ether.
On the other hand, in US-A5980724, record alpha-halogen alcohol solution to be directed into and have in the electrodialysis of Bipolar Membrane, carried out the manufacture method of the epoxy compounds of the ring-closure reaction of alpha-halogen alcohol by electrodialysis reaction.
Summary of the invention
The invention provides a kind of manufacture method of alkyl glycidyl ether, wherein, comprise following operation 1 and operation 2,
Operation 1: by the region 1 of the electrodialysis containing following region 1 and 2, import containing concentration be the chloropharin ether of more than 5 % by weight, the composition (A) (composition (A) hereinafter also referred to containing chloropharin ether) of ionogen and water galvanic current is energized, in zone 1 chloropharin ether transformed to alkyl glycidyl ether and obtain composition (B), making the chlorion (Cl that by-product is raw in zone 1 simultaneously
-) move to carry out the operation of Separation and Recovery as hydrochloric acid in region 2 by anion-exchange membrane,
Region 1: the region delimited between anion-exchange membrane and the anion-exchange membrane side of the 1st Bipolar Membrane,
Region 2: adjacent with region 1 across the above-mentioned anion-exchange membrane of defined area 1, and the region delimited between above-mentioned anion-exchange membrane and the cationic exchange membrane side of the 2nd Bipolar Membrane;
Operation 2: by composition (B) layering obtained in operation 1, is separated into the operation of oil phase layer containing alkyl glycidyl ether and aqueous phase layer.
Detailed description of the invention
In the method described in JP-A2001-240594, can think from the metal-salt of removing by-product life or the viewpoint of minimizing water resources and make moderate progress, but the operation of the organic solvent newly needing again Separation and Recovery to add etc. is not also the method that can fully meet.
In addition, in the method described in US-A5980724, react because of not using alkaline agent, the viewpoint not containing a large amount of metal-salt from waste water makes moderate progress so can be thought, but needing alpha-halogen alcohol to be directed under the state of uniform dissolution in water in electrodialysis (namely needs to import the low aqueous solution of alpha-halogen determining alcohol), therefore relative to the electricity used, the receipts amount of the epoxy compounds obtained is low.In addition, because be the reaction in homogeneous system (aqueous phase system), being therefore not easy by the resultant of reaction layering that obtains to recycle water, from the view point of effective utilization of water resources, is not also the method that can fully meet.
Therefore, the invention provides and effectively can utilize water resources, receive the manufacture method measuring the alkyl glycidyl ether of alkyl glycidyl ether with height.
The present inventors are by importing specific composition to the electrodialysis with Bipolar Membrane, and react in uneven phase system, find thus to use alkaline agent and to obtain alkyl glycidyl ether with high yield, and then effective utilization of water resources, namely, the advantage in the process of water displacement can be reduced, and complete the present invention.
By manufacturing alkyl glycidyl ether according to manufacture method of the present invention, can not alkaline agent be used and carry out the ring-closure reaction of chloropharin ether, thus do not have the raw a large amount of metal-salt (therefore, substantially not needing the removing of metal-salt to operate) of the by-product with the use of alkaline agent.
In addition, because be the ring-closure reaction that the composition high to chloropharin ether concentration carries out being caused by electrodialysis method, the alkyl glycerylether of the q.s suitable with the electricity used can be obtained.
And then, because be not in homogeneous system but carry out the ring-closure reaction that caused by electrodialysis method in uneven phase system (oil phase containing chloropharin ether/be made up of water and ionogen aqueous phase), therefore water easily can be carried out separation recycling by resultant of reaction layering, by effectively utilizing water resources, thus significantly can reduce the generation of waste water.
The invention provides a kind of manufacture method of alkyl glycidyl ether, the removing operation of its metal-salt not needing by-product raw, significantly can reduce the generation of waste water, and then can obtain alkyl glycidyl ether to high receipts amount by effectively utilizing water resources.
Accompanying drawing explanation
An embodiment of [Fig. 1] electrodialysis used in the present invention
Other embodiment of [Fig. 2] electrodialysis used in the present invention
Symbol in following explanatory view,
10 cathode compartments
11 anolyte compartments
12 regions 1
13 regions 2
21 negative plates
22 positive plates
23 anion-exchange membranes
24 the 1st Bipolar Membrane
The anion-exchange membrane side of 24a the 1st Bipolar Membrane
The cationic exchange membrane side of 24b the 1st Bipolar Membrane
25 the 2nd Bipolar Membrane
The anion-exchange membrane side of 25a the 2nd Bipolar Membrane
The cationic exchange membrane side of 25b the 2nd Bipolar Membrane
40,41,42,43 outlets
40,41,42,43 outlets
Embodiment
< operation 1>
Acquisition for the composition (A) containing chloropharin ether used in operation 1 of the present invention is not particularly limited.
Can by adding water and eletrolytes in the composition in the chloropharin ether being synthesized by known method, refine or the response composite obtained in this process or refining way, the receipts amount of alkyl glycidyl ether when reacting from the view point of electrodialysis and current efficiency, the concentration being preferably modulated into chloropharin ether is 5 ~ 70 % by weight, more preferably 10 ~ 65 % by weight, be more preferably 25 ~ 65 % by weight, further be preferably 35 ~ 65 % by weight, be particularly preferably 40 ~ 55 % by weight, thus obtain composition (A).The value calculated by following mathematics formula is referred in this current efficiency.
As concrete example, the reactant composition by being obtained by reacting by the known method of alcohol and Epicholorohydrin, refining thing etc. from these can be enumerated.
If manufacture method of the present invention only considers the production of alkyl glycidyl ether, most preferably use the composition (A) containing chloropharin ether obtained as raw material by chloropharin ether list product, but need to refine to obtain chloropharin ether list product, therefore usual from the view point of operability and productivity, be preferably provided as intermediate and contain the composition of chloropharin ether as raw material.
In addition, from the view point of the productivity of alkyl glycidyl ether, raw material obtain easiness, the chloropharin ether used in modulation is containing the composition (A) of chloropharin ether, the content of preferred use chloropharin ether is 5 ~ 100 % by weight, be more preferably 25 ~ 100 % by weight, be particularly preferably the chloropharin ether composition of 50 ~ 100 % by weight (100 % by weight represent chloropharin ether list product).
Chloropharin ether can, by the presence of acid catalyst, make alcohol and Epicholorohydrin be obtained by reacting usually.
As alcohol, the alcohol represented by following general formula (I) preferably can be used.
R-OH（I）
(in formula, R represents that carbonatoms is the straight chain of 3 ~ 22, the alkyl of side chain or ring-type or thiazolinyl.）
Although as long as the alcohol represented by general formula (I) is all applicable to using, but carry out in nonhomogeneous system from the reaction operation 1, the viewpoint that layering in operation 2 is more easily carried out is set out, and the R in general formula (I) is more preferably carbonatoms and is 3 ~ 18, is more preferably carbonatoms and is 5 ~ 12, is particularly preferably alkyl or the thiazolinyl of the straight chain of 8 ~ 12, side chain or ring-type.As the object lesson of preferred alcohol, butanols, amylalcohol, octanol, 2-Ethylhexyl Alcohol, decyl alcohol, dodecanol can be enumerated, wherein further preferably amylalcohol, octanol, 2-Ethylhexyl Alcohol, decyl alcohol, dodecanol, be more preferably octanol, 2-Ethylhexyl Alcohol, decyl alcohol, dodecanol.
The usage quantity of alcohol and Epicholorohydrin, from the view point of the yield of chloropharin ether, uses Epicholorohydrin 0.1 ~ 10mol relative to 1mol alcohol, preferably uses 0.5 ~ 2mol.
As catalyzer, the homogeneous system Bronsted acid that such as can to enumerate with sulfuric acid etc. be representative; Or the homogeneous system Lewis acid etc. that the catalyzer (JP-A10-36307) be made up of tin tetrachloride or boron trifluoride, aluminium-alcohol salt and phenols or sulphonic acids etc. are representative.
From the view point of reactive and productivity, its usage quantity is preferably 0.001 ~ 10mol relative to 1mol Epicholorohydrin, more preferably 0.002 ~ 5mol, is more preferably 0.003 ~ 1mol.
In addition, described catalyzer preferably removed before carrying out the electrodialysis method of operation 1.Such as, when using the catalyzer be made up of aluminium-alcohol salt and phenols or sulphonic acids as above, can make it by adding the alkali compositions such as sodium hydroxide to separate out solidification, thus can easily remove.
As the addition of alkali composition, because the generation of salt in operation 1 can be reduced further, so the sour composition of the catalyzer used relative to 1mol, be preferably 0.8 ~ 1.2mol, more preferably 0.9 ~ 1.1mol.
Be not particularly limited becoming the acquisition containing the chloropharin ether of the raw material of the composition (A) of chloropharin ether used in operation 1, such as when making alcohol as above and Epicholorohydrin reacts and obtains, composition (A) containing chloropharin ether is except chloropharin ether, the main composition containing unreacted alcohol.
When the raw material of the composition (A) containing chloropharin ether is the response composite containing such chloropharin ether and unreacted alcohol, even if be directly directed in electrodialysis, does not also substantially show powered, electrodialysis can not be caused to react.Therefore, by adding water and ionogen in such response composite, thus make the composition (A) containing chloropharin ether that can be used in electrodialysis reaction.
As water, preferably use ion exchanged water.In addition, as ionogen, sodium-chlor, Repone K, sodium sulfate etc. can be used, preferred sodium-chlor.
When adding water and eletrolytes and obtaining composition (A) containing chloropharin ether, from the view point of by reacted for electrodialysis resultant of reaction layering so that easy recycle-water (and ionogen), importantly the Concentration Modulation of chloropharin ether is become more than 5 % by weight, and the composition (A) obtained containing uneven phase (that is, the oil phase be made up of chloropharin ether (and according to circumstances different and containing unreacted alcohol etc.)/be made up of water and ionogen aqueous phase).
By using containing the composition (A) of uneven phase, can not alkaline agent be used and obtain alkyl glycidyl ether with high yield, also have further and effectively can utilize water resources, namely reduce advantage in the process of water displacement.
The receipts amount containing the alkyl glycidyl ether when concentration of chloropharin ether is reacted from the view point of electrodialysis in the composition (A) of chloropharin ether of the present application and current efficiency, be preferably 5 ~ 70 % by weight, more preferably 10 ~ 65 % by weight, be more preferably 25 ~ 65 % by weight, further be preferably 35 ~ 65 % by weight, be particularly preferably 40 ~ 55 % by weight.
In addition, as the raw material of the composition (A) containing chloropharin ether, when the response composite containing chloropharin ether and unreacted alcohol lifted when being used as above-mentioned object lesson, the receipts amount of alkyl glycidyl ether when reacting from the view point of electrodialysis and current efficiency, the relative concentration forming the oil-phase component of oil phase layer is preferably 10 ~ 90 % by weight in the overall of the composition (A) containing chloropharin ether, more preferably 20 ~ 80 % by weight, be more preferably 35 ~ 75 % by weight.
At the composition (A) containing chloropharin ether if in the reaction of electrolytical concentration electrodialysis be just not particularly limited, but from the view point of current efficiency, be preferably 0.01 ~ 30 % by weight, more preferably 0.1 ~ 10 % by weight, be more preferably 1 ~ 5 % by weight.
In addition, as the water added in the modulation of the composition (A) containing chloropharin ether and electrolytical part or all, the aqueous phase reclaimed by layering in following operation 2 can be recycled.Like this, effective utilization of water resources can be realized, and significantly reduce the generation of waste water.
Further, operation 1 is directed into by the composition (A) containing chloropharin ether to have in the electrodialysis of Bipolar Membrane, reacted the operation transformed to alkyl glycidyl ether by chloropharin ether by electrodialysis.
At this, Bipolar Membrane has the structure of anion-exchange membrane and cationic exchange membrane laminating.Known by using the anion-exchange membrane side of Bipolar Membrane as anode side, cationic exchange membrane side is assembled in electrodialysis as cathode side, thus when applying electric current, on this anion-exchange membrane-cationic exchange membrane interface, water decomposition and produce H
+and OH
-.
In the present invention, by using the OH now produced
-, can not former alkaline agent be used and carry out the ring-closure reaction of chloropharin ether.
In FIG exemplified with an embodiment of the electrodialysis used in operation 1.In the mode shown in Fig. 1, electrodialysis possesses region 1(12 possessing between the cathode compartment of negative plate (21) (10) and the anolyte compartment (11) possessing positive plate (22)) and region 2(13).
Region 1(12) by the anion-exchange membrane side (24a) of the 1st Bipolar Membrane (24) of one end and anion-exchange membrane (23) delimitation of delimiting cathode compartment (10), in addition, region 2(13) by the cationic exchange membrane side (25b) of the 2nd Bipolar Membrane (25) of one end and anion-exchange membrane (23) delimitation of delimiting anolyte compartment (11), region 1(12) and region 2(13) interval anion-exchange membrane (23) and being disposed adjacent.
Cathode compartment (10) also possesses the entrance (30) for importing aqueous electrolyte liquid and the outlet (40) for discharging aqueous electrolyte liquid.Anolyte compartment (11) and region 2(13) also possess the entrance (31,33) for importing aqueous electrolyte liquid and the outlet (41,43) for discharging respectively.
Region 1(12) possess the entrance (32) for importing the composition (A) containing chloropharin ether and the outlet (42) for discharging.
If to region 1(12) in import containing chloropharin ether composition (A) and apply electric current, then the OH produced on anion-exchange membrane (24a)-cationic exchange membrane (24b) interface of the 1st Bipolar Membrane (24)
-region 1(12 is supplied to) by the anion-exchange membrane (24a) of the 1st Bipolar Membrane (24).This OH
-at region 1(12) in react according to following reaction formula with chloropharin ether, generate alkyl glycidyl ether.
Thus, at region 1(12) in, obtain the composition (B) containing alkyl glycidyl ether.
(in formula, R represents the implication identical with the R in general formula (1).）
By above-mentioned reaction at region 1(12) in the raw chloride ion (Cl of by-product
-) by anion-exchange membrane (23) to region 2(13) mobile.On the other hand, at region 2(13) in, when applying electric current, the H that anion-exchange membrane (25a)-cationic exchange membrane (25b) interface of the 2nd Bipolar Membrane (25) produces
+supplied, from region 1(12 by the cationic exchange membrane (25b) of the 2nd Bipolar Membrane (25)) the mobile Cl come
-at region 2(13) in H
+reaction generates HCl(hydrochloric acid).
At region 2(13) in produce hydrochloric acid such as can recycle as the raw material for the manufacture of Epicholorohydrin.
In addition, as being directed into region 2(13) in aqueous electrolyte liquid ionogen used, except the ionogen that the ionogen that can use with use when modulating above-mentioned composition (A) containing chloropharin ether is identical, can also hydrochloric acid be used.
In addition, be supplied to region 2(13) if the electrolyte concentration electrodialysis reaction of aqueous electrolyte liquid carry out just without particular limitation of, from the view point of current efficiency, preferably 0 ~ 35 % by weight, more preferably 0.1 ~ 15 % by weight, be more preferably 0.2 ~ 10 % by weight.
The aqueous electrolyte liquid being directed into cathode compartment (10) and anolyte compartment (11) preferably contains sodium hydroxide, potassium hydroxide etc. as ionogen, electrolytical concentration is from the view point of current efficiency, be preferably 0.1 ~ 30 % by weight, more preferably 0.5 ~ 10 % by weight.
For will containing chloropharin ether composition (A) to region 1(12) importing and by aqueous electrolyte liquid to cathode compartment (10), anolyte compartment (11) and region 2(13) importing in any situation, as long as electrodialysis reaction is carried out, pump can be used make it the logical liquid that circulates, also only can pass through each region/electrode vessel 1 time.
The electric current applied on electrodialysis in operation 1, if the reaction of above-mentioned electrodialysis carry out all without particular limitation of, from the view point of productivity and current efficiency, be preferably with 50 ~ 1500A/m
2, more preferably with 100 ~ 1200A/m
2current density energising.
In addition, be directed in region 1 containing the composition (A) of chloropharin ether between the electrodialysis reaction period, its temperature, from the view point of efficiency, preferably maintains 5 ~ 90 DEG C, more preferably 10 ~ 60 DEG C, is more preferably in the scope of 10 ~ 50 DEG C.
Using the electrodialysis with Bipolar Membrane in the manufacture method of the present invention that chloropharin ether is transformed to alkyl glycidyl ether, not only can not give birth to a large amount of metal-salt by by-product along with the use of alkaline agent, and as mentioned above, can also by chloride ion (Cl raw for by-product
-) carry out Separation and Recovery as the hydrochloric acid such as becoming Epicholorohydrin raw material.
In operation 1, after electrodialysis reaction, from the view point of recycling, in region 2, the concentration of hydrochloric acid of Separation and Recovery is preferably 0.1 ~ 35 % by weight, and more preferably 0.5 ~ 20 % by weight, this manufacture raw material as Epicholorohydrin is also preferred.
In Fig. 1, exemplified with the electrodialysis possessing 1 region 1 and 2 respectively, as shown in Figure 2, those skilled in the art's easy understand can use and region 1 and region 2 are arranged multiple electrodialysis alternately.
In addition, from the view point of efficiency, the weight ratio of being tried to achieve by the composition be directed in region 1/the be directed into ionogen in region 2 is preferably 0.1 ~ 10, and more preferably 0.5 ~ 2, be more preferably 1.0 ~ 1.5.
< operation 2>
Operation 2 is composition (B) layerings will obtained by operation 1, is separated into the operation of oil phase containing alkyl glycidyl ether and aqueous phase.
The composition (B) that obtains in region 1 at electrodialysis through the electrodialysis reaction of operation 1, such as when with alcohol and Epicholorohydrin are obtained by reacting containing the composition (A) of chloropharin ether as raw material, it is the composition be made up of the uneven phase system (that is, the oil phase be made up of alkyl glycidyl ether, chloropharin ether and alcohol/be made up of water and ionogen aqueous phase) containing the unreacted chloropharin ether outside alkyl glycidyl ether or alcohol and water and eletrolytes.
The layering of composition of the present invention (B) without particular limitation of, can carry out according to the method used in general industry process.Specifically, the methods such as stratification method, centrifugal top and bottom process can be used.
Composition of the present invention (B) can easily make oil phase layer and aqueous phase layer layering by leaving standstill.
When making oil phase layer and aqueous phase layer layering making composition (B) leave standstill, the temperature of composition (B) preferably maintains 5 ~ 90 DEG C, more preferably in the scope of 10 ~ 85 DEG C.
The electrolyte concentration of the aqueous phase obtained by layering is preferably 0.1 ~ 20 % by weight, more preferably 0.1 ~ 10 % by weight, be more preferably in the scope of 0.1 ~ 1 % by weight, preferably as interpolation during modulation above-mentioned composition (A) containing chloropharin ether water and electrolytical part or all and recycle.
Thus, through the electrodialysis reaction of operation 1, composition (B) that the uneven phase system that obtains in region 1 at electrodialysis is formed is by making it layering, can receive with height from oil phase and measure alkyl glycidyl ether, and, aqueous phase layer can recycle in the modulation of the composition (A) containing chloropharin ether, significantly can reduce wastewater flow rate.
Embodiment
Below, by embodiment, the present invention is described, but does not limit the present invention by described embodiment.In addition, unless otherwise specified, " % " expression " % by weight ".In addition, in following examples and comparative example, the analysis of each composition is carried out according to following gas chromatography.
< gas chromatographic analysis >
Device: HEWLETTPACKARD company manufactures, HP6850SeriesGCSystem
Post: AgilentTechnologies company manufactures, HP-50+, 30m length × 0.32mm diameter × 0.25 μm thickness
Detector: FID
Elevated Temperature Conditions: 50 DEG C (keeping 2min) → 10 DEG C/min → 280 DEG C (keeping 5min)
Implantation temperature: 280 DEG C
Detector temperature: 280 DEG C
In addition, in following embodiment and comparative example, use following raw material.
2-Ethylhexyl Alcohol: Northeast chemistry manufactures 2-Ethylhexyl Alcohol deer 1 grade
Aluminum isopropylate (aluminiumisopropoxide): KawakenFineChemicalsCo., Ltd. manufacture, aluminum isopropylate (aluminumisopropylate)
98% sulfuric acid: Sigma-AldrichJapan manufactures, and sulfuric acid JIS is superfine
Epicholorohydrin: DOWCHEMICAL manufactures Epicholorohydrin
48% sodium hydroxide: TokuyamaCorporation manufactures caustic soda (48%)
Sodium-chlor: it is superfine that KishidaChemicalCo., Ltd. manufacture sodium-chlor
Become the Production Example of chloropharin ether (A1) (response composite) of the raw material of the composition (A) containing chloropharin ether
The 2-Ethylhexyl Alcohol of 5060.0g, 27.1g aluminum isopropylate, 20.7g98% sulfuric acid is added in glass container, under agitation be adjusted to after 80 ~ 100 DEG C, 2400.0g Epicholorohydrin 240 minutes are dripped to react, be adjusted to after 50 DEG C, add 48% sodium hydroxide of 34.5g, use the PTFE strainer (AdvantecToyoKaisha of 0.2 μm, Ltd. PTFE membrane filter is manufactured) filter, composition (A1) 7400g(obtained containing 5300g chloropharin ether contains unreacted 2-Ethylhexyl Alcohol).By said composition (A1) in following examples 1 ~ 7, comparative example 1.
Embodiment 1
In 60.0g composition (A1), add 12.0g sodium-chlor and 528.0g ion exchanged water, obtain the composition (A) (containing 42.6g chloropharin ether) containing chloropharin ether.
Operation 1: by 10 anion-exchange membranes (ASTOMCorporation manufacture AHA, useful area 55cm
2), 11 Bipolar Membrane (BP-1E that ASTOMCorporation manufactures, useful area 55cm
2) in region 1 according to the electrodialysis (the MicroAcilyzerEX3B type that ASTOMCorporation manufactures) of arrangement mutual shown in Fig. 2, by the composition (A) containing chloropharin ether, or the aqueous electrolyte liquid will be made up of 10.0g sodium-chlor and 490.0g ion exchanged water in region 2, under agitation make it with pump the logical liquid that circulates respectively, voltage constant between K-A is remained 30V, logical galvanic current simultaneously, carries out the electrodialysis reaction of 2 hours.The integrating electric amount of circulation is 11.9Ah, and average current density is 1000A/m
2, the liquid temperature in region 1 is in the scope of 15 ~ 40 DEG C.
After reaction, obtain 354.9g composition (B) in zone 1.Composition (B) is carried out composition analysis by vapor-phase chromatography, and result obtains 31.8g in the chloropharin ether of the composition (A) containing chloropharin ether and transforms to 2-hexyl glycidyl ether, does not use alkaline agent also can carry out conversion reaction.In addition, in region 2, obtain the hydrochloric acid of 644g1.8%.
Operation 2: left standstill at 15 DEG C by composition (B), result easily can be separated into 46.6g oil phase and 308.3g aqueous phase.The sodium chloride concentration of the aqueous phase be separated is 0.2%, even if recycling aqueous phase, sodium-chlor also can not thicken, and therefore, can recycle when obtaining the composition containing chloropharin ether (A).
Embodiment 2
Except adding 12.0g sodium-chlor and 438.0g ion exchanged water in 150.0g composition (A1), thus the composition (A) (containing 106.5g chloropharin ether) obtained containing chloropharin ether, and in operation 1, the described composition (A) containing chloropharin ether is under agitation made it with pump the logical liquid that circulates in the region 1 of electrodialysis, and other all similarly carries out the electrodialysis reaction of 2 hours with embodiment 1.The integrating electric amount of circulation is 12.0Ah, and average current density is 1000A/m
2, the liquid temperature in region 1 is the scope of 15 ~ 40 DEG C.
After reaction, obtain 332.8g composition (B) in zone 1.Composition (B) is carried out composition analysis by vapor-phase chromatography, found that the 49.7g in the chloropharin ether of the composition (A) containing chloropharin ether transforms to 2-hexyl glycidyl ether, do not use alkaline agent also can carry out conversion reaction.In addition, in region 2,645g1.8% hydrochloric acid is obtained.
Left standstill at 15 DEG C by composition (B), result easily can be separated into 116.5g oil phase and 216.3g aqueous phase.The sodium chloride concentration of the aqueous phase be separated is 0.2%, even if recycling aqueous phase, sodium-chlor also can not thicken, and therefore, can recycle when obtaining the composition containing chloropharin ether (A).
Embodiment 3
Except adding 12.0g sodium-chlor and 378.0g ion exchanged water in 210.0g composition (A1), thus the composition (A) (containing 149.1g chloropharin ether) obtained containing chloropharin ether, and in operation 1, the described composition (A) containing chloropharin ether is under agitation made it with pump the logical liquid that circulates in the region 1 of electrodialysis, and other all similarly carries out the electrodialysis reaction of 2 hours with embodiment 1.Integrating electric amount is all 12.0Ah, and average current density is 1000A/m
2, the liquid temperature in region 1 is the scope of 15 ~ 40 DEG C.
After reaction, obtain 319.8g composition (B) in zone 1.Composition (B) is carried out composition analysis by vapor-phase chromatography, found that the 54.8g in the chloropharin ether of the composition (A) containing chloropharin ether transforms to 2-hexyl glycidyl ether, do not use alkaline agent also can carry out conversion reaction.In addition, in region 2,635g1.8% hydrochloric acid is obtained.
Left standstill at 15 DEG C by composition (B), result easily can be separated into 163.1g oil phase and 156.7g aqueous phase.The sodium chloride concentration of the aqueous phase be separated is 0.2%, even if recycling aqueous phase, sodium-chlor also can not thicken, and therefore, can recycle when obtaining the composition containing chloropharin ether (A).
Embodiment 4
Except adding 12.0g sodium-chlor and 288.0g ion exchanged water in 300.0g composition (A1), thus the composition (A) (containing 213.0g chloropharin ether) obtained containing chloropharin ether, and in operation 1, the described composition (A) containing chloropharin ether is under agitation made it with pump the logical liquid that circulates in the region 1 of electrodialysis, and other all similarly carries out the electrodialysis reaction of 2 hours with embodiment 1.The integrating electric amount of circulation is 11.4Ah, and average current density is 1000A/m
2, the liquid temperature in region 1 is the scope of 15 ~ 40 DEG C.
After reaction, obtain 311.0g composition (B) in zone 1.Composition (B) is carried out composition analysis by vapor-phase chromatography, found that the 61.1g in the chloropharin ether of the composition (A) containing chloropharin ether transforms to 2-hexyl glycidyl ether, do not use alkaline agent also can carry out conversion reaction.In addition, in region 2,638g1.7% hydrochloric acid is obtained.
Left standstill at 15 DEG C by composition (B), result easily can be separated into 233.0g oil phase and 78.0g aqueous phase.The sodium chloride concentration of the aqueous phase be separated is 0.2%, even if recycling aqueous phase, sodium-chlor also can not thicken, and therefore, can recycle when obtaining the composition containing chloropharin ether (A).
Embodiment 5
Except adding 12.0g sodium-chlor and 228.0g ion exchanged water in 360.0g composition (A1), thus the composition (A) (containing 255.6g chloropharin ether) obtained containing chloropharin ether, and in operation 1, the described composition (A) containing chloropharin ether is under agitation made it with pump the logical liquid that circulates in the region 1 of electrodialysis, and other all similarly carries out the electrodialysis reaction of 2 hours with embodiment 1.The integrating electric amount of circulation is 9.8Ah, and average current density is 450 ~ 1000A/m
2, the liquid temperature in region 1 is the scope of 15 ~ 40 DEG C.
After reaction, obtain 369.3g composition (B) in zone 1.Composition (B) is carried out composition analysis by vapor-phase chromatography, found that the 60.0g in the chloropharin ether of the composition (A) containing chloropharin ether transforms to 2-hexyl glycidyl ether, do not use alkaline agent also can carry out conversion reaction.In addition, in region 2,596g1.5% hydrochloric acid is obtained.
Left standstill at 15 DEG C by composition (B), result easily can be separated into 305.0g oil phase and 60.0g aqueous phase.The sodium chloride concentration of the aqueous phase be separated is 0.7%, even if recycling aqueous phase, sodium-chlor also can not thicken, and therefore, can recycle when obtaining the composition containing chloropharin ether (A).
Embodiment 6
Except adding 12.0g sodium-chlor and 138.0g ion exchanged water in 450.0g composition (A1), thus the composition (A) (containing 319.5g chloropharin ether) obtained containing chloropharin ether, and in operation 1, the described composition (A) containing chloropharin ether is under agitation made it with pump the logical liquid that circulates in the region 1 of electrodialysis, and other all similarly carries out the electrodialysis reaction of 2 hours with embodiment 1.The integrating electric amount of circulation is 5.5Ah, and average current density is 290 ~ 910A/m
2, the liquid temperature in region 1 is the scope of 15 ~ 40 DEG C.
After reaction, obtain 392.4g composition (B) in zone 1.Composition (B) is carried out composition analysis by vapor-phase chromatography, found that the 46.9g in the chloropharin ether of the composition (A) containing chloropharin ether transforms to 2-hexyl glycidyl ether, do not use alkaline agent also can carry out conversion reaction.In addition, in region 2,567g1.0% hydrochloric acid is obtained.
Left standstill at 15 DEG C by composition (B), result easily can be separated into 349.5g oil phase and 42.9g aqueous phase.The sodium chloride concentration of the aqueous phase be separated is 0.7%, even if recycling aqueous phase, sodium-chlor also can not thicken, and therefore, can recycle when obtaining the composition containing chloropharin ether (A).
Embodiment 7
Except adding the aqueous portion that composition (B) multi_layer extraction in embodiment 4 obtains by 12.0g sodium-chlor and 210.0g ion exchanged water and 78.0g in 300.0g composition (A1), thus the composition (A) (containing 213.0g chloropharin ether) obtained containing chloropharin ether, and in operation 1, the described composition (A) containing chloropharin ether is under agitation made it with pump the logical liquid that circulates in the region 1 of electrodialysis, and other all similarly carries out the electrodialysis reaction of 2 hours with embodiment 1.The integrating electric amount of circulation is 11.6Ah, and average current density is 1000A/m
2, the liquid temperature in region 1 is the scope of 15 ~ 40 DEG C.
After reaction, obtain 307.1g composition (B) in zone 1.Composition (B) is carried out composition analysis by vapor-phase chromatography, found that the 62.6g in the chloropharin ether of the composition (A) containing chloropharin ether transforms to 2-hexyl glycidyl ether, do not use alkaline agent also can carry out conversion reaction.In addition, in region 2,640g1.8% hydrochloric acid is obtained.
Left standstill at 15 DEG C by composition (B), result easily can be separated into 233.0g oil phase and 74.1g aqueous phase.The sodium chloride concentration of the aqueous phase be separated is 0.2%, even if recycling aqueous phase, sodium-chlor also can not thicken, and can also recycle further when obtaining the composition containing chloropharin ether (A).
By in embodiment 1 ~ 7 electrodialysis reaction condition and the results are shown in table 1.
Comparative example 1
250.0g composition (A1) is adjusted to 40 DEG C, under agitation adds 48% sodium hydroxide and the 156.5g ion exchanged water of 93.5g, after carrying out reaction in 3 hours, obtain 500g composition (B).
Composition (B) is left standstill at 15 DEG C, result easily can be separated into the oil phase of 197.9g and the aqueous phase of 226.0g, but, sodium chloride concentration in aqueous phase is up to 12.3%, when recycling aqueous phase, if with removing sodium-chlor someway, then concentration obviously thickens, therefore can not recycle aqueous phase, become waste water.
Claims (30)
1. a manufacture method for alkyl glycidyl ether, wherein,
Comprise following operation 1 and operation 2,
Operation 1: by the region 1 of electrodialysis with following region 1 and 2, import containing concentration be the chloropharin ether of more than 5 % by weight, the composition (A) of ionogen and water galvanic current is energized, thus in zone 1 chloropharin ether transformed to alkyl glycidyl ether and obtain composition (B), make the chlorion (Cl that by-product is raw in zone 1 simultaneously
-) moved in region 2 so that the operation being separated as hydrochloric acid, reclaiming by anion-exchange membrane, below, by containing concentration be more than 5 % by weight chloropharin ether, ionogen and water composition (A) also referred to as the composition (A) containing chloropharin ether
Region 1: the region delimited between anion-exchange membrane and the anion-exchange membrane side of the 1st Bipolar Membrane,
Region 2: adjacent with region 1 across the described anion-exchange membrane of defined area 1, and the region delimited between above-mentioned anion-exchange membrane and the cationic exchange membrane side of the 2nd Bipolar Membrane;
Operation 2: by composition (B) layering obtained in operation 1, is separated into the operation of oil phase layer containing alkyl glycidyl ether and aqueous phase layer.
2. manufacture method as claimed in claim 1, wherein,
The described composition (A) containing chloropharin ether is the composition containing the chloropharin ether making alcohol and Epicholorohydrin be obtained by reacting in the presence of a catalyst.
3. manufacture method as described in claim 2, wherein,
The alcohol of alcohol according to claim 2 represented by following general formula (I),
R-OH(I)
In formula, R represents that carbonatoms is the straight chain of 3 ~ 22, the alkyl of side chain or ring-type or thiazolinyl.
4. the manufacture method according to any one of claims 1 to 3, wherein,
The chloropharin ether concentration of the composition (A) containing chloropharin ether is 5 ~ 70 % by weight.
5. the manufacture method according to any one of claims 1 to 3, wherein,
In operation 1, the concentration of the oil-phase component in the composition (A) containing chloropharin ether is 10 ~ 90 % by weight.
6. the manufacture method according to any one of claims 1 to 3, wherein,
Part or all of water and eletrolytes of the aqueous phase layer obtained in operation 2 as the composition (A) formed containing chloropharin ether is used.
7. the manufacture method according to any one of claims 1 to 3, wherein,
The electrolyte concentration of the composition (A) containing chloropharin ether is 0.01 ~ 30 % by weight.
8. the manufacture method according to any one of claims 1 to 3, wherein,
The concentration of hydrochloric acid being separated in region 2, reclaiming of operation 1 is 0.1 ~ 35 % by weight.
9. the manufacture method according to any one of claims 1 to 3, wherein,
In operation 1, the current density of the galvanic current of energising is 50 ~ 1500A/m
2.
10. manufacture method as claimed in claim 2, wherein,
In the manufacture of the Epicholorohydrin used when obtaining the composition containing chloropharin ether (A), the hydrochloric acid being separated in region 2, reclaiming of operation 1 is recycled.
11. manufacture method according to any one of claims 1 to 3,10, wherein,
The electrolyte concentration of the water layer obtained by the layering of composition (B) is 0.1 ~ 20 % by weight.
12. manufacture method according to any one of claims 1 to 3,10, wherein,
Composition/electrolytical the weight ratio be directed in region 2 be directed in region 1 is 0.1 ~ 10.
13. manufacture method as claimed in claim 3, wherein,
Alcohol represented by general formula (I) be in general formula (I) R to be carbonatoms be 5 ~ 12 straight chain, side chain or the alkyl of ring-type or the alcohol of thiazolinyl.
14. manufacture method as claimed in claim 3, wherein,
Alcohol represented by general formula (I) be in general formula (I) R to be carbonatoms be 8 ~ 12 straight chain, side chain or the alkyl of ring-type or the alcohol of thiazolinyl.
15. manufacture method as claimed in claim 3, wherein,
Alcohol represented by general formula (I) is that in general formula (I), R is the alcohol of alkyl.
16. manufacture method as claimed in claim 3, wherein,
In general formula (I), R is straight chain or side chain.
17. manufacture method as claimed in claim 3, wherein,
Alcohol represented by general formula (I) is butanols, amylalcohol, octanol, 2-Ethylhexyl Alcohol, decyl alcohol, dodecanol.
18. manufacture method as claimed in claim 3, wherein,
Alcohol represented by general formula (I) is amylalcohol, octanol, 2-Ethylhexyl Alcohol, decyl alcohol, dodecanol.
19. manufacture method as claimed in claim 3, wherein,
Alcohol represented by general formula (I) is octanol, 2-Ethylhexyl Alcohol, decyl alcohol, dodecanol.
20. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
The chloropharin ether concentration of the composition (A) containing chloropharin ether is 10 ~ 65 % by weight.
21. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
The chloropharin ether concentration of the composition (A) containing chloropharin ether is 25 ~ 65 % by weight.
22. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
The chloropharin ether concentration of the composition (A) containing chloropharin ether is 35 ~ 65 % by weight.
23. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
The chloropharin ether concentration of the composition (A) containing chloropharin ether is 40 ~ 55 % by weight.
24. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
Relative to the composition (A) containing chloropharin ether, the concentration forming the oil-phase component of oil phase layer is 20 ~ 80 % by weight.
25. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
Relative to the composition (A) containing chloropharin ether, the concentration forming the oil-phase component of oil phase layer is 35 ~ 75 % by weight.
26. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
The electrolyte concentration of the composition (A) containing chloropharin ether is 0.1 ~ 10 % by weight.
27. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
The electrolyte concentration of the composition (A) containing chloropharin ether is 1 ~ 5 % by weight.
28. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
The concentration of hydrochloric acid being separated in region 2, reclaiming of operation 1 is 0.5 ~ 20 % by weight.
29. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
In operation 1, the current density of the galvanic current of energising is 100 ~ 1200A/m
2.
30. manufacture method according to any one of claims 1 to 3,10 and 13 ~ 19, wherein,
The electrolyte concentration of the water layer obtained by the layering of composition (B) is 0.1 ~ 10 % by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010138900 | 2010-06-18 | ||
| JP2010-138900 | 2010-06-18 | ||
| PCT/JP2011/063761 WO2011158891A1 (en) | 2010-06-18 | 2011-06-16 | Method for producing alkylglycidyl ether |
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| CN102971450A CN102971450A (en) | 2013-03-13 |
| CN102971450B true CN102971450B (en) | 2016-01-06 |
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| JP (1) | JP5103545B2 (en) |
| CN (1) | CN102971450B (en) |
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| JP6004962B2 (en) * | 2012-02-16 | 2016-10-12 | 花王株式会社 | Method for producing epoxy compound |
| CN109721569B (en) * | 2017-10-30 | 2022-07-15 | 中国石油化工股份有限公司 | Preparation method of epichlorohydrin |
| CN109721572B (en) * | 2017-10-30 | 2022-07-15 | 中国石油化工股份有限公司 | Preparation method of epichlorohydrin |
| CN109721570B (en) * | 2017-10-30 | 2022-07-15 | 中国石油化工股份有限公司 | Method for producing epoxy chloropropane |
| CN109721573B (en) * | 2017-10-30 | 2022-07-12 | 中国石油化工股份有限公司 | Synthetic method of epichlorohydrin |
| CN109721574B (en) * | 2017-10-30 | 2022-07-15 | 中国石油化工股份有限公司 | Epichlorohydrin production method and epichlorohydrin production system |
| CN109721571B (en) * | 2017-10-30 | 2022-07-15 | 中国石油化工股份有限公司 | Epichlorohydrin production method and epichlorohydrin production system |
| CN108889129A (en) * | 2018-08-29 | 2018-11-27 | 湖北世星能源科技有限公司 | Combination drive nanofiltration membrane component and well mine salt salt producing craft |
| CN112516808A (en) * | 2020-12-31 | 2021-03-19 | 山东天维膜技术有限公司 | Preparation method of cross-linked bipolar membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6167783A (en) * | 1984-09-07 | 1986-04-07 | Kao Corp | Production of glycidyl quaternary ammonium salt |
| JPS61139690A (en) * | 1984-12-10 | 1986-06-26 | Kao Corp | Production of quaternary glycidylammonium salt |
| US5980724A (en) * | 1998-07-09 | 1999-11-09 | Ppg Industries Ohio, Inc. | Method of electrochemically producing epoxides |
-
2011
- 2011-06-15 JP JP2011132810A patent/JP5103545B2/en active Active
- 2011-06-16 MY MYPI2012701180A patent/MY160901A/en unknown
- 2011-06-16 CN CN201180029328.0A patent/CN102971450B/en active Active
- 2011-06-16 WO PCT/JP2011/063761 patent/WO2011158891A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6167783A (en) * | 1984-09-07 | 1986-04-07 | Kao Corp | Production of glycidyl quaternary ammonium salt |
| JPS61139690A (en) * | 1984-12-10 | 1986-06-26 | Kao Corp | Production of quaternary glycidylammonium salt |
| US5980724A (en) * | 1998-07-09 | 1999-11-09 | Ppg Industries Ohio, Inc. | Method of electrochemically producing epoxides |
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| JP2012021228A (en) | 2012-02-02 |
| WO2011158891A1 (en) | 2011-12-22 |
| MY160901A (en) | 2017-03-31 |
| JP5103545B2 (en) | 2012-12-19 |
| CN102971450A (en) | 2013-03-13 |
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