TW200422285A - Method for producing alkylene derivative and method for regenerating catalyst for producing alkylene derivative - Google Patents

Abstract

A method for producing an alkylene derivative such as ethylene glycol or ethylene carbonate wherein ethylene oxide is reacted with water or carbon dioxide in the presence of carbon dioxide by the use of a quaternary phosphonium iodide or bromide catalyst, characterized in that the quaternary phosphonium iodide or bromide catalyst is recovered efficiently from the reaction system and is circulated for use, and in that quaternary phosphonium chloride formed in the reaction system is converted efficiently to quaternary phosphonium iodide or bromide, and the resultant iodide or bromide is recovered and circulated to the reaction system for use. Water and an alkylene glycol, or the alkylene glycol are removed from at least a part of the reaction and/or catalyst solutions in such a way that the molar ratio of the alkylene glycol to the catalyst is 20 times or less, and then the catalyst is recovered by adding water. Or by adding an iodide or a bromide to the mixture containing a quaternary phosphonium chloride and the quaternary phosphonium iodide or bromide obtained in the reaction process to convert the quaternary phosphonium chloride into the quaternary phosphonium iodide or bromide and then depositing the quaternary phosphonium iodide or bromide in water. Or recovering quaternary phosphonium iodide and/or the quaternary phosphonium bromide by depositing the chlorine derived from the quaternary phosphonium chloride as an inorganic chloride in an organic solution, and recycling the recovered quaternary phosphonium iodide or bromide to reaction steps.

Description

200422285 Π) 发明, description of the invention [Technical field to which the invention belongs]

The present invention relates to a method for producing an alkene derivative such as an alkanediol or an alkanediol. In particular, the present invention relates to the use of iodized and / or brominated quaternary catalysts to make epoxides such as ethylene oxide. A method of reacting with water and carbon dioxide to produce glycols such as ethylene glycol, or a method of reacting epoxide with carbon dioxide to produce ethylene carbonate and the like, in particular, efficiently recovering iodine from the reaction system Recycling of quaternary and / or brominated quaternary money. In the present invention, alkanediol means, for example, alkanediol having 2 to 10 carbon atoms, such as ethylene glycol and propylene glycol, and alkene carbonate means, for example, 2 to 10 carbon atoms, such as ethylene carbonate and propylene carbonate. Alkyl carbonate around 10. [Previous technology] Glycol is produced on a large scale by directly reacting and oxidizing ethylene oxide (ethylene oxide) with water to hydrolyze. This method is to suppress by-products such as diethylene glycol and triethylene glycol during hydrolysis. The excess of stoichiometric excess water must be used relative to ethylene oxide. Therefore, a large amount of excess water must be removed by distilling the ethylene glycol aqueous solution to obtain purified ethylene glycol, which has a problem of consuming a large amount of energy. As a solution to this problem, a method of reacting water with ethylene oxide in the presence of carbon dioxide to produce ethylene glycol has been proposed. In this reaction system, ethylene oxide reacts with carbon dioxide to form ethylene carbonate, which is a two-stage reaction in which ethylene carbonate is hydrolyzed to form ethylene glycol. This two-stage reaction is carried out in the same reactor due to the presence of water in the reaction system, and in order to promote the completion of the second-stage reaction -4- (2) (2) 200422285 All ’can also be set up in another reactor in the latter stage. Hydrolysis of ethylene carbonate is due to the by-products of diethylene glycol and triethylene glycol. Hydrolysis can be carried out with water that is slightly more than that in stoichiometry. The cost of dehydration of the produced ethylene glycol aqueous solution can be greatly reduced. The hydrolysis of ethylene carbonate produced by the reaction of ethylene oxide with carbon dioxide produces carbon dioxide, which is recycled for reuse. In addition, this method can reduce the reaction conditions and reduce the amount of raw material water to suppress the amount of ethylene glycol produced, so that ethylene carbonate can also be produced. As catalysts for the production of ethylene glycol and / or ethylene carbonate from ethylene oxide, various proposals have been made. One of the better ones is an organic rust salt, and the most preferable one is an iodized or brominated fourth grade. Scale (Japanese Patent Publication No. 5 5 —476 1 7). In addition, an alkali metal carbonate can also be used as an accelerator for such organic scale salts (Japanese Patent Application Laid-Open No. 1 2-1 28 8 14). The ethylene oxide of the raw material is produced by the oxidation of ethylene. In order to increase the selectivity of the oxidation reaction, the reaction system supplies chlorohydrocarbons such as ethyl chloride as a selectivity regulator (Japanese Patent Application Laid-Open No. 2-1 04579). . The method of reacting ethylene oxide with water or carbon dioxide to produce ethylene glycol or vinyl carbonate in the presence of carbon dioxide is, as mentioned above, an industrially advantageous method without the problem of by-products, but after the reaction continues, there are The problem of decreased reaction efficiency. The present inventors discussed the reason for the decrease in the reaction efficiency, and as a result, it was found that the reason was that the iodized or brominated quaternary scale catalyst in the reaction system was converted into a chloride having a low catalytic activity. In fact, after about one year of operation of the equipment, about 20% by weight of the iodized or brominated quaternary catalyst in the reaction system was converted into chlorinated quaternary scale. -5- (3) 200422285 The iodized or brominated quaternary scale is converted to chlorine by chlorinating the impurities contained in the raw material ethylene oxide. As mentioned above, in the ethylene oxide production process, the supply of chlorocarbons is used as the selectivity. The process of adjusting the purification system so that the chlorine compound remains in the diol or ethylene carbonate is adjusted. Through the introduction of chlorine compounds, the quaternary scale of the reaction mechanism is refined into chlorinated quaternary rust. Therefore, ethylene glycol or ethylene carbonate removes iodinated or brominated quaternary scales with low reactivity and high activity from catalysts of the reaction system. However, the decline is due to the conversion with time and the reaction system catalyst iodization or bromide four methods, or the conversion of chlorinated quaternary rust to iodine have not been discussed at all. [Summary of the Invention] The purpose of the present invention is to solve the chlorination generated in the above-mentioned habit / or brominated quaternary scale catalyst in the reaction of carbon dioxide oxide with water or with carbon dioxide, alkene derivatives such as alkylene carbonates such as vinyl acid esters The quaternary scales are efficiently converted to iodinated and / or brominated quaternary scales to maintain the catalyst activity in the reaction system. The reason for the quaternary scales should be introduced into the reaction system. That is, in order to improve the reaction selectivity to the reactant, the chlorine compound contained in the chlorohydrocarbon is the ethylene oxide institute, so it is mixed with ethylene and the product is mixed with ethylene oxide. The guidance is unknown, but it should be iodized or bromine.

In the process, it is necessary to separate the quaternary chlorinated quaternary scales. Only the chlorides are retained, and the conventional reaction efficiency is not clearly explained at any time. A method for the separation of quaternary scale and chlorinated quaternary scale or quaternary quaternary hydrazone. If the problem is known, we provide the use of iodination and the presence of ethylene oxide and other rings to produce alkanediols or carbons such as ethylene glycol. The method is to remove the reaction, or recycle the chlorinated quaternary scales to the reaction system, so that the alkene derivative production reaction • 6-(4) Long-term stable and efficient method. The gist of the present invention has the following features (1) a method for producing an alkene derivative using iodized or brominated quaternary germanium catalyst in the presence of carbon dioxide to react ethylene oxide with water to form alkanediene, It is characterized in that: at least a part of the reaction liquid and / or the catalyst liquid is used to remove the alkane so that the molar ratio to the catalyst alkanediol becomes 20 times or less, and then the water is combined to recover the catalyst. (2) The method of (1) above, wherein the molar ratio of the alkanediol to the catalyst is 2 times or less. (3) The manufacturing method of (1) or (2) above, wherein the operating temperature when the catalyst is mixed with water to recover the catalyst is 30 ° C or lower. (4) The production method according to any one of (1) to (3), wherein the amount of the mixed water is 0.1 times or more the weight of the catalyst. (5) The manufacturing method of any one of (1) to (4) above, wherein the catalyst is solid-separated after being mixed with water and solid-liquid separation, and then recycled to the above-mentioned reaction step. (6) The manufacturing method of (5) above, wherein the liquid separated by solid-liquid separation is recycled for use as a catalyst washing water. (7) The production method according to any one of (1) to (6) above, wherein the epoxide is ethylene oxide. (8) It is characterized in that it is obtained from a reaction step using iodized and / or tritiated scales as a catalyst to react an epoxide containing an impurity chlorine compound with water in the presence of carbon dioxide to form an alkanediol. Quaternary chloride and iodine (5) (5) 200422285 A mixture of quaternized and / or brominated quaternary, mixed with iodide and / or bromide to convert the quaternary chlorinated quaternary into iodized and / Or catalyst regeneration method of brominated fourth-grade rust precipitated in water. (9) It is characterized in that it is obtained from a reaction step of using iodized and / or brominated quaternary hydrazone as a catalyst to react epoxide with carbon dioxide to form alkylene carbonate, which contains chlorinated quaternary rust and iodized and A catalyst regeneration method for mixing a mixture of quaternary bromide with iodide and / or bromide to convert chlorinated quaternary money into iodized and / or brominated quaternary scale in water. (10) The method of (8) or (9) above, which contains a mixture of quaternary chlorinated quaternary and iodized and / or brominated quaternary rust, which is the reaction liquid taken out from the above reaction step, or from the reaction Residue after distilling off at least a part of water and / or the target product alkene derivative. (1 1) The method of (8) or (9) above, which comprises a mixture of quaternary chlorinated quaternary and iodized and / or brominated quaternary quaternary scale, the reaction solution taken out from the above reaction step, or from the reaction Residue after liquid distillation removes at least a part of water and / or the target product alkene derivative, mixes with water to precipitate the catalyst as a solid, and separates it into an aqueous solution. (12) The method according to any one of (8) to (11), wherein the recovered iodized and / or brominated quaternary thorium is recycled to the above reaction step. (1 3) It is characterized by the reaction step obtained by reacting an epoxide containing an impurity chlorine compound with water to form an alkanediol in the presence of carbon dioxide using iodized and / or brominated quaternary thorium as a catalyst , Contains a mixture of chlorinated quaternary scales and iodized and / or brominated quaternary money. Adding iodide and / or bromide causes the chlorine from chlorinated quaternary scales to precipitate out of organic solvents as inorganic chlorides. 8- (6) (6) 200422285, a catalyst regeneration method for recovering iodized and / or brominated fourth-grade scales. (1 4) It is characterized in that it comprises a reaction step obtained by using iodized and / or brominated quaternary hydrazone as a catalyst to react epoxide with carbon dioxide to form ethylene carbonate, and contains chlorinated quaternary money and iodination And / or brominated quaternary scale, adding iodide and / or bromide to separate the chlorine from quaternary quaternary chloride into inorganic solvent with inorganic chloride to recover iodized and / or brominated quaternary scale Catalyst regeneration method. (15) The method according to (13) or (14) above, which comprises a mixture of quaternary chlorinated scale and iodinated and / or brominated quaternary rust, which is any one of the following (a) to (c). (a) adding the reaction solution obtained from the above reaction step with water to precipitate the catalyst, and separating the separated aqueous solution into a liquid or solid obtained by dehydration; (b) distilling away from the reaction solution obtained from the above reaction step; Water and / or the remainder of at least a part of the target product alkene derivative, add the water to precipitate the above-mentioned catalyst as a solid, and separate the separated aqueous solution into a liquid or solid obtained by dehydration. (A) or (b) The liquid or solid obtained by dehydration is a liquid obtained by dissolving in an organic solvent. (16) The method of (13) or (14) above, which comprises a mixture of chlorinated quaternary rust and iodinated and / or brominated quaternary scales, which is any one of (d) and (e) below. (d) liquid obtained by diluting the reaction solution taken from the above reaction step with an organic solvent, -9- (7) (7) 200422285 (e) removing water and / or the target product from the reaction solution taken from the above reaction step by distillation Residue after at least a part of the alkene derivative, or a liquid obtained by dissolving the residue in an organic solvent. (1 7) The method of any one of (1 3) or (16) above, wherein the recovered iodinated and / or brominated quaternary scale is recycled in the above reaction step. (18) A method for producing an alkene derivative having a reaction step of using iodized and / or brominated quaternary scales as a catalyst to react epoxide with carbon dioxide to form ethylene carbonate, characterized in that: In this reaction step, a mixture containing quaternary chlorinated rust and iodized and / or brominated quaternary scale is added, and iodide and / or bromide are added to convert the chlorinated quaternary scale into iodized and / or brominated The quaternary scale is precipitated and recovered in water, and is recycled to the reaction step. (19) A method for producing an alkene derivative using iodized and / or brominated quaternary scale as a catalyst, including a reaction step of reacting an epoxide with carbon dioxide to form an alkene carbonate, which is characterized by: From this reaction step, a mixture containing chlorinated quaternary scales and iodized and / or brominated quaternary scales is added, and iodide and / or bromide are added to make the chlorine from the chlorinated quaternary scales into inorganic chloride in an organic solvent. Precipitate to recover iodinated and / or brominated quaternary money and recycle to the reaction step. In the present invention, once a reaction liquid and / or a catalyst liquid containing a high concentration of catalyst is mixed with water, the chloride salt from the catalyst remains dissolved in the liquid, and the iodine salt or bromine salt starts to precipitate. That is, any one of the iodonium salt, bromine salt, and chloride salt is more soluble than alkanediol and alkylene carbonate, and the iodonium salt or bromine salt has low solubility in water. The chloride salt has high solubility in water. The precipitated iodized or brominated quaternary mirror, under -10- (9) (9) 200422285, the liquid flowing out from the reactor or the liquid taken out from the reactor is sometimes referred to as the "reaction liquid". The reaction liquid distills and separates water, alkanediol, and alkylene carbonate, and the liquid in which the catalyst is concentrated is sometimes referred to simply as "catalyst liquid". The mixture to be treated in the present invention may be a reaction solution containing a catalyst taken directly from a reaction step of an alkanediol or an alkene carbonate, or a solvent such as an alkanediol or an alkane carbonate may be used. The liquid catalyst liquid or solid residue after the partial or total evaporation and removal of the olefin ester is added with water to precipitate a part of the catalyst and the recovered liquid (hereinafter, the catalyst liquid or solid residue is treated with water The operation of adding a part of the catalyst for precipitation and recovery is sometimes referred to as "pre-recovery".) After such a recovery process, the concentration of the quaternary chlorinated scale of the treatment target mixture can be increased, which becomes iodination and / or bromine The transformation and recovery rate of chemical quaternary scales can be improved. That is, because the solubility of iodinated and / or brominated quaternary quaternary ions in water is lower than that of chlorinated quaternary quaternary scales, so if water is added, iodinated and / or brominated quaternary quaternary scales will precipitate, and Quaternary scales are mostly soluble in water. After the recovery treatment as described above, the concentration of the quaternary chlorinated quaternary scales of the mixture to be treated can be increased, and the conversion and recovery rate of the quaternary quaternary scales can be improved. In another method, instead of adding water to the catalyst liquid or solid residue during the above-mentioned pre-recovery, an aqueous solution of dissolved iodide and / or bromide is used instead, thereby improving iodization and / or bromination. The recovery rate of the fourth scale. In either method, when iodide and / or bromide are added to the quaternary chlorinated scales dissolved in water, the chlorinated quaternary scales are precipitated with iodide and / or bromide. Added compound chloride. Therefore, after the precipitate is separated by solid-liquid separation, the tetra-12-chloride (12) 200422285 scale can be easily separated and recovered by iodination and / or bromide. The thus recovered iodinated and / or brominated quaternary hydrazone can be recycled to the reaction step of alkanediol or alkene carbonate.

Furthermore, according to the present invention, in the mixture obtained from the reaction step or the recovery step described above, a mixture containing quaternary chlorinated scale and iodinated and / or brominated quaternary phosphonium is added with iodide and / or bromide to make it from chlorine. Chlorinated quaternary phosphonium is precipitated into inorganic solvents with inorganic chloride, and iodized and / or brominated quaternary scale can be recovered.

That is, a reaction step obtained by reacting an epoxide with water or carbon dioxide to form an alkanediol or an alkylene carbonate in the presence of carbon dioxide using a quaternary scale catalyst using iodination and / or bromination, containing A mixture of quaternary chlorinated scales and iodized and / or brominated quaternary scales. Adding iodide and / or bromide can convert the quaternary chlorinated scales in the mixture to iodized and / or brominated Grade scales. On the other hand, the chlorine derived from chlorinated quaternary scales is precipitated in an organic solvent with a low solubility in an organic solvent, and the chlorinated iodide and / or bromide dissolved in the organic solvent can be recovered by separation. Four scales. Hereinafter, as described above, the operation of precipitating chlorine derived from chlorinated quaternary rust in an organic solvent as an inorganic chloride is sometimes referred to as "inorganic chloride precipitation operation". In addition, in order to precipitate the chloride of quaternary quaternary rust as inorganic chloride, iodide and / or bromide is added, and a mixture containing chlorinated quaternary scale and iodinated and / or brominated quaternary scale is sometimes called "Processing target mixture". The quaternary chloride is converted into iodide or bromide, and the chloride from the chloride is precipitated into the organic solvent as inorganic chloride. The separated liquid after separation is dissolved in the organic solvent with iodination and / or Liquid of brominated quaternary scale • 13 · (11) 200422285. Therefore, by removing the organic solvent of the separation liquid by evaporation, the iodized and / or brominated quaternary money can be recovered as a solid. The recovered iodinated and / or brominated quaternary money can be directly or dissolved in a suitable solvent after being washed with water if necessary, and can be reused in the reaction step of alkanediol or alkene carbonate. [Embodiment] Hereinafter, an embodiment of the method for producing an alkanediol of the present invention will be described in detail.

〇 The present invention is described below with reference to a reactor suitable for producing ethylene glycol from ethylene oxide using an iodized quaternary catalyst, but it 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. The same applies to those who use quaternary scale bromine for the catalyst system or iodized and brominated quaternary scale for the catalyst system.

Furthermore, as described above, the present invention uses a method similar to the method for producing an alkanediol to change the reaction conditions and lower the reaction temperature to suppress the production of alkanediols such as ethylene glycol. It can also be applied to the production of alkanecarbonates such as ethylene carbonate. The reaction of alkenyl esters is also applicable to the reaction that uses both alkenyl carbonate and alkanyl glycol as target products. The following example shows that iodide is added to the mixture to be treated, and the chlorinated quaternary scale is converted into quaternized quaternary scale and recovered. Method. It can also replace bromide instead of iodide, convert quaternary chloride into quaternary bromide and recover, or use iodide and bromide to convert chlorinated quaternary scale into quaternary iodide. And brominated quaternary scales and recovered. -14- (12) (12) 200422285 The following is an example of the method of adding inorganic iodide to the mixture to be treated to convert the chlorinated quaternary rust into iodized quaternary scale. At the same time, the chlorine from chlorinated quaternary scale is converted to Method for precipitation of inorganic chloride. It can also replace bromide instead of iodide to convert chlorinated grades to quaternary bromide scales. At the same time, the chlorine from chlorinated grades can be precipitated as inorganic chloride; and iodide and bromine can also be used. The compound converts the chlorinated quaternary rust into iodized quaternary scale and brominated quaternary scale, and at the same time, the chlorine from the chlorinated quaternary scale is precipitated as an inorganic chloride. Those suitable for the fourth-order iodine catalyst of the present invention include the compounds described in Japanese Patent Publication No. 5 8-2 2 4 48. Representative examples include triphenylmethyl iodide scale, triphenylpropyl iodide scale, triphenylbenzyl iodide scale, tributylmethyl iodide scale, and the like. Such a quaternary scale iodide catalyst is preferably supplied to the reaction system at a molar ratio of 0.001 to 0.05 times that of ethylene oxide. In the case of using a fourth-grade bromine scale, a bromide catalyst corresponding to the above-mentioned fourth-grade iodine scale can be used, and its preferred amount is equivalent to that of the fourth-grade iodine scale catalyst. In the present invention, an alkali metal carbonate as a promoter can coexist in the reaction system, thereby improving the efficiency of ethylene glycol production. So that the test metal carbonate is present in the reaction system, sodium or sodium may be added, preferably an alkali metal hydroxide such as potassium, carbonate or bicarbonate. Any addition of an alkali metal compound will be added to the reaction system. Exist as carbonate. In this case, an alkali metal carbonate is preferred. Carbonate is preferred, as it has a molar specific energy of 0.01 to 1 relative to the iodized quaternary scale. The amount of water relative to ethylene oxide can be reduced to a stoichiometric amount, and it can be lower than that depending on the reaction form ', but it is generally preferably about 1.0 to 10.0 times moles relative to ethylene oxide. Carbon dioxide is equivalent to ethylene oxide at -15- (13) 200422285 moles or less to obtain a sufficient effect. Under normal conditions, g ears are used at about 0.1 to 5.0 moles. It does not have to be strictly limited. The reaction temperature varies depending on the type of epoxide and the type of catalyst, and the composition of the reaction solution is generally 50 to 18 (the pressure of TC varies with the amount of carbon dioxide, the reaction temperature, etc., but also changes with its passage. Generally In the range of 0.5 to 5.0 million. There are no special restrictions on the form of the reactor, which can be carried out smoothly. The number of reactors and residence time are selected to achieve the desired ethylene glycol, and a reactor can be added if necessary to react olefins. Ester hydrolysis. The reaction solution from the reactor is separated by distillation to separate the water. The remaining catalyst-containing liquid (catalyst solution) is recycled to the reactor for the reaction. The reaction system will be iodized or brominated. When the scales efficiently recover the catalyst recovered from the reaction liquid from the reactor, the catalyst is difficult to precipitate due to the low degree. It is preferred to remove the anti-diol and increase the catalyst concentration (after removing the ethylene glycol). Catalyst 0 When using the catalyst liquid to recover the catalyst, although it can be directly used with the water medium, in order to improve the recovery rate of the catalyst, it is better to make the amount per 1 mole of ethylene oxide. The range is within the range of the reaction process. It is the best conversion rate for gas-liquid reaction. Most of the ethylene glycol carbonate in the production liquid is used as the catalyst in the next cycle. The original catalyst concentrated water and B) are mixed with water to recover. The catalyst is removed by catalytic distillation to remove the -16- (14) (14) 200422285 ethylene glycol, and the catalyst is mixed with water to recover the catalyst. That is, in this reaction, at least a part of the reaction liquid or the catalyst liquid is taken out from such a reaction step. Parts, remove water and alkanediol or alkanediol, so that the molar ratio of alkanediol and catalyst contained in the liquid is more than 20 times, more preferably 2 times or less, and then with water When the molar ratio of the alkanediol contained in the liquid to the catalyst is less than 20 times the molar ratio, only the water is mixed to precipitate the catalyst and recovered. When the liquid taken out from the reaction step is mixed with water, the iodine is precipitated. The quaternary scale must sometimes be cooled. That is, the solubility of iodine quaternary scale in water or ethylene glycol is lower as the temperature is lower. Generally, the reaction solution taken out from the reaction step is about 100 to 180 ° C. It is preferable that the temperature of the reaction solution is reduced to below 30 ° C after mixing the reaction solution with water, and more preferably from about 0 to 20 ° C. The quaternary iodide scales can be more efficiently precipitated. The cooling depends on the temperature of the reaction solution, the temperature of the mixed water and the amount of mixing. For the actual precipitation, not only cooling, the addition of seed crystals or Pre-existing, stable and efficient crystallization. At least a part of the product ethylene glycol is removed from the liquid taken from the reaction step, preferably a large part (also containing water), so that the catalyst concentration becomes, for example, Above 40% by weight, when mixed with water, the iodized quaternary scale can be precipitated without cooling, and it can be precipitated more efficiently when cooled to 4 (TC or lower. The mixing amount of water varies with the iodized quaternary in the reaction solution. The amount of scale, the amount of ethylene glycol, the amount of chlorine salt, the presence or absence of cooling, and the desired recovery efficiency of quaternary iodide grade 4 vary. If it is too small, it will not be easy to filter, and the dissolution efficiency of chlorinated quaternary scale- 17 · (15) (15) 200422285 The tendency to worsen. On the other hand, when it is too much, the amount of the quaternary iodine scale contained in the liquid phase after the quaternary iodine scale is separated is increased. Generally, the amount of water added for one treatment is appropriately determined in the range of 0.1 to 5 times by weight relative to the treatment liquid, preferably 0.1 to 5 times by weight. The liquid phase separated from the solid can be used as a re-reaction liquid, a catalyst liquid, or a washing water for the catalyst after the ethylene glycol is separated. At this time, if the concentration of quaternary chlorinated rust contained in the rinsing rinsing water increases, the concentration of quaternary chlorinated quaternary chloride contained in the recovered iodized quaternary scales increases. After one to five washings, replace with fresh washing water. The rinsing of the reaction solution is carried out many times, and the method of gradually replacing the rinsing water with a low concentration of quaternary chlorinated ore can also be smoothly implemented. The specific aspect of this operation is to store the cooled water or the iodized quaternary scale slurry in a container in advance, and then supply the reaction solution or catalyst solution and water continuously or in batches, and continuously or batch the resulting mixture. It can be taken out in one pass, and the precipitates contained in it can be recovered by filtration. To separate the ethylene glycol from the reaction solution, for example, a distillation separation operation of ethylene glycol can be performed under reduced pressure. Water accompanying ethylene glycol is also separated. The precipitate obtained by mixing the reaction solution and water in this way is usually a high-activity quaternary iodide catalyst with an iodized salt content of 90% by weight or more and a chloride salt content of 10% by weight or less, which can be effectively recycled in the reaction step. The separation solution after separating the quaternary iodide deposits contained chlorinated quaternary scales. The chlorinated quaternary scale system is subjected to dehalogenation treatment with an OH-type anion exchange resin, neutralized with hydrogen iodide, and directly exchanged chloride ions with iodine ions with an anion exchange resin substituted with iodine. For iodized grade IV-18 (16) (16) 200422285 鍈. In this way, the catalyst can be regenerated, and the obtained regenerated catalyst can be effectively recycled for the reaction step. The application of the present invention can be used to continuously or intermittently take out a portion of the reaction liquid from the reactor in continuous operation, and recover the iodized four-stage scale catalyst, and recycle the recovered iodized four-stage scale catalyst to the reactor. . At this time, the amount of the reaction liquid and / or the amount of the catalyst liquid used to recover the iodized quaternary scale catalyst is not particularly limited, and the reaction is highly maintained in order to remove the chlorine salt in the range where the catalyst recovery cost is not too high. For efficiency, it is preferable to take out the reaction solution continuously or intermittently for treatment, so that the weight ratio of the chloride salt to the iodine salt in the reactor becomes 0.01 to 1.0. The amount to be taken out is not particularly limited, and it is preferable that the amount of each reaction solution is about 0.1 to 100% by weight based on the amount of the catalyst solution. The chlorinated quaternary scales in the reaction system are converted into iodized and / or brominated quaternary scales for recycling and used in the reaction system. The present invention relates to a treatment target mixture containing chlorinated and iodized quaternary scales. The ratio and composition of the chlorinated and iodized quaternary rusts vary with the ratio of chlorine to iodine in the ethylene glycol process, the bleed space, and the subsequent processing (the presence or absence of previous recovery operations, etc.) shown below. There are no special restrictions on the ratio and concentration of chlorination and iodized quaternary scales in the mixture to be treated. From the efficiency of the recovery operation, the chloride ratio and chloride concentration relative to the iodide should be higher, preferably the better. The molar ratio of the treatment target mixture to the quaternary iodine scale and chlorinated quaternary scale is 1/20 times or more, and more preferably 1/10 or more. The concentration of quaternary dysprosium chloride in the treatment target is 0.1. More than 1% by weight, particularly preferably more than 1% by weight. -19- (17) 200422285 Specific examples of the present invention include the following methods other than the method for adding an iodide to the mixture to be treated. It is explained in order that the invention is by no means limited to the following methods. [Application Example I] Take out a part of the liquid in the glycol production process as a catalyst. If it is a catalyst-containing liquid that is present in the process, the removal location is restricted. As mentioned above, the reaction of ethylene oxide to form ethylene glycol is the reaction of alkane with carbon dioxide to form ethylene carbonate, and the second step of ethylene carbonate is ethylene glycol. Therefore, when the liquid is taken from the process and the reaction is performed in a reactor arranged in two stages in series, it can be taken out of the reactor or taken out of the second reactor. When the liquid is taken out at the outlet of the reactor, in the subsequent steps, the recovery rate of the fourth-grade scale is improved, and the one having a higher concentration of chlorination and iodination in the mixture to be treated is preferred. The ene ester is preferably concentrated. The distillation method can be a distillation column or a single unit. Preferably, it is concentrated until the fourth order iodination in the mixture to be treated becomes 1/20 mole times or more of the solvent. In consideration of the quaternary scale salt, the distillation and concentration operation is preferably performed under reduced pressure (400 torr), preferably at a temperature of 60 to 21 ° C. The high-concentration catalyst solution obtained by concentrating the reaction solution by distillation contains iodine scales, and chlorinated tetrachloride formed by chlorination of quaternary scales iodized in the ethylene glycol process, and the catalyst liquid can be concentrated by taking the reaction solution out of the system. Or, the method of separating water, ethylene glycol, ethylene carbonate and catalyst liquid in the process, and the two liquids are special I, ethoxy, and c, which can be decomposed into i, and when the reaction is iodized with 3rd-order scale acid (B) Evaporation concentration and thermal properties (53.2: Fourth-grade scale. 5 Catalyst liquid taken out from the distillation column-20- (18) (18) 200422285.) Used to recover the iodide system of fourth-grade iodine iodide Any ionic compound that can be exchanged with quaternary chlorinated quaternary scales and dissociated in water can be used. It can be appropriately selected by the industry. Based on the solubility, toxicity, price and other points, the preferred ones are sodium and potassium salts. Such as alkali metal salt or hydrogen acid, etc. Inorganic iodide system, any ionic compound that can be exchanged with quaternary rust of chloride and dissociated in water can be applied, and sodium salt is used in terms of solubility, toxicity, price, etc. Alkali metal salts such as potassium and potassium salts are preferred. The content of the quaternary chlorinated quaternary chlorinated substance is preferably equal to or more than the same amount. A suitable range is 0.5 to 10 times mol relative to the quaternary chlorinated quaternary scale present in the mixture to be treated. It is 1 to 5 times mole. Addition of iodide above the necessary solid can improve the recovery rate, but excess iodide is wasted. Addition of iodide can be in the form of solid, organic solvent solution or aqueous solution, and industrially Because the liquid is convenient to use, it is preferable to add it as an organic solvent solution or an aqueous solution. In an aqueous solution, the amount of water is sufficient to dissolve the iodide, and the amount depends on the iodide used. For example, when potassium iodide is used, it is due to water. The saturation solubility is 60%, and the concentration of potassium iodide added to the treatment may be less than or equal to it. Generally, it is preferably added to an aqueous solution of about 1 to 60% by weight. The device for adding iodide to the mixture to be treated may be of any form. The container is preferably a container equipped with a stirring device to promote the ion exchange reaction. The chlorinated quaternary scale present in the mixture to be treated by this operation is converted into -21-(19) 200422285 The quaternary scale, together with the iodide existing in the mixture to be treated, is precipitated out of the water. The precipitation temperature is lower, and the iodized quaternary rust is less. It is better to be at 0 to 30 ° C. Precipitation The iodized quaternary rust is filtered and recovered. The filtering method is not prepared. In addition to filtering with a common filter, centrifugal separation can be used to recover the iodized quaternary scales, such as 10% by weight of chlorinated quaternary scales. Iodide. At this concentration, the reaction step of alcohol can be directly recycled, but if necessary, it can be washed with water to improve the purity of iodide IV and recycled. The water used for rinsing will be used for the next time because it contains iodide IV The iodide water used for dissolving the previously described treatment target mixture may be reused for washing, or the recovered fourth-order iodine scale may be dissolved in, for example, an ethylene glycol circulation system. As described above, the transformation of chlorinated quaternary scales into iodized quaternary scales has been described. This operation can also be performed in an organic solvent. The operation of precipitating inorganic chloride in an organic solvent is described below, and the state of recovering quaternary chlorinated quaternary quaternary quaternary iodide quaternary quaternary quart is described. In the obtained high-concentration catalyst liquid, the presence of the solvent ethylene glycol and / vinyl ester can also be applied to the catalyst liquid of the inorganic chlorine extraction operation of the present invention, which is also suitable for the addition of iodide No other organic solvents with low solubility. In addition, it is better to remove the ethylene glycol and / or ethylene carbonate in the catalyst liquid to become a substantial solid, and then re-dissolve it in other organic solvents, and the inorganic chlorination degree is further reduced to improve the precipitation efficiency. The fourth-grade scale remains in the water with a special limit of about 0 to the second-grade rust. It can be added to the reaction to collect the scale conversion or carbonate analyzer to chlorinate the high-concentration solvent-free solvents. 22- (20) 200422285 The organic solvent used here is preferably one with low solubility of inorganic chloride and high solubility of quaternary scale salt. Suitable solvents are aliphatic halogenated hydrocarbons, ketones, alcohols, nitriles, amines, urea compounds, carbonates.

The 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, 1-propanol, 1-hexanol, 2-hexane Alcohol, 3-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol Alcohol, 2-octanol, 2-ethyl-l-hexanol, 1-nonanol, 2-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1,6-hexane Alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, phenethyl alcohol, etc.

Aliphatic halogenated hydrocarbons are, for example, methylene chloride, 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-dichlorobutane, 1,6-dichlorohexyl, etc. Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, adiponitrile, and benzonitrile. Examples of the fluorene amine include dimethylformamide and dimethylacetamide. Examples of urea compounds include tetramethylurea, 1,3-dimethylimidazolidine-2-one and the like. Ketones include acetone, methyl ethyl ketone and methyl isopropyl ketone. Examples of the carbonate include ethylene carbonate, propylene carbonate, and butene carbonate. The organic solvent may be used singly or in combination of two or more kinds. The amount of the organic solvent to be added is not particularly limited, and is usually 1 to 10 times by weight the total of the chlorinated and iodized quaternary scales in the mixture to be treated. -twenty three-

L (21) (21) 200422285 For example, sodium iodide is easily soluble in acetone, so it is a suitable combination. Since potassium iodide is soluble in ethylene glycol, this combination is also suitable. However, the iodide does not have to be completely dissolved in the organic solvent at this time. Even if the saturated dissolving amount of iodide is a trace amount, after it is added to the mixture to be treated, the iodide is further dissolved to make up for the part consumed by the reaction with quaternary chloride. As a result, the increased solubility can react to form inorganic chlorides. The choice of iodide and organic solvent must be that the iodide, and the inorganic chloride produced by the reaction of the iodide with the quaternary scale of chlorination, have a difference in the solubility in organic solvents. Such combinations include, for example, butanol and ethylene glycol relative to potassium iodide. The device for adding iodide to the mixture to be treated may be any type of container, and a container equipped with a stirring device is preferred to promote the ion exchange reaction. After this operation, the quaternary scales of the quaternary scales of chlorination which are present in the mixture to be treated become quaternary scales of iodine, and chlorine is precipitated as an inorganic chloride. The precipitation temperature is not particularly limited, and depends on the solubility temperature dependence of the inorganic chloride, the boiling point of the organic solvent used, the viscosity, and the solubility of the quaternary scale salt. It is usually at room temperature of 0 to 50 ° C. The reaction between iodide and chlorinated quaternary scale is fast when the viscosity of the solvent is low. When the viscosity of the solvent is high and the solubility of the iodide is low, the mixing time should be extended. If appropriate, the reaction will be completed in about 1 minute to 3 hours. Through this operation, the quaternary scale of the chlorinated quaternary scale in the organic solvent was converted into iodide at a conversion rate of 90% or more, and at the same time, inorganic chloride was precipitated. The precipitated inorganic chloride was removed by filtration. There is no particular limitation on the filtering method. In addition to filtering with a common filter, centrifugation can be used. -24- (22) 200422285 The iodized quaternary scale was dissolved in the filtrate after the inorganic chloride was filtered and separated. The organic solvent was evaporated and removed from the filtrate. The iodized quaternary scale and the excessively added iodide were solid. Recycle. Removal of organic solvents can be done with conventional evaporators. The organic solvent is removed by evaporation. As mentioned above, the heat resistance of the recovered iodized quaternary scale is considered. If necessary, it should be decompressed to a temperature below 200 ° C.

The purity of the recovered iodized quaternary scale is such that, in addition to the excess iodide and the remaining solvent, more than 90%, it can be directly or dissolved in an appropriate solvent such as ethylene glycol for recycling in the reaction step, which is preferred. The recovered solids are washed with water to remove the remaining iodide and solvent before being recycled for use in the reaction step. The water washing can be based on the recovery of solids, adding the washing water into a slurry, filtering or centrifugation. In this case, considering the dissolution loss of the washing water, the amount of the washing water added is preferably 2 times or less the weight of the recovered solid.

The method other than the inorganic chloride removal method in the above method may be a method in which the inorganic chloride is not filtered out to remove the solvent at the same time, and then the above water washing is performed to dissolve the inorganic compound in water and remove it. Another embodiment of the present invention is the following method. [Application Example II] Executed in Application Example I. The concentration of quaternary scale iodized is 1/20 mol times or more than that of ethylene glycol, or a high-concentration catalyst solution concentrated to such a concentration is added and mixed with water. After cooling, the iodized quaternary scale was selectively deposited and recovered before recovery. Here, the water system is added in an arbitrary amount, and because the precipitation effect is not sufficient when it is too small, it must be added at least 0.1 to 25- (23) (23) 200422285 times the weight of the dissolved iodized quaternary scale. . The upper limit of the amount of water to be added is not particularly limited, but in order to prevent the processing capacity from being too large, it is preferably about 5 weight times or less with respect to the dissolved fourth-grade iodide. The temperature during the precipitation operation is preferably lower because the remaining amount of quaternary iodide in water is small. Appropriate at 0 to 30 ° C. In the aqueous solution remaining after the recovered fourth-order iodine scale was recovered, there were unprecipitated fourth-order iodine scale and chlorinated fourth-order scale. As the mixture to be treated, the aqueous solution remaining after recovering the quaternary iodine can be converted into quaternary iodine scale and precipitated by adding iodide after concentration if necessary. The concentration is such that the concentration of quaternary chlorinated quaternary chloride in the mixture to be treated before the addition of iodide reaches 1% by weight or more. It is better in the conversion efficiency of chlorinated quaternary scale and the recovery efficiency of iodized quaternary rust. The type of iodide to be added, the concentration to be added, the method of addition, the method of filtering out the precipitates, and subsequent treatments are the same as the method of Application Example I described above. However, at this time, because water already exists in the system, the iodide can be added as a solid. As a result, the amount of water used is reduced, and the dissolution loss of the fourth grade money in the tablet can be reduced to waste water. After the recovery before the implementation, the water containing the aqueous solution of chlorinated and iodized quaternary scales is preferably 90% or more, and more preferably 99% or more. After removal by evaporation, the mixture is treated, and the inorganic chloride precipitation operation can be performed. . That is, the mixture to be treated is dissolved in an organic solvent in an amount of 1 to 10 times by weight based on the total amount of chlorinated and iodized quaternary compounds in the mixture to be treated, and iodide is added thereto. -26- (24) (24) 200422285 The type of iodide to be added, the concentration to be added, and the method of adding ‘precipitates are filtered out. The subsequent treatments are the same as those in Application Example 1 described above. In this method, water added to precipitate iodized quaternary scales in a high-concentration catalyst liquid may be added as an iodide aqueous solution at this time, that is, the addition of iodide in the subsequent stage is not necessary. No matter what, from the organic solvent solution of the inorganic chloride precipitates after solid-liquid separation, the organic solvent can be removed to recover the iodized quaternary scale ', which can be reused together with the previously recovered iodized quaternary scale. In addition, there are the following methods for implementation. [Application Example III] In Application Example I, the concentration of quaternary scale iodized is 1/20 times or more that of ethylene glycol, or the high-concentration catalyst solution concentrated to such a concentration is more concentrated, and the concentration of the solvent More than 90% is distilled off. At this time, the residue (distillation residue) solidifies as it cools. The solidified residue is washed with an appropriate amount of water, so that the quaternary chlorinated scale in the residue can be dissolved in water and removed. At this time, the temperature of the rinsing water is also lower because the amount of iodized quaternary scale in the rinsing water is less, which is better. It is better to work at 0 to 30 ° C. There is no special limit on the amount of water used for washing, but considering the washing efficiency and the loss of iodized quaternary scale in the wastewater, it is appropriate to use 0.5 to 10 times the weight of the solid residue after washing. The washing water does not have to be pure water, and the circulating water in the process can be used. And can be used for any next cycle. If it is an aqueous solution containing quaternary iodine scale, the dissolution loss of quaternary iodine scale in water can be reduced and it is particularly preferable. There are washed out quaternary chlorinated quaternary money and a small amount of dissolved -27- (25) (25) 200422285 iodized quaternary scale in the water after washing. Take this mixture as a treatment object. As mentioned above, if necessary, after concentration, add iodide to convert quaternary chlorinated quaternary iodide into iodized quaternary osmium. At this time, before the addition of iodide, the concentration of the quaternary chlorinated scale of the treatment target mixture is preferably 1% by weight or more. The type, concentration and method of adding the iodide, the method of filtering the precipitate, and thereafter The processing and the like are the same as those of the application example I described above. At this time, because the water already exists in the system, iodide can be added as a solid. As a result, the amount of water used is reduced, and the dissolution loss of fourth-order iodide in wastewater can be reduced. A method of adding the iodide by using the rinsing water as the treatment target mixture after performing the rinsing operation described above, or using an iodide aqueous solution as the rinsing water, becomes an embodiment in which the steps are shortened. At this time, the concentration of the aqueous iodide solution used is the concentration of iodide in the water after washing, and it may be a concentration that can be added and mixed as described above. The water of the chlorinated and iodinated quaternary scale aqueous solution is preferably 90% or more, more preferably 99% or more, and is treated as a mixture after evaporation and removal, and an inorganic chloride precipitation operation may be performed. That is, the mixture to be treated is dissolved with an organic solvent which is 1 to 10 times by weight in total with respect to the chlorinated and iodized quaternary coins in the mixture to be treated, and iodide is added thereto. The type, concentration and method of addition of iodide, the method for filtering out precipitates, and subsequent processing are the same as those in Application Example I described above. In this method, it is also possible to replace the washing water with an iodide aqueous solution. At this time, the addition of iodide in the latter stage is unnecessary. -28- (26) (26) 200422285 No matter which, the inorganic solvent can be recovered from the organic solvent solution after solid-liquid separation of inorganic chloride precipitates, and the fourth-grade iodide iodide can be recovered by removing the organic solvent, together with the previously recovered iodide Four scales are available for reuse. The concentration of the above-mentioned quaternary iodine quaternary iodine is 1/20 times higher than that of ethylene glycol, or the high-concentration catalyst liquid concentrated to this point can be more concentrated, and the temperature of the solvent must be kept above 90 ° C after distilling more than 90% of the solvent. It remains in liquid state, so it can also be cooled to 0 to 40 ° C after adding water, so that quaternary iodide can be precipitated. Alternatively, the above-mentioned concentrated residue can be supplied continuously or simultaneously with water in the existing cold water or slurry to crystallize it. At this time, in the remaining aqueous solution of the precipitated iodinated scales, there were undissolved iodized and chlorinated quaternary scales. Take the mixture as a treatment object, as described above, after concentrating it if necessary, add iodide to convert the quaternary chlorinated scale into quaternary iodide scale and recover. At this time, it is also preferable that the concentration of the quaternary chlorinated scale in the mixture to be treated before the addition of iodide is 1% by weight or more. The type, concentration, and method of adding the iodide, the method of filtering the precipitate, and thereafter The processing is the same as that of the application example I described above. Therefore, water already exists in the system at this time, so the iodide can be added as a solid. As a result, the amount of water used is reduced, and the dissolution loss of the iodized quaternary rust in the wastewater can be reduced. Instead of water, the iodide aqueous solution can be used by heating, which is an embodiment in which the above steps are shortened. The water containing an aqueous solution of chlorinated and quaternary iron iodide is preferably 90% or more, and more preferably 99% or more. After being evaporated and removed, it is treated as a mixture, and an inorganic chloride precipitation operation can be performed. That is, the treatment mixture -29-(27) 200422285 is dissolved in an organic solvent with a total weight of 1 to 10 times by weight based on the chlorination and iodination quaternary money in the treatment mixture, and iodide is added thereto. The type, concentration and method of addition of iodide, the method of filtering and removing the precipitates, and subsequent processing are the same as those of the application example I described above. In this method, it is also possible to replace the above water with an iodide aqueous solution. At this time, it is not necessary to add iodide in the latter stage.

As in all embodiments, iodide is added to precipitate inorganic chloride, and the remaining chlorinated and iodized fourth-grade scales are separated after solid-liquid separation, and the present invention is also applicable. That is, before the desired recovery rate is reached, the addition of iodide and the removal of inorganic chloride can be repeated.

In order to adopt the present invention, at least a part of the reaction liquid and / or the catalyst liquid can be taken out continuously or intermittently from the reaction procedure in the continuous operation, and if necessary, concentrated and / or pre-recovered, the chlorinated quaternary scale is transformed. In order to recover the fourth-order iodine scale, the recovered fourth-order iodine scale catalyst is recycled to the reactor. At this time, the amount of the reaction liquid and / or the catalyst liquid taken out to recover the iodized quaternary scale catalyst is not particularly limited. In order to remove the chlorinated quaternary scale in a range where the catalyst recovery cost is not too high, the reaction efficiency is highly maintained. Preferably, when the weight ratio of the quaternary chlorinated quaternary scale relative to the iodide in the reactor falls within a range of 0.0 1 to 1.0, the reaction solution and / or the catalyst solution are continuously or intermittently taken out for processing. There is no particular limitation on the amount to be taken out, but it is preferably about 0.1 to 100% by weight relative to the amount of the reaction solution or the amount of the catalyst solution in the system. Examples The present invention will be described more specifically with reference to the following examples. Of course, the present invention should not be interpreted as being limited to the related embodiments. Example 1 1 1 1 xinghua pressurized to 2.0 million Pa, retention time 1 hour,

The first reactor at 100 ° C supplied catalyst with 5 parts by weight of tributyl iodide iodide per hour, and potassium carbonate at 0.8 parts by weight per hour. Raw material ethylene oxide aqueous solution (60% by weight) 78 parts by weight / In hours, a reaction solution containing ethylene carbonate and a diol (EG) was obtained. The whole was transferred to a residence time of 2 hours, a pressure of 0.5 million Pa and a temperature of 150 ° C of the second reactor hydrolyzed the contained ethylene carbonate to obtain a catalyst aqueous solution containing 65. 5 parts by weight of ethylene glycol. /hour. The obtained reaction solution was distilled in a vacuum distillation column at a bottom of 140 ° C and a pressure of 11 kPa (80 mm), and a dehydrated liquid was obtained from the bottom of the column, and the stomach was & 140 ° C and 8 kPa (60 mm Hg) Operate a reduced pressure evaporator to evaporate most of the ethylene glycol. The catalyst is recovered from the bottom of the evaporation evaporator, and the concentrated catalyst and liquid are 13 min parts per hour. The recovered catalyst is recycled to the first reactor and used as the catalyst. The composition of the catalyst liquid after continuous operation for _ years is as follows.

[Composition of catalyst liquid] Ethylene glycol: about 59% by weight iodized salt (quaternary iodide scale): about 33% by weight chloride (quaternary phosphonium chloride): about 6% by weight potassium carbonate: about 2% by weight After reaching the above composition, it is changed to the operation of taking out ~ part of the catalyst liquid at 002-31-(29) 200422285 parts by weight / hour. The removed catalyst liquid (hereinafter referred to as "removal liquid A") was supplied to a flash boiler, and about 93% by weight of ethylene glycol contained in the liquid was removed under the conditions of 3 Torr (400 Pa) and 1 2 80 t: . Keep the liquid after removing the ethylene glycol (hereinafter referred to as "Concentrated Liquid A") unchanged at 95 ° C. Add 3% by weight potassium iodide aqueous solution and stir. After cooling to 20 ° C, let stand for 1 hour. The amount of water used is equal to the weight of the concentrated solution A, such as potassium iodide and the chloride salt in the concentrated solution A.

The precipitate was analyzed by solid-liquid separation with a suction filter. The composition of the precipitate was as follows, which is equivalent to 90% by weight of the iodine salt and the chloride salt in the above-mentioned extraction liquid A as iodized four-stage scale catalyst. Separated efficiently. [Precipitate composition]: about 18% by weight: about 2% by weight: about 80% by weight: about 2% by weight: 1% by weight or less

Water Ethylene glycol Iodized salt (quaternary scale iodine) Chloride (quaternary scale chloride) Potassium carbonate This precipitate was dissolved in ethylene glycol and recycled to the reactor. In this way, the recovery and circulation of the catalyst is carried out. When the catalyst is continuously operated, there is no problem of reduction in reaction efficiency in the ethylene glycol process, and the operation is continued and efficient. Example 1-2 In Example 1-11, the concentrated solution A 'after the separation and removal of ethylene glycol was taken from -32- (30) (30) 200422285 instead of potassium iodide aqueous solution was added with the same amount of distilled water as the concentrated solution A. The same operation precipitated a solid. The precipitate was analyzed by solid-liquid separation, and the precipitate contained 94% by weight of the iodine salt and about 13% by weight of the chloride salt in the above-mentioned extraction liquid A. It was confirmed that the iodized quaternary scale catalyst could be efficiently removed from Chloride isolated. About 6% by weight of the iodide salt and about 87% by weight of the chloride salt were dissolved in the liquid after separation of the precipitate (hereinafter referred to as "separation liquid A"). To this separation liquid A, 1.2 mol times potassium iodide with respect to the chlorine salt in the liquid was added as a 50% by weight aqueous solution, and it was left 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 extraction liquid A had been efficiently separated with a iodized quaternary rust catalyst. Example 1 to 3 The separation liquid A obtained in Example 1 to 2 was steamed, 50% by weight of water in the separation liquid A was saturated, and concentrated. To this concentrated solution, 1.2 mol times of potassium stiltite was added as a 50% by weight aqueous solution with respect to the gas salt in the liquid, and the mixture was left to stand at 20 ° C for 1 hour. The solid-liquid separation of the precipitate was analyzed, and it was confirmed that about 75% by weight of the chloride salt in the above-mentioned extraction liquid A had been efficiently separated with an iodized quaternary scale catalyst. Example 2 — 1 In a first reactor at 1000 ° C, 5 parts by weight of tributyl iodide iodide was supplied to a potassium carbonate at a pressure of 2.0 MPa with carbon dioxide and a residence time of 1 hour. 0.8 parts by weight / hour, raw material ethylene oxide aqueous solution (-33- (31) (31) 200422285 60% by weight) 78 parts by weight / hour to obtain a reaction solution containing ethylene carbonate and ethylene glycol (EG) . The whole was transferred to a second reactor with a residence time of 2 hours, a pressure of 0.5 MPa, and a temperature of 150 ° C. The contained ethylene carbonate was hydrolyzed to obtain an aqueous solution of ethylene glycol containing catalyst 6 6 · 5 parts by weight /hour. The obtained reaction solution was distilled in a vacuum distillation tower with a combined bottom of 140C and 11 kPa (80¾ m seeking column), and a dehydrated liquid was obtained from the bottom of the tower, and the mixture was further heated at 140 ° C and 8 kPa (60 mmHg). Column) Operate the reduced-pressure evaporator to evaporate most of the ethylene glycol. The catalyst is recovered from the bottom of the evaporator and the concentrated catalyst liquid is 13 parts by weight / hour. The recovered catalyst liquid is circulated to the first reactor and used as a catalyst. After one year of continuous operation, the composition of the catalyst liquid is as follows. [Composition of catalyst liquid] Ethylene glycol: about 59% by weight iodized salt (quaternary scale iodized): about 33% by weight chlorate (quaternary scale chlorinated): about 6% by weight rhenium carbonate: about 2% by weight After the composition is obtained, a part of the catalyst liquid is changed to an operation of taking out 0.02 parts by weight / hour. The extracted catalyst liquid (hereinafter referred to as "extracted liquid A") was supplied in a flash boiler at 3 Torr (400 Pa) at 1 280 ° C to remove about 93% by weight of ethylene glycol contained in the liquid. Keep the liquid after removing the ethylene glycol (hereinafter referred to as "Concentrate A") unchanged at 95 ° C, add water equal to the weight of Concentrate A, stir and mix while cooling to 20 ° C, and let it stand. 1 hour. -34- (32) 200422285 The precipitate (hereinafter referred to as "precipitate A") is separated by solid-liquid with a suction filter, and the obtained filtrate (hereinafter referred to as "filtrate A") is analyzed. The composition of filtrate A is as follows. About 80% by weight of the chlorine salt in the extraction liquid A described above. [Composition of filtrate A] Approximately 78% by weight Approximately 7% by weight Approximately 1% by weight Approximately 10% by weight Approximately 4% by weight Water ethylene glycol iodonium salt (quaternary scale iodine) Chloride (quaternary scale chlorinated) potassium carbonate On the other hand, when the precipitate A is analyzed, the composition of the precipitate A is as follows, and it contains about 98% by weight of the iodized salt in the extraction liquid A. [Composition of precipitate A]: about 16% by weight: about 1% by weight: about 80% by weight: about 2% by weight: 1% by weight or less

Water Ethylene glycol Iodized salt (quaternary scale iodized) Chloride (quaternary scale chlorinated) Potassium carbonate Water and glycol contained in filtrate A were removed using an evaporator operating at 140 ° C. The pressure was reduced with the removal of water and glycol, and finally held at 5 Torr (660 Pa) for 30 minutes. After this operation, the water and ethylene contained in the distillation residue -35- (33)

OOP Ο C

The amount of ZpU4zzz〇j alcohol was reduced to 10% by weight or less. After the water and ethylene glycol were removed in this manner, the residue was added with an equal weight of acetone. Next, the obtained liquid was transferred to a storage tank equipped with a stirrer, and 1.2 mol times of sodium iodide with respect to the contained chlorine salt was directly added as a solid, and stirred at room temperature for 1 hour.

The precipitate precipitated by this inorganic chloride precipitation operation was analyzed by solid-liquid separation using a suction filter, and sodium chloride corresponding to 98% by weight or more of the chloride salt in the filtrate A was present in the precipitate. On the other hand, the filtrate (hereinafter referred to as "filtrate B") obtained by separating the solid and liquid was introduced into an evaporator operated at 5 Torr (660 Pa) and 110 ° C, and acetone and ethylene glycol in the filtrate B It is substantially completely evaporated, and the obtained solid is mixed and washed with water of equal weight, and then solid-liquid separation is performed with a suction filter. The obtained solid (hereinafter referred to as "solid B") was analyzed as follows. [Solid B composition] Water glycol iodide salt (quaternary scale iodine) Chloride salt (quaternary scale chlorinated) Sodium iodide about 17% by weight 1% by weight or less about 8 1% by weight 1% by weight or less % If this solid B is combined with the above-mentioned precipitate A, about 98% by weight of the iodized salt and the chloride salt in the taken-out solution A are taken out on a quaternary scale of iodization, which is dissolved in an equal weight of ethylene glycol and recycled. Used in the reactor. In this way, while the catalyst is recovered and recycled, while continuing to operate, there is no problem of reduction in reaction efficiency in the process of ethylene second-36- (34) 200422285. The operation can be continued and efficient. Example 2-2 In Example 2-1, an organic solvent was added to the concentrate A after the ethylene glycol was separated and removed, and an equal weight of n-butanol was dissolved. This solution was sent to a storage tank equipped with a stirrer, and a molar amount of solid potassium iodide such as chloride salt contained in the solution was added, and mixed at room temperature for 2 hours.

The precipitate was analyzed by solid-liquid separation using a suction filter. The precipitate contained 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 110 ° C. The butanol and ethylene glycol in the filtrate were substantially completely evaporated, and the obtained solid was mixed and washed with water of equal weight. After that, solid-liquid separation was performed with a suction filter. When the obtained solid was analyzed, the composition was as follows, and it contained about 95% by weight of the iodine salt and the chloride salt in the taken-out liquid A on a quaternary scale.

[Solid composition]: about 18% by weight: 2% by weight: about 80% by weight: 1% by weight or less: about 1% by weight or less Water glycol iodonium salt (quaternary scale iodine) Chloride (quaternary scale chloride) (Money) Iodization dissolves the solid in equal weight of ethylene glycol and recycles it to the reactor -37- (35) 200422285 Thus the recovery and circulation of the catalyst is carried out, and while the operation continues, there is no reduction in reaction efficiency in the alcohol production process. The problem is that, in Comparative Example 1, in Example 1-1, 1000 g of the dehydrated liquid was taken out from the bottom of the vacuum distillation column. Relative to the catalyst contained in it, the ratio of ethylene glycol is. Add an equal weight of water to it and cool to 0 ° c, no precipitates appear. Example 1-4 The filtrate obtained in Examples 1 to 2 was added with 1% molar chlorate potassium iodide in 50% by weight aqueous solution to the solution, and the precipitate was allowed to stand at 20 ° C for 1 hour for solid-liquid separation for analysis. . As a result, it was confirmed that about 87% by weight of the above-mentioned chlorate in the precipitate had been efficiently converted to iodized fourth-grade rust. Response 87%

Relative. Separate fluid

INDUSTRIAL APPLICABILITY According to the present invention, an iodized and / or brominated quaternary scale catalyst is used to react ethylene oxide and other epoxides with water or with oxygen in the presence of carbon oxide to produce ethylene glycol. In methods such as alkanediol derivatives such as alkanediols or ethylene carbonates, the iodized or brominated tetracatalysts are efficiently recovered and recycled from the reaction system, or the chlorine grade produced in the reaction system is recycled. Scales are efficiently converted to iodized and / or brominated quaternary rust and recovered for recycling and used in the reaction system. Therefore, it is possible to prevent chlorination with low catalytic activity from carbon dioxide and ester-level squamousness. It can accumulate quaternary -38- (36) 200422285 money in the system and convert it into iodine with high catalytic activity. The quaternary scale and / or brominated scale can be recycled and used to maintain the catalyst activity in the system, and to stably and efficiently perform the alkene derivative formation reaction for a long time.

• 39-

Claims (1)

(1) (1) 200422285 Patent application scope 1. A method for producing an alkene derivative, which is characterized by using an iodized or brominated four-stage scale catalyst to make epoxide and water in the presence of carbon dioxide The method for producing an alkylene derivative in the reaction step of generating an alkanediol, which is characterized in that: the alkanediol is removed from at least a part of the reaction liquid and / or the catalyst liquid so that The molar ratio becomes 20 times or less, and it is mixed with water to recover the catalyst. 2. The manufacturing method of the suspected derivative as described in the first patent application, wherein the molar ratio of the alkanediol to the catalyst is less than 2 times. 3. The method for producing an alkene derivative according to item 1 or 2 of the scope of patent application, wherein the operating temperature when the catalyst is recovered by mixing with water is 30. (: The following. 4 · Rushen g 靑 Patent 轺 Waidi's method for producing a yard burning derivative of any one of items 1 to 3 'wherein the amount of water mixed is 0 · 1 times the weight of the recovered catalyst 5. The method for producing an alkene derivative according to any one of claims 1 to 4 in the scope of the patent application, wherein after mixing with water, solid-liquid separation separates the catalyst into solids, and then it is recycled to the reaction step. · A method for producing an alkene derivative according to item 5 of the patent application, wherein the liquid separated by solid-liquid separation is used as a catalyst and washing water is recycled. 7 · Any one of the items 1 to 6 of the patent application A method for producing an alkene derivative, in which an epoxide is ethylene oxide. 8 · —A catalyst regeneration method, characterized in that it is obtained from the use of iodination and -40- (2) (2) 200422285 / Or a brominated quaternary scale as a catalyst, a reaction step of reacting an epoxide containing chlorine compound as an impurity with water in the presence of carbon dioxide to form an alkanediol, which contains chlorinated quaternary scale and iodination and / or bromination Mixture of quaternary scales, mixed with iodide and / or bromide to convert the chlorine The quaternary money is converted into iodized and / or brominated quaternary money and precipitated in water. 9. A catalyst regeneration method, characterized in that it is obtained by using iodized and / or brominated quaternary money as a catalyst to make the ring A reaction step in which an oxide reacts with carbon dioxide to form an alkenyl carbonate, a mixture containing quaternary chlorinated rust and iodinated and / or brominated quaternary money, mixed with iodide and / or bromide to form the tetrachloride The scales are converted into iodized and / or brominated quaternary money and precipitated in water. 10. The catalyst regeneration method according to item 8 or 9 of the patent application scope, which contains chlorinated quaternary scales and iodized and / or brominated The mixture of quaternary scales is the reaction liquid taken out from the reaction step, or the residue after distilling off at least a part of water and / or the target product alkene derivative from the reaction liquid. 1 1 · If applied The catalyst regeneration method according to item 8 or 9 of the patent, which comprises a mixture of chlorinated quaternary scale and iodinated and / or brominated quaternary scale, the reaction liquid taken out from the reaction step, or the reaction liquid Residues after partial distillation of water and / or a target product alkene derivative, The catalyst is mixed with water to separate out the solid solution and separate it into an aqueous solution. 1 2 · The catalyst regeneration method according to any one of claims 8 to 11 in the patent application scope, wherein the precipitated iodide and / or bromine is recovered Four-stage hydrazone is circulated to the reaction step. 1 3-A catalyst regeneration method, characterized in that the catalyst is obtained by using iodized and / or brominated fourth-grade scale as a catalyst, and containing it in the presence of carbon dioxide. -41-(3) 200422285 Reaction step in which epoxide with chlorine compound as impurity reacts with water to form alkanediol. 'A mixture containing quaternary phosphonium chloride and iodized and / or brominated quaternary phosphonium, adding iodide and The bromide precipitates chlorine from the quaternary chlorinated scale as inorganic chloride in an organic solvent to recover the iodized and / or brominated quaternary hydrazone. 14. A catalyst regeneration method, characterized in that it is obtained from a reaction step in which an epoxide and carbon dioxide are reacted to form an alkenyl carbonate by using iodized and / or brominated four-stage scale as a catalyst, and contains a fourth-stage chloride A mixture of rust and iodized and / or brominated quaternary scales. Addition of iodide and / or bromide causes the chlorine from quaternary phosphonium chloride to precipitate as inorganic chloride in an organic solvent to recover iodized and / or bromine. Quaternary scales. 15. The catalyst regeneration method according to item 13 or 14 of the patent application scope, which contains a mixture of quaternary phosphonium chloride and iodized and / or brominated quaternary rust, which are among the following (a) to (c) Either: (a) a liquid or solid obtained by adding water to the reaction solution taken from the reaction step to precipitate the catalyst, and dehydrating the separated aqueous solution, (b) Residues obtained by distilling off at least a part of water and / or the target product alkene derivative from the reaction liquid obtained from the reaction step, adding water to precipitate the catalyst as a solid, and separating it A liquid or solid obtained by dehydrating the aqueous solution after the dehydration, (c) A liquid obtained by dissolving the liquid or solid obtained by dehydrating in (a) or (b) in an organic solvent. 16. The catalyst regeneration method according to item 13 or 14 of the scope of patent application, which contains a mixture of chlorinated quaternary scales and iodinated and / or brominated quaternary scales, which are (d), (e Any one of the following: • 42 · (3) (3) 200422285 A reaction step in which an epoxide in which a chlorine compound is an impurity reacts with water to form an alkanediol, which contains quaternary chlorinated quaternary and iodinated and / or brominated quaternary Adding iodide and / or bromide to the mixture of money, the chlorine from quaternary chlorinated scale is precipitated as inorganic chloride in organic solvent to recover iodized and / or brominated quaternary hydrazone. 14. A catalyst regeneration method, characterized in that it comprises a reaction step obtained by using iodized and / or brominated quaternary money as a catalyst to react epoxide with carbon dioxide to form alkenyl carbonate. A mixture of rust and iodinated and / or brominated quaternary, adding iodide and / or bromide to precipitate chlorine from chlorinated quaternary scales as inorganic chloride in an organic solvent to recover iodized and / or bromine Quaternary scales. 15. The catalyst regeneration method according to item 13 or 14 of the scope of patent application, which contains a mixture of chlorinated quaternary scales and iodinated and / or brominated quaternary scales, which are among the following (a) to (c) Either: (a) a liquid or solid obtained by adding water to the reaction solution obtained from the reaction step to precipitate the catalyst, and separating the separated aqueous solution from dehydration, (b) from the reaction obtained from the reaction step Residue after distilling off at least a part of water and / or the target product alkene derivative, adding water to precipitate the catalyst as a solid, and dehydrating the separated aqueous solution to obtain a liquid or solid (C) A liquid obtained by dehydrating a liquid or solid obtained in (a) or (b) by dissolving it in an organic solvent. 16. If the catalyst regeneration method according to item 13 or 14 of the patent application scope contains a mixture of quaternary phosphonium chloride and iodinated and / or brominated quaternary scale, it is any of the following (d), (e) One: -42-(4) 200422285 (d) a liquid obtained by diluting the reaction solution obtained from the reaction step with an organic solvent, (e) water and / or a target product alkene from the reaction solution obtained from the reaction step Residue after at least a part of the derivative is distilled off, or a liquid obtained by dissolving the residue in an organic solvent. 17 · The catalyst regeneration method according to any one of claims 13 to 16 in the scope of patent application, wherein the recovered iodinated and / or brominated fourth-order scale is recycled to the reaction step. 18. A method for producing an alkene derivative, comprising an alkene having a reaction step of using an iodized and / or brominated quaternary coin as a catalyst to react an epoxide with carbon dioxide to form an alkene carbonate. The method for producing derivatives is characterized by: In the reaction step obtained, a mixture containing quaternary chlorinated quaternary and iodized and / or brominated quaternary quaternary scale is added, and iodide and / or bromide are added to convert the chlorinated quaternary scale into iodized and / Or the brominated quaternary scale is precipitated and recovered in water and recycled to the reaction step. 19. A method for producing an alkene derivative, comprising an alkene derivative having a reaction step of using an iodized and / or brominated quaternary scale as a catalyst to react an epoxide with carbon dioxide to form an alkene carbonate. A method for producing a substance, characterized in that: in the step obtained from the reaction step, a mixture containing quaternary chlorinated quaternary scale and iodinated and / or brominated quaternary quaternary scale is added, and iodide and / or bromide is added to make the quaternary chlorinated The scale chlorine is precipitated into the organic solvent as an inorganic chloride to recover iodized and / or brominated quaternary money, and is recycled to the reaction step. -43- 200422285 柒, (a) (two), the designated representative picture in this case is: None. Brief description of the component representative symbols in this case: Μ Μ, if there is a chemical formula in this case, please reveal the chemical formula that can best show the characteristics of the invention: no