CN101210007B - Method for preparing ethylene sulfite - Google Patents
Method for preparing ethylene sulfite Download PDFInfo
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- CN101210007B CN101210007B CN2006101562016A CN200610156201A CN101210007B CN 101210007 B CN101210007 B CN 101210007B CN 2006101562016 A CN2006101562016 A CN 2006101562016A CN 200610156201 A CN200610156201 A CN 200610156201A CN 101210007 B CN101210007 B CN 101210007B
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Abstract
The invention relates to a preparation method of ethylene sulfite, which comprises that epoxy ethane and sulfur dioxide are subject to contact reaction with the existence of catalyst. The catalyst is halide of aluminum. The method for preparing the ethylene sulfite provided by the invention carries out reaction under the condition of halide catalysis of the catalyst aluminum, thus greatly improving the yield of the resultant ethylene sulfite.
Description
Technical field
The invention relates to a kind of preparation method of ethylene sulfite.
Background technology
Ethylene sulfite is a kind of important organic chemical industry's product, is used as the intermediate of synthetic other Chemicals etc.Ethylene sulfite also is a kind of good electrolyte of lithium-ion secondary battery solvent or electrolysis additive, and it can form good SEI film between battery cathode and electrolysis liquid phase, therefore can greatly improve the various performances of battery.Flourish along with the lithium ion battery industry, more and more higher to the requirement of battery performance, ethylene sulfite is as a kind of excellent solvent or additive, to its also corresponding increase of demand.
At present, the method that is used to prepare ethylene sulfite has a variety of, for example, can prepare by the reaction of ethylene glycol and sulfur oxychloride, but sulfur oxychloride toxicity is very big in this method, and this byproduct of reaction is more in addition, the aftertreatment purification difficult.Especially when ethylene sulfite is used as lithium-ion battery electrolytes solvent or electrolysis additive, its requirement to impurity is very high, and contain more by product chloroethanol in the ethylene sulfite that obtains by this prepared in reaction, and chloroethanol can greatly influence electrolytical stability in storage in the electrolytic solution, thereby can influence the stability of lithium-ion secondary cell.And the content that will reduce chloroethanol in the ethylene sulfite will be a process that complexity is time-consuming.
In addition, also have reaction to prepare, but this method exist speed of reaction slow by ethylene glycol and dimethyl sulfite, the problem that reaction yield is low, even under the condition that catalyzer exists, reaction yield is still very low.For example, CN 1803767A discloses a kind of method for preparing ethylene sulfite, it is characterized in that, this method is a raw material with dimethyl sulfite and ethylene glycol, is catalyzer with the toluenesulphonic acids, and catalyst consumption is the 0.01%-5% of reactant weight; In reaction process, progressively be warming up to 160-180 ℃ from 60-70 ℃, constantly remove the methyl alcohol that generates in the reaction process simultaneously; And the further fractionation purification of warp obtains highly purified ethylene sulfite.This catalysts consumption is less, and directly carry out the reacting phase ratio with traditional ethylene glycol and dimethyl sulfite, on speed of reaction, be greatly improved, but still there is the lower problem of reaction yield in this method, for example, the yield of the ethylene sulfite that makes by this inventive embodiments only is about 56%.
In addition, also having mentioned with oxyethane and sulfurous gas in the prior art is raw material, at high temperature, carries out the prepared in reaction ethylene sulfite under the high pressure under the condition that catalyzer exists.Described catalyzer for example has alkali metal halide, the halogenide of alkaline earth metal halide and iron, cobalt, nickel.But these methods all exist operational condition to require the problem that by product is more, yield is lower high, that generate.
Summary of the invention
Purpose of the present invention provides the preparation method of the high ethylene sulfite of a kind of yield for the low shortcoming of yield of ethylene sulfite among the preparation method of the ethylene sulfite that overcomes prior art.
The invention provides a kind of preparation method of ethylene sulfite, this method is included in catalyzer and exists down, and with oxyethane and sulfurous gas contact reacts, wherein, described catalyzer is the halogenide of aluminium.
The preparation method of ethylene sulfite provided by the invention is by reacting under the catalytic condition of the halogenide of catalyzer aluminium, increased substantially the yield of reaction product ethylene sulfite, for example, the yield of ethylene sulfite is all more than 90% among the preparation method of the present invention, and the method for employing prior art, the yield of ethylene sulfite only is 65.4%.In addition, side reaction is less among the preparation method of ethylene sulfite of the present invention, impurity in products content is low, and the purity of ethylene sulfite is all more than 98% in the thick product that makes, and the purity of ethylene sulfite is 96.5% in the thick product that prior art makes.
In addition, method catalyst levels provided by the invention is few, cheap and easy to get, and reaction conditions requires low, is fit to large-scale industrial production.
Embodiment
The preparation method of ethylene sulfite provided by the invention is included in catalyzer and exists down, with oxyethane and sulfurous gas contact reacts.Catalyzer of the present invention is the halogenide of aluminium.The halogenide of described aluminium for example, can be in aluminum trifluoride, aluminum chloride, alchlor or the aluminium triiodide one or more, and the halogenide of described aluminium is preferably aluminum chloride.The halid consumption of aluminium of the present invention is at least 0.05 weight % of epoxy hexane, and the halid consumption of aluminium is very few, and catalytic effect is bad.The upper limit to the halid consumption of described aluminium does not have special restriction, but the halid consumption of aluminium does not too much have further raising to the contact speed of reaction on the one hand, the too much corresponding cost of the halid consumption of aluminium also improves in addition, and the purity of reduction reaction product, therefore, the halid consumption of described aluminium is preferably the 0.05-5 weight % of epoxy hexane, more preferably 0.1-1 weight %.
Because reactant sulfurous gas and epoxy hexane are gaseous state at normal temperatures, therefore, the halogenide of described aluminium dispersity in reaction system is not high, but along with progressively carrying out of reaction, after generating a large amount of ethylene sulfites, the halide based of described aluminium originally scatter, thereby makes its performance effect more fully.But, because the generation of ethylene sulfite must need certain hour, it is slower that this will certainly cause reacting the initial stage speed of reaction, therefore, under the preferable case, the halogenide of the described aluminium of halogenide of aluminium of the present invention exists with the form of the halid dispersion liquid of aluminium, participate in catalyzed reaction, the halid dispersion liquid of described aluminium contains the halogenide and the dispersion agent of aluminium, described dispersion agent be in a liquid state under the normal temperature and not with the solvent of described oxyethane or sulfurous gas reaction, in addition, this solvent is easy and the isolating solvent of ethylene sulfite, it for example can be ethylene sulfite, carbonatoms is the alcohols of 1-4, tetrahydrofuran (THF), sherwood oil, or in the toluene one or more, in order to reduce the foreign matter content in the product, and be convenient to the subsequent products fractionation, described dispersion agent is preferably ethylene sulfite, the consumption of described dispersion agent be aluminium halid consumption 100-1500 doubly.
According to the present invention, the catalytic temperature of described oxyethane and sulfurous gas can be 50-300 ℃, and suitable elevated temperature helps reaction to carry out to positive dirction, improves reaction-ure conversion-age, but the also corresponding raising of the too high requirement of temperature to production unit.Therefore the catalytic temperature of preferred described sulfurous gas of the present invention and epoxy hexane is 100-250 ℃.The pressure of described sulfurous gas can be more than 1 MPa, but pressure is excessive, and to the also corresponding raising of the requirement of production unit, therefore the pressure of preferred described sulfurous gas is the 1-10 MPa, more preferably the 2-8 MPa.The present invention remains at sulfurous gas under the condition of above-mentioned pressure, and described epoxy hexane can continuously feeding.
The catalytic time of the present invention is according to the difference of reactant concn, reaction pressure, warm isocratic condition and difference.Generally, reactant concn is high more, and the reaction times is also short relatively more; Reaction pressure is high more or temperature of reaction is high more, the also corresponding quickening of speed of response, and the reaction times that reaches same transformation efficiency is short more.The catalytic time of the present invention can be more than 0.5 hour.But the catalytic time is too short, and reaction conversion ratio is too low, and the time is oversize, and various side reactions take place easily, and therefore, the described catalytic time is preferably 1-10 hour.
Contact reacts of the present invention can be carried out in the reaction vessel that can satisfy the required condition of reaction arbitrarily, for example, can carry out described reaction in autoclave.Owing to always there is air in the reaction vessel, the increase of side reaction during it can cause reacting, foreign matter content raises in the product thereby make, therefore, under the preferable case, before the contact reacts of described oxyethane and sulfurous gas, with the air in the inert gas replacement reaction vessel, described rare gas element can be one or more in helium, neon, argon gas, krypton gas, radon gas or the nitrogen earlier.Under situation, also can come air in the replacement(metathesis)reaction container with sulfurous gas with reactant sulfurous gas conditioned reaction pressure.In addition, in order to react fully, the present invention preferably under agitation carries out contact reacts, and described stirring method can be conventional method, for example, can be induction stirring etc.
In addition, according to preparation method provided by the invention, can also comprise and separate purification contacting reacted product.The method that described separation is purified can be conventional the whole bag of tricks.Therefore boiling point owing to the product ethylene sulfite among the present invention will just can obtain highly purified ethylene sulfite by the distillatory method at an easy rate far above the boiling point of reactant.
The present invention adopts the mode of gas-matter coupling (GC-MS) to judge the generation and the purity thereof of ethylene sulfite.Used gas chromatograph-mass spectrometer is that the model that U.S. Hewlett Packard produces is the gas chromatograph-mass spectrometer of HP5890, and helium is carrier gas.
Below by embodiment method of the present invention is described further.
Embodiment 1
Present embodiment is used to illustrate the preparation method of ethylene sulfite provided by the invention.
(Dalian Ke Mao experimental installation company, model: FCZ0.4L), add 108 gram ethylene sulfites, 0.1 restrains aluminum trichloride (anhydrous) to the autoclave that stirs at 400 milliliters of charged magnetic, and 100 gram oxyethane are opened induction stirring.The heat temperature raising reaction mixture when temperature of reaction is raised to 130 ℃, feeds sulfurous gas to 5 MPa, and kept this temperature, stress reaction 1 hour then.Logical water coolant in autoclave is cooled to 50 ℃ then, emits product in the still, weighs to such an extent that thick product ethylene sulfite 348.6 restrains, and recording purity is 98.09%.The thick product of gained is carried out the vacuum decompression distillation, collect 172-174 ℃ cut, get ethylene sulfite 342.4 grams, purity is 99.5%, and the yield of ethylene sulfite is 95.5%.Product is carried out GC-MS analyze, recording purity is 99.5% ethylene sulfite product, and the peak of appearance 108 is the molecular ion peak of ethylene sulfite in the MS spectrogram, proves that further products therefrom is an ethylene sulfite.
Comparative Examples 1
The preparation method of the ethylene sulfite that this Comparative Examples is used to illustrate that prior art provides.
In the autoclave that 400 milliliters of charged magnetic stir, add 108 gram ethylene sulfites, 0.1 gram catalyzer potassiumiodide, 100 gram oxyethane are opened induction stirring.The heat temperature raising reaction mixture when temperature of reaction is raised to 130 ℃, feeds sulfurous gas to 5 MPa, and kept this temperature, stress reaction 1 hour then.Logical water coolant in autoclave is cooled to 50 ℃ then, emits product in the still, weighs to such an extent that thick product ethylene sulfite 274.4 restrains, and recording purity is 96.50%.The thick product of gained is carried out the vacuum decompression distillation, collect 172-174 ℃ cut, get ethylene sulfite 268.6 grams, recording purity is 98.8%, and the yield of ethylene sulfite is 65.4%.
Embodiment 2
Present embodiment is used to illustrate the preparation method of ethylene sulfite provided by the invention.
In the autoclave of 400 milliliters of charged magnetic stirrings, add 108 gram ethylene sulfites, the anhydrous alchlor of 0.3 gram is used N
2Add 100 gram oxyethane behind the air in the displacement autoclave again, open induction stirring.The heat temperature raising reaction mixture when temperature of reaction is raised to 190 ℃, feeds sulfurous gas to 4 MPa, and kept this temperature, stress reaction 3 hours then.Logical water coolant in autoclave is cooled to 50 ℃ then, emits product in the still, weighs to such an extent that thick product ethylene sulfite 349.3 restrains, and recording purity is 98.60%.The thick product of gained is carried out the vacuum decompression distillation, collect 172-174 ℃ cut, get ethylene sulfite 343.5 grams, recording purity is 99.7%, and the yield of ethylene sulfite is 96.0%.
Embodiment 3
Present embodiment is used to illustrate the preparation method of ethylene sulfite provided by the invention.
In the autoclave of 400 milliliters of charged magnetic stirrings, add 108 gram ethylene sulfites, the anhydrous aluminium triiodide of 0.5 gram is used N
2Add 100 gram oxyethane behind the air in the displacement autoclave again, open induction stirring.The heat temperature raising reaction mixture when temperature of reaction is raised to 120 ℃, feeds sulfurous gas to 2 MPa, and kept this temperature, stress reaction 6 hours then.Logical water coolant in autoclave is cooled to 50 ℃ then, emits product in the still, weighs to such an extent that thick product ethylene sulfite 345.1 restrains, and recording purity is 98.20%.The thick product of gained is carried out the vacuum decompression distillation, collect 172-174 ℃ cut, get ethylene sulfite 339.2 grams, recording purity is 99.6%, and the yield of ethylene sulfite is 94.2%.
Embodiment 4
Present embodiment is used to illustrate the preparation method of ethylene sulfite provided by the invention.
In the autoclave of 400 milliliters of charged magnetic stirrings, add 0.8 gram aluminum trichloride (anhydrous), use N
2Add 100 gram oxyethane behind the air in the displacement autoclave again, open induction stirring.The heat temperature raising reaction mixture when temperature of reaction is raised to 120 ℃, feeds sulfurous gas to 6 MPa, and kept this temperature, stress reaction 7 hours then.Logical water coolant in autoclave is cooled to 50 ℃ then, emits product in the still, weighs to such an extent that thick product ethylene sulfite 227.5 restrains, and recording purity is 98.10%.The thick product of gained is carried out the vacuum decompression distillation, collect 172-174 ℃ cut, get ethylene sulfite 221.6 grams, recording purity is 99.6%, and the yield of ethylene sulfite is 90.2%.
Claims (8)
1. the preparation method of an ethylene sulfite, this method is included in catalyzer and exists down, with oxyethane and sulfurous gas contact reacts, it is characterized in that, described catalyzer is the halogenide of aluminium, the catalytic temperature of described oxyethane and sulfurous gas is 50-300 ℃, and the catalytic time is at least 0.5 hour, and the pressure of described sulfurous gas is the 1-10 MPa.
2. method according to claim 1, wherein, the halid consumption of described aluminium is at least 0.05 weight % of epoxy hexane.
3. method according to claim 2, wherein, the halid consumption of described aluminium is the 0.1-1 weight % of epoxy hexane.
4. according to any described method among the claim 1-3, wherein, the halogenide of described aluminium is one or more in aluminum trifluoride, aluminum chloride, alchlor or the aluminium triiodide.
5. method according to claim 1, wherein, the catalytic temperature of described oxyethane and sulfurous gas is 100-250 ℃, and the catalytic time is 1-10 hour, and the pressure of described sulfurous gas is the 2-8 MPa.
6. method according to claim 1, wherein, the halogenide of described aluminium exists with the form of the halid dispersion liquid of aluminium, the halid dispersion liquid of described aluminium contains the halogenide and the dispersion agent of aluminium, described dispersion agent is that ethylene sulfite, carbonatoms are one or more in alcohols, tetrahydrofuran (THF), sherwood oil and the toluene of 1-4, the consumption of described dispersion agent be aluminium halid consumption 100-1500 doubly.
7. method according to claim 1 wherein, before the contact reacts of described oxyethane and sulfurous gas, earlier goes out air in the reaction vessel with inert gas replacement.
8. method according to claim 7, wherein, described rare gas element is one or more in nitrogen, helium, neon, argon gas, krypton gas and the xenon.
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| CN2006101562016A CN101210007B (en) | 2006-12-31 | 2006-12-31 | Method for preparing ethylene sulfite |
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| CN2006101562016A CN101210007B (en) | 2006-12-31 | 2006-12-31 | Method for preparing ethylene sulfite |
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| CN101210007B true CN101210007B (en) | 2011-06-15 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101747315A (en) * | 2008-12-08 | 2010-06-23 | 中国科学院福建物质结构研究所 | Catalytic ester exchange synthetic method of propylene sulfite and purification method |
| CN109485632B (en) * | 2017-09-13 | 2021-05-07 | 山东石大胜华化工集团股份有限公司 | Method for preparing cyclic sulfite |
| CN115745952B (en) * | 2022-11-29 | 2024-05-31 | 香河昆仑新能源材料股份有限公司 | Preparation method of ethylene sulfite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2833785A (en) * | 1954-10-21 | 1958-05-06 | Huels Chemische Werke Ag | Process for the production of glycol sulfite |
| CN1343200A (en) * | 1999-02-03 | 2002-04-03 | Basf公司 | Method for producing alkanesulfonic acids |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2833785A (en) * | 1954-10-21 | 1958-05-06 | Huels Chemische Werke Ag | Process for the production of glycol sulfite |
| CN1343200A (en) * | 1999-02-03 | 2002-04-03 | Basf公司 | Method for producing alkanesulfonic acids |
Non-Patent Citations (1)
| Title |
|---|
| Zbigniew Florjanczyk,Dorota Raducha.Copolymerization of ethylene oxide and sulfur dioxide initiated by Lewis bases.Makromol. Chem..1993,194(9),2605-2613. * |
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