TWI313260B - - Google Patents

Description

TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a method for producing an alkene derivative such as an alkanediol or an alkanediol, and in particular relates to the use of iodized and/or brominated four-dimensional money touches. A method in which an epoxide such as ethylene oxide is reacted with water in the presence of carbon dioxide to produce an alkanediol such as ethylene glycol, or an epoxide is reacted with cerium oxide to produce a vinyl carbonate or the like. The method, in particular, is an efficient recovery of the iodide and/or brominated quaternary recycle from the reaction system.

In the present invention, the alkanediol means, for example, an alkanediol having 2 to 10 carbon atoms such as ethylene glycol or propylene glycol, and an alkylene carbonate means, for example, a carbon number of ethylene carbonate such as propylene carbonate to 2 Approximately 10 alkyl carbonates. [Prior Art] Ethylene glycol is a large-scale production process in which ethylene oxide (ethylene oxide) is directly reacted with water and hydrolyzed, and this method suppresses by-products such as diethylene glycol and S glycol. Water that is much larger than stoichiometry must be used relative to ethylene oxide. Therefore, the aqueous ethylene glycol solution to be distilled is used to remove a large amount of excess water to obtain purified ethylene glycol, which is a problem of a large amount of energy. A solution to this problem is a proposal for a method of producing ethylene glycol by reacting water with ethylene oxide in the presence of carbon dioxide. This reaction is a two-stage reaction in which ethylene oxide reacts with carbon dioxide to form ethylene carbonate, which is hydrolyzed by ethylene carbonate to form ethylene glycol. The two-stage reaction may be carried out in the same reactor due to the presence of water in the reaction system, and the second stage of the reaction may be carried out. -4 - (2) All of the reactors may be provided in the latter stage. The hydrolysis of ethylene carbonate is a by-product of a few ethylene glycols such as triethylene glycol, and the hydrolysis can be carried out by using a slightly excess amount of water than the stoichiometric amount of water. Less. Hydrolysis of ethylene carbonate formed by the reaction of ethylene oxide with carbon dioxide produces carbon dioxide which is recycled for reuse. Further, in this method, ethylene carbonate can be produced by lowering the reaction conditions and reducing the amount of the raw material water to suppress the amount of ethylene glycol formed. As a catalyst for the production of ethylene glycol and/or ethylene carbonate from ethylene oxide, there have been various proposals, one of which is preferably an organic money salt, and a particularly good one is iodinated or brominated.鋳 (Japanese Patent Publication No. 5 5 - 4 7 6 1 7). Further, in such an organic money salt, an alkali metal carbonate can also be used as a promoter (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. The ethylene oxide of the raw material is produced by the oxidation of ethylene. In this case, the selectivity of the oxidation reaction is increased, and the chlorine gas such as ethyl chloride is supplied as a selectivity adjuster in the reaction system (Special Kaiping 2 - 1 0 4 5 7 Bulletin No. 9). A method for producing ethylene glycol or ethylene carbonate by reacting ethylene oxide with water or with carbon dioxide in the presence of carbon dioxide, as described above, is an industrially advantageous method without the problem of by-products, but the reaction continues The problem of reduced reaction efficiency. The inventors of the present invention have investigated the reason for the decrease in the efficiency of the reaction. As a result, it has been found that the reason is that the iodinated or brominated tetradecene catalyst in the reaction system is converted into a chloride having low catalytic activity. In fact, after about one year of operation of the equipment, about 20% by weight of the iodinated or brominated quaternary catalyst in the reaction system is converted into chlorinated quaternary scales. -5- 1313260 (3) The reason for the conversion of iodinated or brominated quaternary phosphonium to quaternary chlorinated tetrachloride is due to the introduction of the impurity chlorine compound contained in the raw material ethylene oxide into the reaction system. That is, as described above, in the process of ethylene oxide, in order to increase the reaction selectivity, the supply of chlorocarbon in the reaction system is used as a selectivity adjuster, and the chlorine contained in the chlorocarbon is passed through the purification system to leave the chlorine compound in the product. Ethylene oxide is then mixed into ethylene glycol or ethylene carbonate. The details of the reaction mechanism of the chlorine compound introduced by the incorporation of the product into ethylene oxide are not known, but should be converted into chlorinated quaternary scales by iodinated or brominated quaternary scales. Therefore, in the process of ethylene glycol or ethylene carbonate, it is necessary to separate the low-reactivity chlorinated quaternary acid from the catalyst of the reaction system, and only retain the highly active iodinated or brominated quaternary phosphonium. However, the long-term decline in the efficiency of the reaction has been due to the fact that the conversion to chloride over time is not clearly explained. Moreover, the method of separating the catalyst iodinated or brominated quaternary tetrachloride and quaternary chlorinated ruthenium or the method of converting quaternary phosphonium tetrachloride into iodinated or brominated quaternary ruthenium is also not discussed at all. . SUMMARY OF THE INVENTION The object of the present invention is to solve the above problems and to provide an epoxide such as ethylene oxide or a reaction with carbon dioxide by using an iodinated and/or brominated quaternary catalyst in the presence of carbon dioxide. A method for producing an alkene derivative such as an alkanediol such as ethylene glycol or an ethylene carbonate such as a vinyl carbonate, which is capable of efficiently removing a chlorinated quaternary scale formed in a reaction system, or a chlorinated four-stage The conversion of hydrazine to iodine and/or bromine quaternary recovery is used in the reaction system to maintain the catalytic activity in the reaction system, and the formation reaction of the alkene derivative is -6-(4) 1313260. The method of doing it efficiently. The gist of the present invention has the following features. (1) A method for producing a dilute derivative of a diol which is formed by using a iodinated or brominated fourth-stage scaly catalyst to react with epoxide in the presence of carbon dioxide to form a diol, which is characterized by at least a portion The reaction liquid and/or the catalyst liquid removes the alkanediol so that the molar ratio of the phase-sealing catalyst to the alkanol monool is 2 times or less, and is secondarily mixed with water to recover the catalyst. (2) The production method according to (1) above, wherein the molar ratio of the alkanediol is twice or less with respect to the catalyst. (3) The manufacturing method according to the above (!) or (2), wherein the operating temperature at the time of mixing and recovering the catalyst with water is 3 Torr or less. (4) The production method according to any one of the above (1), wherein the amount of the mixed water is more than the weight of the catalyst. (5) The production method according to any one of the above (1) to (4), wherein after mixing with water, the solid-liquid separation separates the catalyst by solids, and then circulates to the above-mentioned reaction step. (6) The production method according to (5) above, wherein the liquid separated by the solid-liquid separation is recycled as a catalyst wash water. (7) The production method according to any one of the above (1) to (6) wherein the epoxide is ethylene oxide. (8) characterized by: a reaction step of reacting an epoxide containing an impurity chlorine compound with water to form an alkanediol in the presence of carbon dioxide using an iodinated and/or brominated quaternary scale as a catalyst a mixture of chlorinated quaternary scales and iodine-7-(5) 1313260 and/or brominated tetrabases, mixed with iodide and/or bromide to convert the quaternary phosphonium chloride to iodide and/or Or a catalyst regeneration method in which quaternary tetramine is precipitated in water.

(9) characterized by: a reaction step obtained by using iodinated and/or brominated quaternary phosphonium as a catalyst to react an epoxide with carbon dioxide to form an alkylene carbonate, containing chlorinated quaternary acid and iodide and / or a mixture of brominated quaternary money 'mixed with iodide and / or bromide to convert chlorinated quaternary money into a catalyst regeneration method for iodinated and / or brominated quaternary ammonium in water. (10) The method according to the above (8) or (9), which comprises a mixture of chlorinated quaternary phosphonium chloride and iodinated and/or quaternary phosphonium bromide, which is a reaction liquid taken out from the above reaction step, or from the reaction liquid The remainder of the water and/or at least a portion of the desired alkene derivative is distilled off.

(U) The method according to the above (8) or (9), which comprises a mixture of chlorinated quaternary scales and iodinated and/or quaternary phosphonium bromide, a reaction liquid taken out from the above reaction step, or from the reaction liquid The remaining residue after distilling off at least a portion of the water and/or the target alkene derivative is mixed with water to precipitate the above-mentioned catalyst as a solid, and the separated aqueous solution. (12) The method according to any one of the above (8) to (11) wherein the iodinated and/or brominated quaternary acid which is recovered is recycled to the above reaction step. (1 3 ) characterized by: a reaction step of reacting an epoxide containing an impurity chlorine compound with water to form an alkanediol in the presence of carbon dioxide by using iodinated and/or brominated tetradecene as a catalyst a mixture of chlorinated quaternary scales and iodinated and/or quaternary phosphonium bromide, added with iodide and/or bromide to precipitate chlorine from chlorinated tetrabasic as inorganic chloride in an organic solvent -8- (6) 1313260, a catalyst regeneration method for recovering iodinated and/or brominated tetradecene. (1 4 ) characterized by the step of reacting epoxide with carbon dioxide to form ethylene carbonate by using iodinated and/or brominated quaternary money as a catalyst, containing chlorinated quaternary acid and iodide And/or a mixture of quaternary phosphonium ruthenium, adding iodide and/or bromide to precipitate chlorine from chlorinated tetradecene fluorene as an inorganic chloride in an organic solvent to recover iodinated and/or brominated quaternary money Catalyst regeneration method. (15) The method according to the above (13) or (14), which comprises a mixture of quaternary phosphonium chloride and iodinated and/or quaternary phosphonium bromide, which is any one of the following (a) to (c). (a) the reaction liquid obtained from the above reaction step is added with water to precipitate the above-mentioned catalyst, and the separated aqueous solution is dehydrated to obtain a liquid or solid, and (b) is distilled off from the reaction liquid taken from the above reaction step. a residue of at least a portion of the water and/or the target product alkene derivative, which is added with water to precipitate the catalyst as a solid, and the separated aqueous solution is dehydrated to obtain a liquid or solid, (c) A liquid obtained by dissolving a liquid or solid obtained by dehydration in (a) or (b) in an organic solvent. (16) The method according to the above (13) or (14), which comprises a mixture of chlorinated quaternary scales and iodinated and/or quaternary phosphonium ruthenium, which is any one of the following (d) and (e). (d) a liquid which is taken out from the above reaction step and diluted with an organic solvent, -9-(7) 1313260 (e) is distilled from the reaction liquid taken from the above reaction step to remove water and/or a target alkene derivative At least a portion of the remaining residue 'or a liquid obtained by dissolving the residue in an organic solvent. (1) The method according to any one of the above (1 3) or (6), wherein the recovered iodide and/or brominated quaternary acid is circulated in the above reaction step. (18) A method for producing an alkene derivative using a reaction step of reacting epoxide with carbon dioxide to form ethylene carbonate using iodinated and/or brominated quaternary phosphonium as a catalyst, characterized by: The reaction step comprises a mixture of quaternary phosphonium chloride and iodinated and/or quaternary phosphonium bromide, and an iodide and/or bromide is added to convert the chlorinated quaternary scale to iodination and/or bromination. The fourth grade is recovered in water and recovered, and recycled to the reaction step. (1) A method for producing an alkene derivative using a iodinated and/or brominated quaternary scale as a catalyst, comprising a reaction step of reacting an epoxide with carbon dioxide to form an alkylene carbonate, characterized by: From the reaction step, containing a mixture of chlorinated quaternary scales and iodinated and/or brominated quaternary scales, adding iodide and/or bromide to cause chlorine from the chlorinated quaternary scale to be in the organic solvent in the organic solvent. Precipitation to recover iodinated and/or brominated quaternary phosphonium, and recycled to the reaction step. In the present invention, when a reaction liquid and/or a catalyst liquid containing a high concentration of a catalyst is mixed with water, the chloride salt from the catalyst remains dissolved in the liquid, and the iodide salt or the bromine salt starts to precipitate. That is, any of the iodide salt, the bromine salt, and the chlorine salt is more soluble than the alkanediol or the alkylene carbonate, and the solubility of the iodized salt or the bromine salt in water is low, and the solubility of the chloride salt in water is high. The precipitated iodinated or brominated tetrabasic, -10-(8) 1313260 can be easily separated and recovered by solid-liquid separation. In the present invention, for example, a catalyst can be precipitated as follows. 1 The reaction solution containing the catalyst and/or the catalyst solution is mixed with water and cooled. 2 After removing at least a portion of the alkanediol from the catalyst-containing reaction solution and/or the catalyst solution, mix with water. There is no need to cool down the operation at this time. However, in order to reduce the solubility of the catalyst, it is preferred to cool. Thus, the recovered iodized or brominated quaternary scales can be recycled to the reaction step. On the other hand, the separation liquid after separation and recovery of iodine or brominated quaternary solid solution contains chlorine salt chlorinated four-grade money, which can be converted into iodination or bromination by ion exchange or the like. The scales are recovered after recycling, or recycled to the reaction step in a solution state. Further, in the present invention, the reaction step of reacting an epoxide with water or carbon dioxide to form an alkanediol or an alkylene carbonate in the presence of carbon dioxide by using an iodinated and/or brominated quaternary catalyst a mixture of chlorinated quaternary phosphonium chloride and iodinated and/or quaternary quaternary ammonium, added with iodide and/or bromide to convert the chlorinated quaternary scales in the mixture to iodide and/or bromine Compound. Thereby, the iodinated and/or brominated quaternary scales formed by reacting the previously existing iodinated and/or brominated quaternary phosphonium ′ and chlorinated quaternary acid with the compound and/or bromide can be precipitated in water. It is recovered as a precipitate. In the following, a mixture containing chlorinated tetrabasin and iodized and/or brominated quaternary rust for the conversion of chlorinated quaternary scales to iodinated and/or brominated quaternary scales with iodide and/or bromide Sometimes called "processing object mixture." Under -11 - (9) 1313260, the liquid flowing out of the reactor or the liquid taken out from the reactor, sometimes referred to as "reaction liquid", is separated from the reaction liquid by water, alkanediol and alkylene carbonate. The liquid concentrated by the catalyst is sometimes simply referred to as "catalyst liquid". The treatment target mixture of the present invention may be a reaction solution containing a catalyst directly from a reaction step of an alkanediol or an alkylene carbonate, or a solvent alkanediol or alkylene carbonate in the reaction solution. The liquid catalyst liquid or the solid residue after partial or complete evaporation of the enester is added with water to precipitate a part of the catalyst after the recovered liquid (hereinafter, the water in the catalyst liquid or the solid residue is water) The addition of a portion of the catalyst for precipitation and recovery is sometimes referred to as "pre-recovery.") The recovery of the chlorinated quaternary scale of the treated mixture can be increased to iodide and/or bromine. The conversion and recovery rate of the four-grade money can be improved. That is, since the solubility of iodinated and/or brominated quaternary acid in water is lower than that of chlorinated quaternary money, such as water addition, iodinated and/or brominated quaternary carbon precipitates, and chlorination The fourth grade is dissolved in water. By recycling as described above, the concentration of the quaternary chlorination of the mixture to be treated can be increased, and the conversion of the iodinated and/or brominated quaternary scales can be improved. In still another method, when the above-mentioned pre-recovery is carried out, instead of the water added to the catalyst liquid or the solid residue, the iodide and/or the bromide aqueous solution is used instead, whereby the iodization and/or bromination can be improved. The recovery rate of the fourth grade money. In either method, the addition of iodide and/or bromide to the chlorinated tetrabasic dissolved in water causes the quaternary phosphonium chloride to precipitate as iodide and/or bromide, leaving a solution in the solution that remains dissolved. Chloride of the added compound. Therefore, the precipitated precipitate can be easily separated and recovered by iodination and/or brominated quaternary rust by solid-liquid separation. The thus recovered iodide and/or brominated quaternary acid can be recycled to the reaction step of an alkanediol or an alkylene carbonate. Further, according to the present invention, from the reaction step, or from the above-mentioned recovery step 'mixture containing quaternary phosphonium chloride and iodinated and/or brominated quaternary phosphonium, iodide and/or bromide is added to give chlorine. The chlorinated and/or brominated quaternary scales can be recovered by dissolving the chlorine of the fourth-grade bismuth with an inorganic chloride in an organic solvent. That is, a reaction step of reacting an epoxide with water or with carbon dioxide to form an alkanediol or an alkylene carbonate in the presence of carbon dioxide using an iodide and/or a brominated quaternary catalyst, A mixture of chlorinated tetrabasin and iodized and/or brominated tetrabasin, with the addition of iodide and/or bromide, converts the quaternary tetrachloride in the mixture to iodide and/or bromide Level money. On the other hand, an inorganic chloride having a low solubility in an organic solvent from chlorine of a chlorinated quaternary scale is precipitated in an organic solvent, and is separated to recover iodinated and/or brominated dissolved in an organic solvent. Four levels of 辚. Hereinafter, as described above, the operation of precipitating the chlorine derived from the chlorinated quaternary acid in the organic solvent to the inorganic chloride may be referred to as "inorganic chloride precipitation operation". Further, in order to precipitate chlorine of chlorinated quaternary ammonium as inorganic chloride, and to add iodide and/or bromide, a mixture containing chlorinated quaternary phosphonium and iodinated and/or brominated quaternary phosphonium is sometimes called "Processing the mixture of objects." The chlorinated quaternary scale is converted into an iodide or a bromide, and the chloride derived from the chloride is separated into an organic solvent by an inorganic chloride, and the separated separation liquid is dissolved in an organic solvent to be iodinated and/or Brominated quaternary rust liquid-13- (11) 1313260. Therefore, the iodinated and/or brominated quaternary scales can be recovered as a solid by evaporating the organic solvent of the separation liquid. The recovered iodide and/or brominated quaternary money may be recycled to the appropriate solvent to be recycled to the alkanediol or alkylene carbonate reaction step if necessary after washing with water. [Embodiment] Hereinafter, an embodiment of a method for producing an alkanediol of the present invention will be described in detail.

Hereinafter, the present invention is mainly described as a reaction product suitable for producing ethylene glycol from ethylene oxide using an iodide quaternary catalyst, but is not limited thereto. For example, the present invention is also applicable to the production of various alkanediols such as propylene glycol from propylene oxide. Further, if the catalyst is brominated to a quaternary scale, or the catalyst is iodinated or brominated to a quaternary cerium, the same applies. Further, in the present invention, as described above, the reaction conditions are changed as in the method for producing the alkanediol, and the reaction temperature is lowered to suppress the formation of an alkanediol such as ethylene glycol, and it is also applicable to the production of an alkylene carbonate such as ethylene carbonate. The reaction of the enester is also applicable to the reaction of the alkylene carbonate and the alkylene glycol as the target product. The following is exemplified by adding an iodide to the treatment target mixture to convert the chlorinated quaternary scale into a monumental quaternary phosphonium. The method of recycling. It can also be used instead of iodide to add bromide, convert chlorinated quaternary scales into brominated quaternary scales, or use iodide and bromide to convert chlorinated quaternary scales into iodinated quaternary lanthanum. And brominated quaternary phosphonium and recovered. -14- (12) 1313260 The following is a method of adding inorganic iodide to a treatment target mixture to convert a chlorinated quaternary scale into a iodinated cesium iodide, and at the same time, a chlorine derived from chlorinated quaternary ammonium is inorganic chloride. The method of precipitation. It is also possible to replace the iodide with the addition of bromide to convert the fluorinated F-grade rust into the quaternary phosphonium bromide, and at the same time, the chlorine from the chlorinated quaternary scale is precipitated as an inorganic chloride; The bromide 'converts the chlorinated quaternary scale to the iodinated quaternary phosphonium and the brominated quaternary scale', while precipitating the chlorine from the chlorinated quaternary scale with inorganic chloride. The compound described in the publication of Japanese Patent Publication No. Sho-58-8-2 4 4 8 is suitable for use in the iodized fourth-order scaly catalyst of the present invention. Representative examples include triphenylmethyl iodide, triphenylpropyl iodide, triphenylbenzilium iodide, and tributylmethylhydrazine iodide. Such a iodinated fourth-grade rust catalyst preferably has a mass ratio of 0 〇 〇 1 to 〇 with respect to ethylene oxide. 〇 5 times mole is supplied to the reaction system. When a quaternary phosphonium bromide is used, the bromide catalyst corresponding to the above-mentioned iodinated cesium iodide can be used in a preferred amount comparable to that of the iodinated tetradecene catalyst. In the present invention, the alkali metal carbonate as a promoter can be coexisted in the reaction system, whereby the production efficiency of ethylene glycol can be improved. The alkali metal carbonate is present in the reaction system, and a sodium hydroxide or a hydrazine, preferably a hydroxide, a carbonate or a hydrogencarbonate of an alkali metal such as potassium, may be added, and any alkali metal compound may be added to the reaction system. It is present as an acid salt. At this time, the preferred one is the metal carbonate, which is preferably cesium carbonate, and is present in a molar ratio of 0.01 to 1 with respect to the iodized quaternary scale. The amount of water relative to ethylene oxide can be reduced to a stoichiometric amount, and may be below the reaction form, but it is usually preferably about 1.0 to I 0 〇 〇 摩尔 摩尔 relative to ethylene oxide. . Carbon dioxide is sufficient to be equivalent to -15- (13) 1313260 moles relative to Epoxide. Under normal conditions, it is used in g ears. 1 to 5 · 0 m. But there is no strict limit. The reaction temperature varies depending on the type of the epoxide, the composition of the catalyst type, and the like. Generally, the pressure at 50 to 18 varies depending on the amount of carbon dioxide, the reaction temperature, and the like, and varies depending on the passage, generally In the range of 0.5 to 5.0 million. The form of the reactor is not particularly limited and can be smoothly carried out. The number of reactors and the residence time are selected so as to achieve the desired ethylene glycol, and if necessary, a reactor may be added to hydrolyze the reaction enester. The reaction liquid from the reactor was separated and the water was separated by distillation. The remaining catalyst-containing liquid (catalyst liquid) is recycled to the reactor for the reaction. When the reaction system recovers the catalyst of the reaction liquid from the reactor by efficiently recovering the iodinated or brominated quaternary acid, the catalyst is difficult to precipitate due to the low degree of the catalyst, and the preferred one is to remove the anti-diol to improve the contact. After the concentration of the medium (the catalyst after the removal of ethylene glycol is used to recover the catalyst by using the catalyst liquid, although it can be directly used with the water medium, in order to improve the recovery rate of the catalyst, it is preferable to further pass I through the oxygen. The amount of the reaction is within the range of the reaction. In the range of the reaction, the gas-liquid reaction is the conversion rate. The majority of the ethylene carbonate in the liquid is used in the next step. The recycled water of the original catalyst concentrated liquid and B) are mixed with water to recover the ethylene glycol contained in the-16- 1313260 (14) after the distillation, and then mixed with water to recover the catalyst. That is, in the reaction, at least a part of the reaction liquid or the catalyst liquid is taken out from such a reaction step to remove water and an alkanediol or an alkanediol, so that the alkanediol and the catalyst are contained in the liquid. When the ratio is higher than 20 times, it can be 20 times or less, preferably 2 times or less, and then mixed with water. When the molar ratio of the alkanediol to the catalyst contained in the liquid is less than 20 times the molar ratio, only the water is mixed and precipitated to recover the catalyst. When the liquid taken out from the reaction step is mixed with water, it is sometimes necessary to cool the precipitated iodized quaternary scale. That is, the solubility of the iodinated quaternary scale in water or ethylene glycol is lower as the temperature is lower. The reaction liquid generally taken out from the reaction step is about 100 to 180 °C. Preferably, the reaction liquid is mixed with water to lower the liquid temperature to below 30 ° C, preferably to about 20 ° C, whereby the iodinated quaternary scale can be more efficiently precipitated. The presence or absence of this cooling depends on the temperature of the reaction liquid, the temperature and mixing amount of the mixed water. In order to precipitate, not only cooling, but also adding or pre-existing seed crystals can stabilize the high-efficiency crystallization. At least a portion of the product ethylene glycol is removed from the liquid taken from the reaction step, preferably most of it (may also contain water), so that the catalyst concentration becomes, for example, 40% by weight or more 'and then it is not necessary to mix with water Cooling can cause the iodine quaternary rust to precipitate out', and cooling to 40 °C or less can be more efficiently precipitated. The amount of water mixed varies with the amount of iodine in the reaction solution, the amount of ethylene glycol, the amount of chloride, the presence or absence of cooling, the recovery efficiency of the desired cesium iodide, etc. And there is a tendency for the dissolution efficiency of the chlorinated four-grade scale to be -17-(15) 1313260. On the other hand, if there is too much, the amount of iodized quaternary money contained in the liquid phase after the separation of the iodine tetradecene is increased. In general, the amount of water to be added in one treatment is appropriately determined in the range of 1 to 5 weights with respect to the treatment liquid 〇 1 or more. The liquid phase separated from the solid can be used as a rinse liquid for a re-reaction liquid, a catalyst liquid or a catalyst after separating ethylene glycol. At this time, when it is repeatedly used as the washing water, the concentration of the chlorinated quaternary acid contained in the washing water is increased, and the concentration of the chlorinated quaternary scale contained in the recovered quaternary strontium is increased. After one to five washes, replace with fresh wash water. The washing of the reaction liquid is carried out many times, and the method of gradually replacing the washing water with a low concentration of chlorinated quaternary acid can be smoothly carried out. The specific aspect of the operation is that the slurry of the cooled water or the iodinated quaternary scale is stored in the container in advance, and the reaction liquid or the catalyst liquid and the water are continuously or batch-wisely supplied, and the obtained mixture is continuously or batchwise. The sub-type is taken out, and the precipitate contained therein can be recovered by filtration. To separate the ethylene glycol from the reaction liquid, the distillation separation operation of ethylene glycol can be carried out, for example, under reduced pressure. The water accompanying ethylene glycol is also separated. The precipitate obtained by mixing the reaction liquid and water in this manner is usually a highly active iodinated quaternary catalyst having an iodide content of 90% by weight or more and a chlorine salt content of 0% by weight or less, which can be effectively recycled to the reaction step. The separation liquid obtained by separating the iodinated quaternary precipitates contains a chlorine chloride chlorinated four-stage scale. The chlorinated quaternary carbon is converted, and the separation liquid is subjected to dehalogenation treatment with an OH type anion exchange resin, neutralized with hydrogen iodide, and directly exchanges chloride ions into iodide ions by an anion exchange resin substituted with iodine, and the like. For iodized four levels -18- (16) 1313260 money. Thus, the catalyst can be regenerated and the resulting regenerated catalyst can be effectively recycled to the reaction step. The invention can be carried out by continuously or intermittently taking out part of the reaction liquid from the reactor in continuous operation, recovering the cesium iodide cerium catalyst, and recycling the recovered cesium iodide catalyst to the reactor. . At this time, the amount of the reaction liquid and/or the amount of the catalyst liquid to be taken out for recovering the iodized fourth-stage catalyst is not particularly limited, and the chlorine salt is highly maintained in a range in which the catalyst recovery cost is not excessively high. The efficiency is preferably that the reaction liquid is continuously or intermittently taken out for treatment so that the weight ratio of the chlorine salt in the reactor to the iodide salt becomes 〇1 to 1.0. The amount of the extraction is not particularly limited, and it is preferred that the amount of each reaction liquid is from about 0.1 to 100% by weight based on the amount of the catalyst solution. Converting the chlorinated quaternary scales in the reaction system to iodinated and/or brominated quaternary money for recycling and recycling to the reaction system. The present invention relates to a mixture of treated objects containing chlorinated and iodinated quaternary phosphonium The ratio of the chlorinated and iodinated quaternary scales and the composition are varied according to the ratio of chlorine to iodine in the ethylene glycol process, the venting space, and the subsequent treatment (pre-recovery operation, etc.). The ratio of the chlorination to the quaternary quaternary scale in the treatment target mixture is not particularly limited, and the efficiency ratio of the recovery operation is preferably higher than the chloride ratio of the iodide and the concentration of the chloride. Therefore, the molar ratio of the treated object mixture to the iodinated quaternary scale and the chlorinated quaternary acid is more than 1 / 20 times '1 / 10 or more, and the concentration of the chlorinated quaternary phosphonium in the treated object is 〇 1% by weight or more, preferably 1% by weight or more. -19- 1313260 (17) ί In the specific example of the present invention, the following methods other than the method of adding the W compound of the target mixture can be obtained. In order to explain, the invention is by no means limited to the following methods. [Application Example I] A part of the liquid in the ethylene glycol process is taken out as a catalyst. If it is contained in the catalyst-containing liquid in the process, the removal location is limited. As described above, the reaction of ethylene glycol to ethylene glycol reacts with carbon dioxide to form ethylene carbonate and ethylene carbonate into a two-stage reaction of ethylene glycol. Therefore, when the reaction from the liquid of the process is carried out in a reactor in which two stages are connected in series, it can be taken out from the reactor or taken out from the two reactors. When the liquid is taken out at the outlet of the reactor, the recovery rate of the fourth-stage hydrazine is mentioned in the subsequent step, and the concentration of chlorination and iodination in the treated mixture is preferably high, so the solvent water, ethylene glycol or It is preferred to concentrate the dilute ester. The method of satiety can be used for steaming towers or single units. Preferably, it is concentrated to 丨/20 mol times or more of the iodine quaternary solution in the mixture to be treated. Considering the four-grade money salt, the distillation concentration operation is preferably performed under reduced pressure, suitably 400 Torr, and the temperature of 60 to 210 ° C is preferably carried out. The reaction solution is concentrated by distillation to obtain a high concentration of the catalyst liquid containing iodine money and the chlorination of the iodinated quaternary chlorination in the ethylene glycol process, and the catalyst liquid can be obtained by taking the reaction liquid out of the system. Alternatively, the method of separating water, ethylene glycol, ethylene carbonate and catalyst liquid can be used as well as the liquid. Special: Oxygen B: Decomposition; When • Reacting iodine 3 grade sulphate B1 Evaporation t is rich in f heat (53.2: 四4 铙. 5 from the laughing tower -20- (18) 1313260 Take out the catalyst liquid. Used to recover the iodized iodine iodine iodide system, any energy It can be used in the ion exchange of chlorinated quaternary ions, which can be dissociated in water. It can be suitably selected by the industry, and based on solubility, toxicity, price, etc., it is preferably an alkali metal such as sodium salt or potassium salt. Salt or hydrogen acid.

Inorganic iodide system, any ionic compound which can be ion exchanged with quaternary chloride and dissociated in water, is suitable for alkali metal salts such as sodium salt and potassium salt in terms of solubility, toxicity and price. . The amount of the iodide added is preferably equal to or more than the equivalent amount of the chlorinated four-dimensional amount in the mixture to be treated. A suitable range is from 0.5 to 10 moles per mole of chlorinated quaternary phosphonium 1 mole present in the mixture of the treatment target, preferably from 1 to 5 moles per mole. The addition of solids to the iodide increases the recovery, but excess iodide is wasted.

The iodide may be added in the form of a solid, an organic solvent solution or a water. The solution is industrially convenient for liquid use, preferably in an organic solvent solution or an aqueous solution. In the case of an aqueous solution, the amount of water is sufficient to dissolve the amount of iodide, the amount of which depends on the iodide used. For example, when potassium iodide is used, since the saturated solubility of water is 60%, the concentration of potassium iodide added to the treatment may be below. It is usually preferred to add to an aqueous solution of about 1 to 60% by weight. The means for adding the iodide to the treatment target mixture may be a container of any form, and it is preferred to promote the ion exchange reaction to a vessel having a stirring device. The chlorinated quaternary phosphonium present in the treatment target mixture is converted into -21 - (19) 1313260 iodinated quaternary acid, which is decomposed into the water together with the iodinated quaternary solution existing in the treatment target mixture. When the precipitation temperature is low, it is preferred that the iodine quaternary hydrazine is left in the water. It is better to go to 3〇t. The precipitated iodide tetradecane is filtered and recovered. The filtration method is not particularly limited, and centrifugal filtration or the like may be employed in addition to filtration using a usual filter. The iodinated quaternary phosphonium recovered as a solid sometimes contains about 10% by weight of chlorinated quaternary scales and added iodide. At this concentration, it can be directly recycled to the reaction step of ethylene glycol, but if necessary, the purity of the iodinated quaternary scale can be increased by using water rinsing and then recycled. The water used for rinsing may be used for the next rinsing because it contains iodized quaternary money, or may be reused as water for dissolving the iodide added to the treatment mixture as described above. The recovered iodized quaternary scale can be, for example, dissolved in ethylene glycol to be recycled to the reaction system. As above, the state in which the chlorinated quaternary money is converted into the iodine quaternary money is recovered. This operation can also be carried out in an organic solvent. In the following, an operation of precipitating an inorganic chloride in an organic solvent, converting a chlorinated quaternary scale into an iodinated quaternary acid, and recovering it will be described. In the obtained high concentration of the catalyst liquid, the solvent may be subjected to the inorganic chloride precipitation operation of the present invention due to the presence of the solvent ethylene glycol and/or ethylene carbonate, and is also suitable for addition to the iodide. Other organic solvents having a low solubility of inorganic chlorides when added. Moreover, it is preferred to remove the ethylene glycol and/or ethylene carbonate in the high concentration catalyst liquid to become a substantially solvent-free solid, and redissolve it in other organic solvents, and the solubility of the inorganic chloride is further reduced. Improve the efficiency of precipitation. -22 - 1313260 (20) The organic solvent used herein is preferably 'the solubility of the inorganic chloride is low' and the solubility of the quaternary phosphonium salt is high. Suitable solvents are 'aliphatic halogenated hydrocarbons, ketones, alcohols, nitriles, guanamines, urea compounds, carbonates. Among them, alcohols are, for example, 'ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1,1-dimethylethanol, 1-pentanol , 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 1,1-dimethyl-1-propanol, 1-hexanol, 2 -hexanol, 3-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1 Monooctanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 2-nonanol '1-sterol, 1-undecyl alcohol, 1 -dodecanol, 1,6 — Hexanediol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, and the like. The aliphatic halogenated hydrocarbon is, for example, dichloromethane, chloroform, 1,2-dichloroethane ' 1,1,1 -trichloroethane, 1,1,2-trichloroethane ' 1,2-dichloro Propane, 1,3 - dichloropropane, 1,2,3 -trichloropropane, 1,4 - chloroprene, 1 ' 6 - dichlorohexan, etc. The nitrile is, for example, acetonitrile, propionitrile, butyronitrile, adiponitrile, benzonitrile or the like. The guanamine is, for example, dimethylformamide, dimethylacetamide or the like. The urea compound is, for example, tetramethylurea or 1,3 -dimethylimidazolidin-2-one. The ketone includes acetone, methyl ethyl ketone, methyl isopropyl ketone and the like. The carbonates are ethylene carbonate, propylene carbonate, butylene carbonate, and the like. The organic solvent may be used alone or in combination of two or more. The amount of the organic solvent to be added is not particularly limited, and is usually 5% by weight of the chlorinated and iodinated quaternary scale in the treatment target mixture. -23- (21) 1313260 For example, sodium iodide is easily soluble in acetone, so it is a suitable combination. While cesium iodide is dissolved in ethylene glycol, such a combination is also suitable. However, at this time, the iodide A must be completely dissolved in the organic solvent. Even if the saturated dissolved amount of the iodide is added to the treated target mixture, the iodide is further dissolved to make up the portion consumed by the reaction with the chlorinated tetrabasic. As a result, the solubility of the stomach can be reacted to form an inorganic chloride. The iodide and organic solvent are selected to be 'iodide,' and the inorganic chloride formed by the reaction of the iodide with chlorinated tetrabasic, which has a difference in molar solubility in organic solvents. Such a combination is, for example, butanol or ethylene glycol relative to potassium iodide. The means for adding the iodide to the treatment target mixture may be in any form of the apparatus, and it is preferred to carry out the ion exchange reaction for the vessel having the stirring means. Through this operation, the fourth chlorinated quaternary scale present in the target mixture is treated, the grade 鍈 becomes the iodine quaternary scale, and the chlorine is precipitated as the inorganic chloride. The precipitation temperature is not particularly limited and depends on the solubility dependence of the inorganic chloride, the boiling point of the organic solvent used, the viscosity, and the solubility of the quaternary phosphonium salt. It is usually at room temperature of 50 °C. The reaction of iodide with chlorinated quaternary scales is carried out when the solvent viscosity is low, the solvent viscosity is high, and the solubility of the iodide is low. The appropriate person will complete the reaction from 1 minute to 3 hours. By this operation, the quaternary phosphonium of the chlorinated quaternary acid in the organic solvent is converted into the iodide at a conversion ratio of 90% or more, and at the same time, the inorganic chloride is precipitated. The precipitated inorganic chloride is removed by hydrazine. The filtration method is not particularly limited. In addition to filtration using a usual filter, centrifugal separation or the like can be employed. -24- (22) 1313260 The filtration of the inorganic vapor is separated by filtration. The liquid is evaporated from the filtrate to remove the 'iodinated four-stage scales and the excess is added. The iodide is recovered as a solid. The removal of the organic 'solubilization' can be carried out using a conventional evaporator. The evaporation of the organic solvent is carried out as described above, and the heat resistance of the recovered iodized quaternary acid is considered to be carried out at a temperature of 200 or less under reduced pressure if necessary.

The purity of the thus recovered iodized quaternary phosphonium is 'excessively added iodide and the remaining solvent 'more than 90%' can be directly or dissolved in a suitable solvent such as ethylene glycol for recycling in the reaction step' Preferably, the recovered solid is washed with water to remove the remaining iodide and solvent before being recycled to the reaction step. The water washing may be carried out by collecting the solid addition washing water into a slurry, filtering or centrifuging. At this time, the dissolution loss of the wash water is considered, and the amount of the wash water to be added is preferably 2 parts by weight or less with respect to the recovered solid.

In addition to the method of removing the inorganic chloride in the above method, the inorganic chloride may be removed by filtration without removing the solvent, and then the water washing may be carried out to dissolve the inorganic compound in water. Another embodiment of the present invention is the following method. [Applicable Example I1] In the application example I, the concentration of the iodine tetrabasic is more than 1 / 20 mole times relative to the ethylene glycol, or concentrated to a high concentration of the catalyst liquid of such concentration, added with water After mixing and cooling, the iodinated quaternary acid is selectively precipitated and recovered before being recovered. Here, the 'water system is added in an arbitrary amount, and when it is too small, the precipitation effect is not sufficiently sufficient', so it is necessary to add at least the weight of 0. 1 -25-(23) 1313260 or more of the dissolved iodized quaternary money. The upper limit of the amount of water to be added is not particularly limited, and it is preferably about 5 times by weight or less with respect to the dissolved iodized fourth-grade money in order to prevent the treatment capacity from being excessively large. The temperature at the time of the precipitation operation is preferably such that the remaining amount of the iodine quaternary acid in the water is small. It is suitable for 〇 to 30 °c. In the aqueous solution remaining after the precipitation of the precipitated iodide quaternary money, there are undeuterated iodinated quaternary scales and chlorinated quaternary rust. The aqueous solution remaining after the above-mentioned iodinated quaternary scales are recovered as the treatment target mixture, and if necessary, iodide is added after the concentration, and the chlorinated quaternary scale can be converted into iodine quaternary money and precipitated. The concentration is preferably such that the concentration of the chlorinated quaternary scale in the treatment target mixture before the addition of the iodide is 1% by weight or more, and the conversion efficiency of the chlorinated quaternary scale and the recovery efficiency of the cesium iodide bismuth are better. The type of iodide added, the concentration to be added, the method of addition, the method of filtering the precipitate, and the subsequent treatment are the same as those of the above-described application example I. However, at this time, since water is present in the system, the iodide can be added as a solid, whereby the amount of water used is reduced, and the dissolution of the iodinated quaternary scale is lost to the waste water. After the pre-implementation, the water containing the aqueous solution containing the chlorinated and iodinated four-stage scale is preferably 90% or more, and more preferably 99% or more, which is removed by evaporation, and the inorganic chloride precipitation operation can be performed. . In other words, the treatment target mixture is dissolved in an organic solvent in an amount of 1 to 1 part by weight based on the total of the chlorinated and iodinated quaternary grains in the treatment target mixture, and iodide is added thereto. -26- (24) 1313260 The type, concentration, and addition method of the iodide added, the method of filtering the precipitates, and the subsequent treatment are the same as those of the above-mentioned application example I. In the present method, the water added to precipitate the iodinated quaternary acid in the high concentration of the catalyst liquid may be added as an aqueous solution of the iodide. In this case, the addition of the iodide in the latter stage is not required. In any case, the organic solvent is removed from the inorganic chloride precipitate by solid-liquid separation, and the organic solvent is removed to recover the iodized quaternary acid, which can be reused together with the previously recovered iodized quaternary scale. In addition, there are the following methods. [Applicable Example III] In the application example I, the concentration of the iodinated quaternary scale is more than 1 / 20 times relative to the ethylene glycol, or the concentration of the catalyst liquid concentrated to such a concentration is further concentrated, and the solvent is More than 90% is distilled off. At this time, the residue (distillation residue) solidifies as it cools. The solidified residue is rinsed with an appropriate amount of water to remove the chlorinated quaternary scales in the residue by dissolving it in water. At this time, the temperature of the washing water is also lower because the amount of dissolution of the iodinated quaternary scale in the washing water is small. It is better to go to 30 °C. The amount of water used for washing is not particularly limited, but considering the washing efficiency and the loss of the fourth-grade rust in the waste water, it is preferably from 0.5 to 10 times the weight of the solid residue remaining. The flushing water does not have to be pure water. Circulating water in the available process. Can be used for any secondary recycling. If it is a water-soluble solution containing a monumental four-grade money, the dissolution loss of the iodinated quaternary scale in water can be reduced, and it is particularly preferable. In the water after washing, there are washed chlorinated quaternary scales and a small amount of dissolved -27-1313260 (25) iodinated quaternary rust. As the treatment target mixture, as described above, if necessary, after the concentration thereof, the addition of iodide can convert the chlorinated quaternary phosphonium into the iodinated quaternary scale. In this case, before the addition of the iodide, the chlorinated quaternary phosphonium concentration of the treatment target mixture is preferably 1% by weight or more, the type of the iodide added, the added concentration and the addition method, and the filtration method of the precipitate, and thereafter The processing and the like are the same as those of the foregoing application example 1. At this time, since water is present in the system, the iodide can be added as a solid, and as a result, the amount of water used is reduced, and the dissolution loss of the iodine quaternary acid in the wastewater can be reduced. The above-described rinsing operation is carried out, and the water after washing is used as a method of adding iodide to the mixture to be treated, and an aqueous solution of iodide may be used as the rinsing water, and the step is shortened. In this case, the concentration of the iodide aqueous solution used may be the concentration of the iodide in the water after the rinsing, and the concentration of the iodide in the state to be added may be the concentration of the previously added state. The water containing the aqueous solution of the chlorinated and iodinated quaternary scales is preferably a mixture of 90% or more and more preferably 99% or more as a mixture to be treated, and an inorganic chloride precipitation operation can be applied. In other words, the mixture of the treatment target is dissolved in an organic solvent of 1 to 10 times by weight with respect to the chlorinated and iodinated quaternary particles in the treatment target mixture, and an iodide is added thereto. The type of iodide to be added, the concentration to be added, the method of addition, the method of filtering the precipitates, and the subsequent treatments are the same as in the first application example I. In this method, it is also possible to use an iodide aqueous solution instead of the rinse water, and the iodide addition in the latter stage is unnecessary. -28- 1313260 (26) In either case, the organic solvent solution after the solid-liquid separation of the inorganic chloride precipitates can be further recovered by the removal of the organic solvent, together with the previously recovered iodinated quaternary phosphonium For reuse. The concentration of the above-mentioned cesium iodide is more than 1 / 20 times that of the ethylene glycol system, or the concentration of the high-concentration catalyst liquid concentrated thereto can be more concentrated, and after removing the solvent of 90% or more, it is kept at 90 ° C or higher. The temperature is maintained in a liquid state, so that after it is added with water, it can be cooled to 40 ° C to precipitate the cesium iodide. Alternatively, the above-mentioned concentrated residue may be continuously supplied to the existing cold water or slurry separately or simultaneously with water to be crystallized. At this time, the remaining aqueous solution of the precipitated iodized scale was separated and recovered, and there were undecided iodized and chlorinated quaternary scales. As the treatment target mixture, as described above, if necessary, it is concentrated, and iodide is added to convert the chlorinated quaternary acid into the iodinated quaternary rust and recover. In this case, in the treatment target mixture before the addition of the iodide, the chlorinated quaternary concentration is preferably 1% by weight or more, the added iodide type, the added concentration and the addition method, and the filtration method of the precipitate, and thereafter The processing and the like are the same as those of the foregoing application example 1. Therefore, water is already present in the system at this time, so that the iodide can be added as a solid, whereby the amount of water used is reduced, and the dissolution loss of the iodinated quaternary scale in the wastewater can be reduced. Instead of water, the aqueous solution of the iodide may be heated and used, which is an embodiment in which the above steps are shortened. The water containing the aqueous solution of the chlorinated and iodinated quaternary scales is preferably 90% or more, more preferably 99% or more, which is evaporated and removed as a treatment target mixture, and an inorganic chloride precipitation operation can be carried out. That is, the treatment is carried out by dissolving the -29-(27) 1313260-like mixture '1 to 10 times by weight of the organic solvent with respect to the chlorinated and iodinated quaternary rust in the treatment target mixture, and adding iodide thereto. The type of iodide to be added, the concentration to be added, the method of addition, the method of filtering the precipitate, and the subsequent treatment are the same as those of the above-mentioned application example I. In the present method, it is also possible to replace the above-mentioned water with an aqueous iodide solution, and the addition of iodide in the latter stage is unnecessary.

In all of the embodiments, the present invention is also applicable to the case where an iodide is added to precipitate an inorganic chloride, and the solid-liquid separation is carried out to remove the remaining chlorinated and iodinated quaternary scale. That is, the addition of iodide and the removal of inorganic chloride can be repeated before the desired recovery rate is achieved.

In order to employ the present invention, it is possible to continuously or intermittently take out at least a portion of the reaction liquid and/or the catalyst liquid from a reaction process in continuous operation, and if necessary, perform concentration and/or pre-recovery to convert the chlorinated quaternary scale It is the iodine quaternary scale and is used for the recovery of iodinated quaternary hydrazine. The recycled iodine tetrabasic catalyst is recycled to the reactor. At this time, the amount of the reaction liquid and/or the catalyst liquid taken out for recovering the iodinated quaternary catalyst is not particularly limited. In order to remove the chlorinated quaternary scale from the catalyst recovery cost, the reaction efficiency is highly maintained. Preferably, when the weight ratio of chlorinated quaternary phosphonium in the reactor relative to the iodide falls within the range of 〇_0 1 to 1.0, the reaction liquid and/or the catalyst liquid are continuously or intermittently taken out for treatment. The amount of withdrawal is not particularly limited, and is preferably from about 0.1 to 100% by weight based on the amount of the reaction liquid or the amount of the catalyst liquid in the system. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. Of course, the invention should not be construed as being limited to the related embodiments only -30-(28) 1313260. Example 1 _ 1 was pressurized with carbon dioxide to 2 · 〇 million Pa, with a residence time of 1 hour, and the first reactor supplied with catalyst was supplied with tributylmethyl iodide 5 parts by weight per hour 'potassium carbonate 〇 8 parts by weight/hour, a raw material ethylene oxide aqueous solution (60% by weight) 78 parts by weight/hour, and a reaction liquid containing ethylene carbonate and diol (EG) was obtained. The whole reactor was moved to a residence time of 2 hours, and the pressure was 〇. 5 million Pa's temperature Ϊ 50 ° C. The second reactor hydrolyzed the ethylene carbonate to obtain an aqueous solution of a catalyst containing ethyl alcohol 6 6 · 5 Parts by weight per hour. The obtained reaction liquid is distilled in a vacuum distillation column of 1 4 〇 ° C, 1 1 kPa (80 mm Hg) at the bottom of the column, and the dehydrated liquid is obtained from the bottom of the column, and is further reduced to 140 t, 8 kPa. (60 mm Hg) The operated reduced pressure evaporator evaporates most of the ethylene glycol, and the catalyst is concentrated from the bottom of the evaporator to a concentration of 13 parts by weight per hour. The recovered catalyst is recycled to the first reactor for use as a catalyst. After one year of continuous operation, the catalyst liquid is as follows: [compatibility of the catalyst liquid] Ethylene glycol: about 59 wt% iodized salt (confirmed grade 4 rust) · about 33 wt% chloride salt (chlorinated grade 4) Rust): about 6% by weight potassium carbonate: about 2% by weight After the above composition is reached, 'change to one part of the catalyst liquid is taken out at 0.0 2 -31 - 1313260 (29) parts by weight per hour. The extracted catalyst liquid (hereinafter referred to as "extraction liquid A") is supplied to the ablator, and is removed in a liquid of about 93% by weight under the conditions of 3 Torr (40 kPa) and 280 °C. Ethylene glycol. The liquid after removing the ethylene glycol (hereinafter referred to as "concentrate A") was kept at 95 ° C, and a 3 wt% aqueous potassium hydroxide solution was added thereto, stirred and mixed, and cooled to 20 ° C, and allowed to stand for 1 hour. The amount of water used in the potassium iodide and the concentrate A in the concentrate A, the amount of water used, and the weight of the concentrate A are equal. The precipitate is analyzed by a solid-liquid separation of a suction filter, and the composition of the precipitate is as follows, which is equivalent to 90% by weight of the iodide salt and the chloride salt in the above-mentioned extract A to be iodinated four-stage scale catalyst. Effectively separated. [Precipitate composition]: about 18% by weight: about 2% by weight: about 80% by weight: about 2% by weight: 1% by weight or less of water-glycol iodide salt (Iodized quaternary scale) Chloride salt (chlorinated four Scales) Potassium carbonate The precipitate was dissolved in ethylene glycol and recycled to the reactor. By performing the recovery and recycling of the catalyst as described above, the ethylene glycol process can be used without any decrease in the efficiency of the reaction, and the operation can be continued efficiently. EXAMPLE I - 2 In Example 1-1, 'concentration A after separation and removal of ethylene glycol' is taken as -32 - (30) 1313260 generation of potassium iodide aqueous solution is added with the same amount of distilled water as concentrate A, and the same operation is carried out. The solid is precipitated. When the precipitate was subjected to solid-liquid separation and analysis, the precipitate contained 94% by weight of the iodide salt in the extract A and about 13% by weight of the chloride salt, and it was confirmed that the iodinated quaternary catalyst was efficiently Chlorine salt separation. The liquid after separation of the precipitate (hereinafter referred to as "separation liquid A") was dissolved in about 6% by weight of the iodide salt in the extract A and about 87% by weight of the chloride salt. To the separation liquid A, 1.2 mol of potassium iodide relative to the chloride salt in the liquid was added to a 50% by weight aqueous solution, and the mixture was allowed to stand at 20 ° C for 1 hour. When the precipitate was subjected to solid-liquid separation and analysis, it was confirmed that 50% by weight of the chlorine salt in the above-mentioned extract A was efficiently separated by the iodide quaternary catalyst. Example 1 - 3 The separating liquid A obtained in Example 1 - 2 was distilled, and 50% by weight of water in the separating liquid A was distilled off and concentrated. To the concentrate, 1.2 mol of potassium iodide relative to the chloride salt in the solution was added to an aqueous solution of 50% by weight, and the mixture was allowed to stand at 20 ° C for 1 hour. When the precipitate was subjected to solid-liquid separation for analysis, it was confirmed that about 75 wt% of the chloride salt in the above-mentioned extract A was efficiently separated by the Yaohua quaternary catalyst. Example 2 - 1 was pressurized to 2.0 MPa with carbon dioxide, and the residence time was 丨 hr, 1 〇〇 ° C of the first reactor was supplied with 3 wt. of tributylmethyl sulfonium iodide / hour, potassium carbonate 〇 8 parts by weight/hour, a raw material ethylene oxide aqueous solution (-33-(31) 1313260 60% by weight) 78 parts by weight/hour, and a reaction liquid containing ethylene carbonate and ethylene glycol (EG) was obtained. The whole reactor was transferred to a second reactor with a residence time of 2 hours 'pressure 〇. 5 MPa, a temperature of 15 〇t, and the ethyl carbonate vinegar contained therein was hydrolyzed to obtain an aqueous solution of a catalyst containing ethylene glycol. Shares/hour. The obtained reaction liquid is distilled in a vacuum distillation tower of 1 40 ° C '1 1 kPa (80 mmHg) at the bottom of the column, and the dehydrated liquid is obtained from the bottom of the column, and then it is further reduced to l4 〇t, 8,000. The reduced pressure evaporator operated by Pa (60 mm Hg) evaporates most of the ethylene glycol, and the catalyst is concentrated from the bottom of the evaporator to a concentration of 3 parts by weight per hour. The recovered catalyst liquid is recycled to the first reactor for use as a touch. After one year of continuous operation, the composition of the catalyst liquid is as follows. [Tactile liquid composition] Ethylene glycol iodide salt (Iodized quaternary scale) Chloride salt (chlorinated tetrabasic) Potassium carbonate about 59% by weight About 33% by weight About 6% by weight About 2% by weight After the above composition is reached 'Change to take out one part of the catalyst liquid at 0.02 parts by weight/hour. The catalyst liquid to be taken out (hereinafter referred to as "extraction liquid A") is about the ethylene glycol contained in the ablation device at a condition of 3 Torr (400 Pa) and 1280 ° C. 93% by weight. The liquid after removing the ethylene glycol (hereinafter referred to as "concentrate A") is kept at 95 ° C, and water such as concentrate A is added, stirred and mixed, and cooled to 2 (TC, and then allowed to stand 1). -34- (32) 1313260 Precipitate (hereinafter referred to as "precipitate A"). The filtrate is solidified by a suction filter, and the resulting filtrate (hereinafter referred to as "filtrate A") is filtered. ''Liquid A$ is as follows, which contains about 8% by weight of the chlorine salt in the above-mentioned extract A. On the other hand, the above precipitate A is analyzed as follows, which is contained in the iodide salt in the above-mentioned extract A About 98% by weight [Melted filtrate A composition] Water ethylene glycol iodide salt (Iodized quaternary acid) Chloride salt (chlorinated tetrabasic) Potassium carbonate: about 78% by weight: About 7% by weight: About 1% by weight : about 10% by weight: about 4% by weight, the composition of the precipitate A [precipitate A composition]: about 16% by weight: about 1% by weight: about 80% by weight: about 2% by weight: 1% by weight The following water ethylene glycol iodide salt (Iodized Quaternary Ammonium) Chloride salt (chlorinated quaternary scale) The water and ethylene glycol contained in the potassium carbonate filtrate A are removed by an evaporator operated at 140 ° C. And the removal of ethylene glycol reduced the pressure and finally maintained at 5 Torr (6 60 Pa) for 30 minutes. After this operation, the amount of water contained in the distillation residue and the amount of ethylene-35-(33) 1313260 alcohol were reduced to 1. 〇% by weight or less. After removing water and ethylene glycol, the fc and residue are added in equal weight of acetone. Secondly, the liquid obtained is transferred to a storage tank equipped with a mixer, which will be 1.2 moles relative to the chloride salt contained. The sodium iodide is directly added as a solid and stirred at room temperature for 1 hour. The precipitate precipitated by the inorganic chloride precipitation operation is analyzed by solid-liquid separation with a suction filter, and the precipitate is equivalent to the filtrate A. The sodium chloride of 98% by weight or more of the chlorine salt in the middle is present. On the other hand, the filtrate obtained by separating the solid solution (hereinafter referred to as "filtrate B") is introduced at 5 Torr (660 Pa), 110 ° C. In the operated evaporator, the acetone and ethylene glycol in the filtrate B were substantially completely evaporated, and the obtained solid was mixed and washed with water of equal weight, and then separated by solid filtration with a suction filter. The obtained solid was analyzed (hereinafter referred to as "solid B". The composition is as follows. [Solid B composition]: about 17% by weight: 1% by weight Bottom: about 81% by weight: 1% by weight or less: about 1% by weight Water ethylene glycol iodide salt (Iodized quaternary scale) Chloride salt (Four grade iron chloride) Sodium iodide The solid B and the above precipitate When A is combined, about 98% by weight of the iodide salt and the chlorine salt in the extract A is contained in the iodine quaternary rust, and it is dissolved in an equal weight of ethylene glycol' to be recycled to the reactor. In the recovery and recycling, while continuing to operate, there is no problem of a decrease in reaction efficiency in the ethylene-36-(34) 1313260 alcohol process, and it can operate continuously and efficiently. Embodiment 2 - 2 In Example 2 - 1, The concentrate a after separating and removing ethylene glycol is added with an organic solvent 'equation weight of n-butanol to dissolve. This solution was sent to a storage tank equipped with a stirrer to add a molar amount of solid potassium iodide such as a chloride salt contained in the liquid, and mixed at room temperature for 2 hours. When the precipitate is analyzed by solid-liquid separation by suction, the precipitate contains an amount of potassium chloride equivalent to 95% by weight or more of the chloride salt contained in the concentrate A. On the other hand, the filtrate was introduced into an evaporator operated at 5 Torr (660 Pa) and 1 l ° C, and the butanol and ethylene glycol in the filtrate were substantially completely evaporated, and the resulting solid was mixed with an equal weight of water. After 'separating the solid-liquid with a suction filter. The solid obtained was analyzed to have a composition of about 9.5 wt% of the iodide salt and the chloride salt in the extract A in terms of cesium iodide. [Solid composition]: about 18% by weight: 2% by weight: about 80% by weight: 1% by weight or less: about 1% by weight or less of water-glycol iodide salt (deuterated four-stage scale) Chloride salt (chlorinated four Stage 鍈) Iodine dissolves the solid in an equal weight of ethylene glycol, and recycles it to the reactor -37- (35) 1313260. The catalyst is recovered and recycled, and the operation is continued without any reaction in the ethylene glycol process. The problem of reduced efficiency 'sustainably and efficiently. Comparative Example 1 In Example 1, a 100 g of the dehydrated reaction liquid was taken out from the bottom of the vacuum distillation column. The ratio of ethylene glycol is 87% relative to the catalyst contained therein. Add equal weight of water to it and cool to 〇 °c ’ no precipitates appear. Example 1 - 4 The filtrate obtained in Example 1-2 was added to a 50% by weight aqueous solution of potassium iodate relative to the chlorate 1 mol of the solution, and allowed to stand at 20 ° C for 1 hour. The precipitates were separated from solid and liquid for analysis. As a result, it was confirmed that about 87% by weight of the chlorate in the filtrate had been efficiently separated by the iodide quaternary scale in the precipitate. Industrial use possibility According to the present invention, iodination and/or bromination was used. In the presence of carbon dioxide, an epoxide such as ethylene oxide is reacted with water or carbon dioxide to produce an alkene derivative such as an alkylene glycol such as ethylene glycol or an alkylene carbonate such as ethylene carbonate. In the method, the iodinated or brominated quaternary catalyst is efficiently recycled from the reaction system, or the chlorinated quaternary scale formed in the reaction system is efficiently converted into iodinated and/or brominated four. The scale is recovered and can be recycled to the reaction system. Therefore, the chlorinated quaternary-38-(36) 1313260 hydrazine, which has low activity against the catalyst, is accumulated in the system, and at the same time, it is converted into iodinated and/or brominated quaternary acid with high catalytic activity and recycled. The catalyst activity in the system can be highly maintained, and the formation reaction of the alkene derivative can be carried out efficiently and stably for a long period of time.

-39 -

Claims (1)

Patent Application No. 93 1 03 109 Patent Application Revision of Chinese Patent Application Revision Amendment of the Republic of China on March 11, 1998 1. A method for producing an alkene derivative, which is provided with iodine or bromine A method for producing an alkene derivative in a reaction step of reacting an epoxide with water to form an alkanediol in the presence of carbon dioxide, characterized by: φ by weight ratio of iodide salt to chloride salt in the reaction solution For at least one part of the reaction liquid and/or the catalyst liquid of 0.01 to 1.0, the alkanediol is removed until the molar ratio of the catalyst to the alkanediol is 20 or less, and then the catalyst is recovered by mixing with water. 2. The method for producing an alkene derivative according to claim 1, wherein the molar ratio of the catalyst to the alkanediol is at most 2 times. 3. The method for producing an alkene derivative according to claim 1 or 2, wherein the operating temperature when the catalyst is mixed with water is 3 (TC or less). 4. The alkene according to claim 1 a method for producing a derivative, wherein the amount of water to be mixed is 0. 1 to 5 times by weight with respect to the recovered catalyst. 5. The method for producing an alkene derivative according to claim 1, wherein the mixture is mixed with water. After the solid-liquid separation, the catalyst is separated as a solid, and then recycled to the reaction step. 6. The method for producing an alkene derivative according to claim 5, wherein the liquid separated by solid-liquid separation is used as a contact The washing liquid is used in the circulation. 1313260 7 · The method for producing an alkene derivative according to the first aspect of the patent application, wherein the epoxide is a epoxide. 8 _ - a catalyst regeneration method is characterized by: Containing chlorine obtained by a reaction step of reacting an epoxide containing a chlorinated compound as an impurity with water to form an alkanediol by using iodinated and/or brominated ferrous iron as a catalyst in the presence of carbon dioxide Four-level scales and And/or brominated quaternary scales _ mixture 'by mixing with iodide and/or bromide, converting the chlorinated quaternary ' money into iodinated and/or brominated quaternary money and precipitated in water Φ 9. A catalyst regeneration method characterized by comprising: a reaction step obtained by reacting an epoxide with carbon dioxide to form an alkylene carbonate by using an iodinated and/or brominated quaternary scale as a catalyst a mixture of quaternary chlorinated tetrachloride and iodinated and/or brominated quaternary iron, converted to iodinated and/or brominated quaternary scales by mixing with iodide and/or bromide And precipitated in water. 10. The catalyst regeneration method according to claim 8 or 9, which comprises a mixture of chlorinated quaternary scales and iodinated and/or brominated quaternary scales, from 0 to the reaction step The reaction liquid taken out from the reaction liquid or the residue of the water and/or the alkene derivative of the target product obtained by distillation from the reaction liquid. 11. If the application scope is 8 or 9 Catalyst regeneration method comprising a mixture of quaternary phosphonium chloride and iodinated and/or quaternary phosphonium a system, a reaction liquid taken out from the reaction step, or a residue obtained by distilling off a part of the water and/or an alkene derivative of the target product from the reaction liquid, mixed with water After the medium is precipitated as a solid, the separated aqueous solution is used in the catalyst regeneration method of any one of claims 8 or 9 of the invention, wherein the precipitated iodide and/or bromide is recovered. Level of money, recycled to the reaction step. 13. - Catalyst regeneration method, characterized by: using iodinated and / or brominated ferrous iron as a catalyst, in the presence of carbon dioxide to contain chlorine compounds as impurities a mixture of chlorinated tetrabasin and iodinated and/or brominated quaternary scale obtained by the reaction step of reacting epoxide with water to form an alkanediol, which is obtained by adding iodide and/or bromide. The chlorine of the chlorinated quaternary acid is precipitated as an inorganic chloride from the organic solvent, and the iodinated and/or brominated quaternary scale is recovered. A catalyst regeneration method characterized by using a chlorinated four obtained by a reaction step of reacting an epoxide with carbon dioxide to form an alkylene carbonate using iodinated and/or brominated quaternary acid as a catalyst. In a mixture of scales and iodized and/or brominated quaternary rust, 'chlorine from chlorinated tetrabasic as an inorganic chloride is precipitated from an organic solvent by adding iodide and/or bromide to recover iodide And / or brominated four money. 1 5 . The catalyst regeneration method according to claim 13 or 14 of the patent application 'containing a mixture of chlorinated quaternary scales and iodinated and/or brominated quaternary scales' is as follows (a) to (c) Any one of: (a) adding water to the reaction liquid taken from the reaction step to precipitate the catalyst, and dehydrating the separated aqueous solution to obtain a liquid or a solid, (b) taking the reaction from the reaction In the reaction liquid of the step, the remaining part of the water and/or the target product alkene derivative is distilled off and removed. -3- 1313260 Water is added to precipitate the catalyst as a solid, and the separated aqueous solution is separated. a liquid or solid obtained by dehydration, (c) a liquid obtained by dissolving a liquid or solid obtained by dehydration of (a) or (b) in an organic solvent. 16. The catalyst regeneration method according to claim 13 or 14, which comprises a mixture of chlorinated quaternary acid and iodinated and/or brominated quaternary rust, _ (d), (e) Any one of: (d) diluting the reaction liquid from the reaction step with a liquid of φ in an organic solvent, (e) at least one of the water and/or the target product alkene derivative from the reaction liquid taken from the reaction step. A portion of the residue obtained by distillation or a solution obtained by dissolving the residue in an organic solvent. 17. The catalyst regeneration process of claim 13 or 14, wherein the recovered iodide and/or brominated quaternary rust is recycled to the reaction step. A method for producing an alkene derivative, which comprises the step of reacting an epoxide with carbon dioxide to form an alkylene carbonate using iodinated and/or brominated quaternary acid as a catalyst. A method for producing an alkene derivative, characterized by: adding an iodide and/or a bromide in a mixture containing chlorinated tetrabasic and iodinated and/or brominated quaternary scales obtained by the reaction step The chlorinated quaternary acid is converted into iodinated and/or brominated quaternary scales which are precipitated in water and recovered, and recycled to the reaction step. A method for producing an alkene derivative, which comprises reacting an epoxide with carbon dioxide by -4- 1313260 to form an alkylene carbonate using iodinated and/or brominated quaternary scales as a catalyst. A method for producing a dilute derivative of a step, characterized by: adding iodide and/or to a mixture containing chlorinated quaternary acid and iodinated and/or brominated quaternary scale obtained by the reaction step The bromide precipitates chlorine from the chlorinated quaternary scale as an inorganic chloride in an organic solvent, recovers the iodinated and/or brominated quaternary scales, and recycles to the reaction step.