WO2011136127A1 - アルキレンカーボネート及び/又はアルキレングリコールの製造方法 - Google Patents
アルキレンカーボネート及び/又はアルキレングリコールの製造方法 Download PDFInfo
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- WO2011136127A1 WO2011136127A1 PCT/JP2011/059855 JP2011059855W WO2011136127A1 WO 2011136127 A1 WO2011136127 A1 WO 2011136127A1 JP 2011059855 W JP2011059855 W JP 2011059855W WO 2011136127 A1 WO2011136127 A1 WO 2011136127A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
Definitions
- alkylene oxide and carbon dioxide are reacted to produce alkylene carbonate, and further, alkylene glycol in the reaction liquid is hydrolyzed to produce alkylene glycol.
- the present invention relates to a method for producing alkylene carbonate and / or alkylene glycol.
- Ethylene glycol is produced on a large scale by a direct hydrolysis of ethylene oxide and water, but in this method, in order to control by-products such as diethylene glycol and triethylene glycol, hydrolysis is performed on ethylene glycol. In contrast, a greater excess of water than stoichiometric amounts must be used. Therefore, it is necessary to dehydrate the generated ethylene glycol aqueous solution to dehydrate a large excess of water, and there is a problem that a great deal of energy is required to obtain purified ethylene glycol.
- the present invention relates to a reaction step in which alkylene oxide, water and carbon dioxide are reacted in the presence of a catalyst and an alkali metal carbonate to produce alkylene carbonate and / or alkylene glycol, and a reaction liquid obtained in the reaction step.
- a method for producing alkylene carbonate and / or alkylene glycol comprising recovering alkylene carbonate and / or alkylene glycol from the catalyst and circulating a catalyst solution containing the catalyst to the reaction step, while maintaining the hydrolysis rate. It is an object of the present invention to provide a production method in which precipitates do not accumulate therein and can be stably operated for a long period of time.
- the present inventors first examined the cause of the decrease in the activity of the hydrolysis catalyst.
- potassium carbonate present in the reaction system changed to potassium chloride as the reaction proceeded,
- the rate of hydrolysis reaction of ethylene carbonate fell.
- the cause of the decrease in the rate of hydrolysis reaction is the production process of ethylene oxide, which is a raw material, and chlorohydrocarbon is supplied as a selectivity regulator to improve the selectivity of the reaction.
- Hydrogen is mixed in the ethylene glycol or ethylene carbonate production process and further decomposes into chlorine ions, so that the potassium carbonate contained in the reaction solution is converted into potassium chloride, and the ethylene carbonate hydrolysis reaction is gradually performed. It was thought to be slowing down.
- the organic chloro compound that causes a decrease in the hydrolysis reaction is concentrated in a liquid obtained by condensing a gas containing carbon dioxide released from the carbonation reactor or the hydrolysis reactor, and this liquid is recovered.
- organic chloro compounds gradually accumulate in the process, and the accumulated organic chloro compounds gradually decompose, and potassium carbonate used as a hydrolysis catalyst is neutralized with chloride ions. It turned out to be.
- bleeding the liquid containing the organic chloro compound out of the system can prevent chlorination of the hydrolysis catalyst and decrease the activity of the hydrolysis catalyst.
- the condensate of carbon dioxide released from the carbonation step or the hydrolysis reactor contains about 5% to 30% of ethylene glycol.
- ethylene glycol At the same time when bleeding chlorine ions (organic chloro compounds), this ethylene
- glycol has a problem of bleeding, it has been found that an organic chloro compound can be separated from ethylene glycol by distillation without being decomposed when distilled under conditions without potassium carbonate.
- the present inventors removed alkali metal chloride derived from the alkali metal carbonate (hydrolysis catalyst) in the reaction solution or chlorine ions derived from the alkali metal chloride. By carrying out the reaction, it was found that precipitates are not generated in the reaction system while maintaining the hydrolysis rate, and that it can be stably operated for a long period of time.
- the gist of the present invention is as follows. (1) a reaction step in which alkylene oxide, water and carbon dioxide are reacted in the presence of a catalyst and an alkali metal carbonate to produce alkylene carbonate and / or alkylene glycol, and a reaction solution obtained in the reaction step
- a reaction step in which alkylene oxide, water and carbon dioxide are reacted in the presence of a catalyst and an alkali metal carbonate to produce alkylene carbonate and / or alkylene glycol, and a reaction solution obtained in the reaction step
- the method for producing alkylene carbonate and / or alkylene glycol comprising a step of recovering alkylene carbonate and / or alkylene glycol, and a catalyst circulation step of circulating a catalyst solution containing a catalyst to the reaction step
- At least a part of the alkylene glycol is separated by distillation, and the solid precipitated in the distillation separation is separated.
- the catalyst circulation step further supplies the residual liquid from which the solid precipitated in the distillation separation is separated to the reaction step.
- the step of removing the alkali metal chloride derived from the alkali metal carbonate in the reaction solution acquires a part or all of the reaction solution containing the catalyst in the reaction step and is included in the reaction solution.
- At least a part of the alkylene glycol is separated by distillation, and further, the solid precipitated in the distillation separation is separated.
- the catalyst circulation step further comprises a catalyst from the residual liquid from which the solid precipitated in the distillation separation is separated.
- the step of removing chlorine ions derived from the alkali metal chloride comprises: The condensing step for cooling the gas containing carbon dioxide released in the carbonation step and / or the hydrolysis step, and the alkalinity of the catalyst liquid circulated to the reaction step in the catalyst circulation step is 0.03 mol / mol with respect to the catalyst concentration.
- the method for producing alkylene carbonate and / or alkylene glycol according to (1) including a step of discharging the condensate obtained in the condensation step so as to become the above.
- the condensate is further subjected to dehydration distillation to remove water and organic chloro compounds contained therein, and then the remaining liquid is circulated to the reaction step.
- a reaction system that discharges the condensate obtained in the hydrolysis process to the outside of the reaction system, and a catalyst with the alkalinity (concentration of OH groups of the hydrolysis catalyst contained in the catalyst liquid) circulated to the carbonation process It is the graph which showed the relationship between the ratio with respect to a density
- the present invention relates to a reaction step in which alkylene oxide, water and carbon dioxide are reacted in the presence of a catalyst and an alkali metal carbonate to produce alkylene carbonate and / or alkylene glycol, and a reaction liquid obtained in the reaction step.
- a catalyst and an alkali metal carbonate to produce alkylene carbonate and / or alkylene glycol
- a reaction liquid obtained in the reaction step.
- the alkali metal in the reaction solution comprising the step of recovering alkylene carbonate and / or alkylene glycol from the catalyst, and the catalyst circulation step of circulating the catalyst solution containing the catalyst to the reaction step, the alkali metal in the reaction solution
- the method further comprises a step of removing alkali metal chloride derived from the carbonate or chlorine ions derived from the alkali metal chloride.
- the reaction step of the present invention means both “a carbonate step for producing alkylene carbonate” and “a hydrolysis step for further hydrolyzing the alkylene carbonate in the reaction solution after the carbonate step”.
- a carbonation process and a hydrolysis process are demonstrated, you may carry out in the same reactor not only in the reaction system isolate
- Carbonation step As a catalyst for the carbonation step (in the present specification, this may be referred to as "carbonated catalyst"), an alkali metal bromide or iodide, an alkaline earth metal halide, What is necessary is just to select suitably from well-known things, such as an alkylamine, a quaternary ammonium salt, an organic tin, a germanium or tellurium compound, and a halogenated organic phosphonium salt. Of these, quaternary phosphonium iodide or bromide is preferably used.
- Such a carbonation catalyst is preferably supplied to the reaction system in an amount of 0.001 to 0.05 times mol of alkylene oxide.
- an alkali metal carbonate is allowed to coexist in the reaction system as a hydrolysis catalyst.
- sodium or potassium, preferably potassium hydroxide, carbonate or bicarbonate may be added to the carbonation step, and any alkali metal compound may be added to the reaction system.
- the alkali metal carbonate, preferably potassium carbonate is preferably present in a molar ratio of 0.01 to 1.0 with respect to the carbonated catalyst such as quaternary phosphonium iodide. In order to maintain the above concentration, it is also preferable to add an alkali metal carbonate to the reaction system.
- the method of the present invention is characterized by including a step of removing the alkali metal chloride derived from the alkali metal carbonate or chlorine ions derived from the alkali metal chloride from the reaction system.
- the raw material alkylene oxide ethylene oxide, propylene oxide or the like is used.
- the alkylene oxide purified alkylene oxide with high purity may be used or a crude product may be used, but usually contains a small amount of a chlorine compound such as chlorohydrocarbon.
- a chlorine compound such as chlorohydrocarbon.
- the produced alkylene carbonate is ethylene carbonate.
- alkylene oxide is converted not only to alkylene carbonate but also to alkylene glycol, so that the reaction is easy even with a supply amount of carbon dioxide equal to or less than equimolar to alkylene oxide.
- the amount of water relative to the alkylene oxide is usually preferably about 1.0 to 10 times moles relative to the alkylene oxide.
- Carbon dioxide provides a sufficient effect in an amount of equimolar or less with respect to the alkylene oxide, but the quantitative ratio is not necessarily strictly limited. Preferably they are 0.1 times mole or more and 5.0 times mole or less.
- the reaction temperature in the carbonation step is usually 50 to 200 ° C., but it is preferable to carry out the reaction at 100 to 170 ° C.
- the reaction pressure is usually 0.5 to 5.0 MPa, preferably 1.0 to 3.0 MPa.
- the carbonation reaction can be carried out using any apparatus, but is preferably carried out using a bubble column.
- the reaction temperature is controlled by circulating the reaction liquid in the tower through the liquid circulation conduit using a bubble tower having a liquid circulation conduit equipped with a heat exchanger for heat removal and a circulation pump in the middle.
- the raw material alkylene oxide, carbon dioxide, catalyst, and water as necessary are continuously supplied from the bottom of the column to continuously react.
- reaction solution obtained in the carbonation step is sent to the hydrolysis step.
- a part or all of the reaction solution may be sent to the alkylene carbonate production process to recover the alkylene carbonate.
- the remaining reaction liquid from which the alkylene carbonate is recovered is sent to the hydrolysis process together with the remaining liquid obtained in the carbonation process.
- the hydrolysis reaction is advantageous in terms of reaction rate at high temperatures. However, if the temperature is too high, the quality of the alkylene glycol may be lowered, so it is usually carried out at 100 to 180 ° C. Is preferred.
- the reaction pressure is arbitrary as long as it is in the range up to the boiling point of the liquid, but it is usually preferable to carry out at normal pressure to 2.1 MPa. Also, as the hydrolysis proceeds, the reaction temperature is increased or the reaction pressure is increased. It is also preferable to promote the hydrolysis by lowering the temperature.
- the amount of water with respect to the reaction solution obtained from the carbonation step is sufficient if the amount is equal to or more than the molar amount of the alkylene carbonate contained, but considering the water accompanying the carbon dioxide gas as the hydrolysis proceeds. It is preferable to add in excess, and it is usually carried out in an amount of 10 moles or less, preferably 1 to 5 moles of the alkylene oxide used as a raw material. Water is added at the beginning of the carbonation step, added at the hydrolysis step, added several times as the reaction proceeds in the hydrolysis step, and supplied by steam There are methods, but any method may be used.
- the alkylene glycol produced by hydrolysis can be separated and obtained from the reaction solution by a known method.
- a crude alkylene glycol composed of alkylene glycol, dialkylene glycol, other high-boiling components, a carbonated catalyst, etc. is obtained through a dehydration step in which water is separated by distillation in a distillation facility, preferably vacuum distillation.
- the liquid containing the catalyst in the reaction step of the present invention is circulated to any of the reaction steps after separating the catalyst by an appropriate method.
- the step of separating the catalyst is referred to as the catalyst separation step
- the step of circulating the liquid containing the catalyst obtained by the catalyst separation step to the reaction step is referred to as the catalyst circulation step.
- the liquid containing the catalyst used for the catalyst separation step is obtained from the reaction step after the carbonation step.
- the catalyst solution here is preferably circulated in the carbonation step.
- the catalyst separation is preferably performed under reduced pressure in order to promote evaporation of alkylene glycol and dialkylene glycol.
- An evaporator equipped with a reboiler is used to replenish energy necessary for evaporation and control the evaporation amount.
- Step of removing alkali metal chloride derived from alkali metal carbonate the alkali metal carbonate that has been present as a hydrolysis catalyst is neutralized to become a chloride (in the present specification) Then, it may be referred to as “alkali metal chloride”).
- alkali metal chloride any method can be used as long as the alkali metal chloride present in the reaction system can be removed, but preferably the reaction of the present invention.
- a method is adopted in which any one of the reaction solutions in the step is taken out and the alkali metal chloride contained in the reaction solution is removed, and then recycled to any of the reaction steps of the present invention.
- inorganic bromide or iodide may or may not be added in order to remove chloride derived from the carbonated catalyst.
- the alkali metal chloride concentration is preferably 2% by weight or less, more specifically 0.1% by weight to 1% by weight. If the concentration of the alkali metal chloride in the extracted reaction solution is too high, the chloride itself is deposited, which may cause a clogging trouble.
- the reaction solution used for the alkali metal chloride removal treatment may be any reaction solution after the carbonation step, but it may be the reaction solution in the hydrolysis step during continuous operation, or from the hydrolysis step. Examples thereof include a reaction liquid obtained or a liquid obtained by removing alkylene glycol and water from the reaction liquid obtained from the hydrolysis step (this may be referred to as “catalyst liquid” in the present specification).
- the extraction of the reaction solution may be continuous or intermittent.
- the whole reaction solution may be extracted, but if a part of the reaction solution is extracted, the amount of the reaction solution to be processed is smaller and the processing is easier.
- the method for removing the alkali metal chloride from the reaction solution may be any method known per se. Specifically, at least a part of the alkylene glycol contained in the reaction solution obtained above is distilled and separated. Examples thereof include a method of removing a solid content precipitated in the distillation separation and a method of using an ion exchange resin. The method by removing the solid content which precipitates when the alkylene glycol and the high boiling point component contained in the reaction solution are evaporated and recovered will be described below.
- the extracted reaction solution is subjected to a step of distilling and separating at least a part of the alkylene glycol contained in the obtained reaction solution (hereinafter sometimes referred to as “distillation step”).
- the distillation step is carried out until the alkali metal chloride concentration in the liquid is 0.5% by weight or more, preferably 1% by weight or more, and more preferably 2% by weight or more.
- alkylene glycol is distilled and separated.
- high-boiling components such as dialkylene glycol and trialkylene glycol are added. It may be separated.
- the distillation is performed under reduced pressure, specifically 500 torr or less, preferably 30 to 200 torr, at a temperature at which the catalyst does not deteriorate, 120 to 200 ° C., preferably 120 to 180 ° C.
- a distillation apparatus an apparatus equipped with a reboiler is used to replenish energy required for evaporation and control the evaporation amount.
- At least alkylene glycol if necessary, high-boiling compounds are separated by distillation.
- the alkali metal chloride concentration in the liquid exceeds 0.5% by weight, the alkali metal chloride Will be deposited.
- the solid substance which is the precipitated alkali metal chloride is separated from the solution part.
- filtration separation, centrifugation, precipitation separation, or the like can be performed, and any method has no problem.
- the precipitate when the precipitate is separated via a precipitation tank, generally, the lower the temperature, the lower the solubility and the higher the removal effect. Since the viscosity of a certain catalyst solution increases and the fluidity is lost, it is preferable to heat or keep the temperature so that it is preferably handled at 80 ° C. or higher, more preferably 90 ° C. or higher and 180 ° C. or lower.
- the precipitation tank may be installed separately from the evaporation apparatus, but it is preferable to flush the reaction liquid heated by the heat exchanger with the distillation apparatus and the precipitation tank integrally from the middle or upper part to the precipitation tank.
- the precipitated alkali metal chloride is separated into solid and liquid, then recovered as a solid, or the residual liquid in the precipitation tank is extracted from the drain line, and then the remaining alkali metal chloride is dissolved in the solvent. Thereafter, it is preferable to perform the detoxification treatment or to perform the detoxification treatment by extracting the solid from the manhole as it is.
- the solution part separated and recovered above can be used as a catalyst by supplying it to a reactor, preferably a reactor in a carbonation step, as a liquid containing the catalyst subjected to the catalyst separation step (catalyst) Circulation process).
- the catalyst liquid which is the solution part after removing the solid matter can further be separated from the catalyst as a catalyst separation step and used for the catalyst circulation step. Examples of the catalyst recovery method include the method described in Japanese Patent No. 4273802.
- chloride ions derived from alkali metal chlorides which have been neutralized with alkali metal carbonates present as hydrolysis catalysts, are also removed from the reaction system.
- the second feature is to include a process. Any method may be used to remove the chlorine ions derived from the alkali metal chloride as long as the chlorine ions present in the reaction system can be removed.
- the alkali of the catalyst liquid to be circulated to the reaction step is used. The condensate described below is discharged out of the system so that the degree (concentration of the OH group of the hydrolysis catalyst contained in the catalyst solution) is 0.03 mol / mol or more with respect to the catalyst concentration.
- the alkalinity of the catalyst solution is 0.03 mol / mol or less with respect to the catalyst concentration, the hydrolysis rate decreases, and it is difficult to say that this is an industrially advantageous method for producing alkylene carbonate and / or alkylene glycol.
- the alkalinity of the catalyst solution is adjusted to 0.03 mol / mol or more with respect to the catalyst concentration, and more preferably 0.05 mol / mol or more with respect to the catalyst concentration.
- the alkalinity can be measured by a known method. Specifically, the catalyst solution can be titrated with an acid. In addition, as an index for discharging the condensate out of the system, it can be used that the chlorine ions contained in the catalyst liquid are less than 3 in molar ratio with respect to the contained alkali metal.
- the alkali metal added as a hydrolysis catalyst may be neutralized and may not function as a hydrolysis catalyst.
- the molar ratio of chlorine ions to alkali metal in the catalyst solution to be circulated is less than 3, preferably less than 2, and most preferably less than 1.
- the concentration of chlorine ions in the catalyst solution to be circulated can be measured by a commonly used method such as precipitation titration or ion chromatography. If the condensate discharge amount in which the molar ratio falls within the above range is known as an empirical value, a method of discharging the condensate amount without monitoring the chlorine ion concentration in the circulating catalyst solution can be used.
- the gas containing carbon dioxide released in the carbonation step and / or hydrolysis step is cooled.
- Condensation step is included.
- the gas phase portion of the reactor is cooled to recover the condensate, which is extracted and discharged.
- the discharge amount may be the whole amount or an amount sufficient for the alkalinity in the catalyst solution to be circulated to the reaction step to be 0.03 mol / mol or more with respect to the catalyst concentration. Since the condensate contains raw material alkylene oxide in addition to chlorine ions (organic chloro compound), if necessary, the alkylene oxide is recovered and then discharged as a solution containing chlorine ions (organic chloro compound).
- the accumulated amount of chlorine ions is small, and the alkalinity of the catalyst solution is 0.03 mol / mol or more with respect to the catalyst concentration, so it may be returned to the hydrolysis reactor as it is.
- the condensate may be extracted after chlorine ions have accumulated, but it is also preferable to extract the condensate in advance in order to prevent the accumulation of chlorine ions.
- the extraction is preferably carried out continuously or intermittently while adjusting the extraction amount while monitoring the chlorine ion concentration in the catalyst solution and the state of the hydrolysis reaction.
- the remainder of the condensate extracted and discharged out of the reaction system can be circulated to the carbonation step or the hydrolysis step.
- the condensate withdrawn from the reaction system may be discarded after detoxification if necessary as wastewater, but it contains organic substances such as alkylene glycol. It is preferable to collect it as a product.
- dehydration distillation is performed in advance, and the organic chloro compounds are distilled and separated together with water, and then alkylene glycol is recovered. Is preferred.
- Another method for removing chlorine ions is to supply the condensate to the hydrolysis reaction solution supply stage of the distillation column in the above dehydration step or to a stage above it, so that chlorine ions (organic chloro compound) together with moisture
- a method of discharging from the tank is also used.
- the reaction solution coming from the hydrolysis step contains a hydrolysis catalyst. For this reason, when it is supplied to a stage below the supply stage, chlorine ions (organic chloro compounds) may react with the hydrolysis catalyst and neutralize the hydrolysis catalyst as chlorine. In order to avoid this, it is necessary to supply the hydrolysis reaction liquid to the supply stage of the hydrolysis reaction liquid or to a higher stage to avoid contact with the hydrolysis catalyst.
- an alkali metal carbonate which is present as a hydrolysis catalyst is first added to the reaction process.
- the alkali metal carbonate to be added preferably potassium carbonate, should be maintained at a concentration of 0.01 to 1.0 with respect to the carbonated catalyst such as quaternary phosphonium iodide. preferable.
- a method for adding carbonate solids may be added directly, but a method of adding by dissolving in water or a method of adding by dissolving in alkylene glycol is effective in terms of handling.
- the alkali metal carbonate may be added continuously, but the operation can be continued without any problem by adding an appropriate amount when the reaction rate decreases while monitoring the state of the hydrolysis reaction.
- Example 1 Carbonation step A carbonation reaction portion containing a carbonation reactor at 100 ° C. with a residence time of 1 hour pressurized with carbon dioxide at 2.0 MPa, 5 parts by weight of tributylmethylphosphonium iodide / Hr, potassium carbonate 0
- the carbonation process reaction liquid containing ethylene carbonate and ethylene glycol (EG) was obtained by supplying 0.8 weight part / Hr and raw material ethylene oxide aqueous solution (60 weight%) 78 weight part / Hr.
- reaction liquid obtained from the hydrolysis step is distilled by a vacuum distillation tower at 140 ° C. and 80 torr to obtain a dehydrated liquid from the tower bottom, which is further operated at 140 ° C. and 60 torr.
- Most of the ethylene glycol was evaporated using a vacuum evaporator, and 13 parts by weight / hr of the catalyst solution in which the catalyst was concentrated was recovered from the bottom of the evaporator.
- the recovered catalyst solution was recycled to the carbonation reactor as a catalyst.
- the hydrolysis reaction became insufficient, so the operation was continued while adding potassium carbonate.
- reaction solution was extracted from the hydrolysis step that continued operation for 3 months, and 100 parts of the reaction solution was charged into a glass evaporator, followed by distillation separation of ethylene glycol.
- the pressure was 30 torr, and heating was performed by heating the oil bath to 170 ° C.
- Example 1 In Example 1, the operation was continued in the same manner as in Example 1 except that potassium chloride was not removed from the catalyst solution. As a result, potassium chloride was precipitated in the catalyst solution, making it difficult to circulate the catalyst solution, and the operation was stopped.
- Example 2 Carbonation step A carbonation reaction portion containing a carbonation reactor at 100 ° C. with a residence time of 1 hour pressurized with carbon dioxide at 2.0 MPa, 5 parts by weight of tributylmethylphosphonium iodide / Hr, potassium carbonate 0
- the carbonation process reaction liquid containing ethylene carbonate and ethylene glycol (EG) was obtained by supplying 0.8 weight part / Hr and raw material ethylene oxide aqueous solution (60 weight%) 78 weight part / Hr.
- the carbon dioxide gas generated in the first hydrolysis reactor was cooled, and the condensate of water vapor accompanying the carbon dioxide gas was analyzed.
- 167 ppm ethylene chlorohydrin was contained in the condensate. It contained 273 ppm of methyldioxolane and 17.2% by weight of ethylene glycol. Therefore, continuous extraction of the entire amount of the condensate was started.
- the operation was performed for 100 days, and the evaluation was performed using the alkalinity which is an index of the hydrolysis rate.
- the alkalinity was measured by titrating the number of moles of OH groups serving as a hydrolysis catalyst contained in the catalyst solution circulated to the carbonation step with an acid. The value is also divided by the number of moles of tributylmethylphosphonium iodide in order to eliminate the influence of changes in the concentration of the catalyst solution. The result is shown in FIG. As shown in FIG. 1, no decrease in the reaction rate of the hydrolysis reaction was observed, and the alkalinity of the catalyst solution was maintained at 0.03 mol / mol or more with respect to the catalyst concentration.
- the chlorine ion concentration and potassium concentration contained in the catalyst solution were measured.
- the measuring method of potassium is ICP (Inductively Coupled Plasma) emission spectroscopy.
- the measuring method of chloride ion is precipitation titration analysis. The results are shown in Table 1 and FIG. As apparent from Table 1 and FIG. 2, the concentration of chlorine ions contained in the catalyst solution was less than 3 in terms of molar ratio with respect to the alkali metal concentration.
- Example 3 The condensate and hydrolysis reaction liquid extracted in Example 2 above were distilled in a theoretical eight-stage distillation column, and ethylene chlorohydrin and chloromethyldioxolane were distilled off together with moisture from the top of the column. From this, ethylene glycol containing no organic chloro compound was recovered.
- Example 2 Ethylene glycol was produced in the same manner as in Example 2 except that the condensate of water vapor accompanying the carbon dioxide gas obtained by cooling the carbon dioxide gas generated in the first hydrolysis reactor was directly supplied to the hydrolysis step. went. The operation was continued for 230 days, and the alkalinity of the hydrolysis catalyst in the catalyst solution to be circulated to the carbonation step was measured in the same manner as in Example 2. The result is shown in FIG. As apparent from FIG. 3, the alkalinity of the hydrolysis catalyst decreased, the reaction rate of the hydrolysis reaction gradually decreased, and the conversion of ethylene carbonate was 99.9% or more, up to 98.8%. Declined.
- a method for producing alkylene carbonate and / or alkylene glycol which can prevent deterioration of the catalyst in the hydrolysis step and can stably operate for a long period of time while maintaining the hydrolysis rate and no precipitate is formed in the reaction system.
- alkylene carbonate and / or alkylene glycol can be efficiently produced with little loss.
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Abstract
Description
しかしながら、加水分解工程における触媒の活性の低下及びその防止方法は、これまで開示されているものはない。
(1)触媒及びアルカリ金属の炭酸塩の存在下に、アルキレンオキシド、水及び二酸化炭素を反応させて、アルキレンカーボネート及び/又はアルキレングリコールを生成させる反応工程と、該反応工程で得られる反応液からアルキレンカーボネート及び/又はアルキレングリコールを回収する工程と、触媒を含む触媒液を反応工程へ循環させる触媒循環工程とを備えるアルキレンカーボネート及び/又はアルキレングリコールの製造方法において、
反応液中の前記アルカリ金属の炭酸塩由来のアルカリ金属塩化物、又は該アルカリ金属塩化物由来の塩素イオンを除去する工程を含むことを特徴とするアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(2)反応液中の前記アルカリ金属の炭酸塩由来のアルカリ金属塩化物を除去する工程が、前記反応工程中の触媒を含む反応液の一部又は全量を取得して該反応液に含まれるアルキレングリコールの少なくとも一部を蒸留分離し、更に、該蒸留分離において析出する固体を分離するものであり、前記触媒循環工程が更に、該蒸留分離において析出する固体を分離した残液を反応工程へ循環させるものである(1)に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(3)反応液中の前記アルカリ金属の炭酸塩由来のアルカリ金属塩化物を除去する工程が、前記反応工程中の触媒を含む反応液の一部又は全量を取得して該反応液に含まれるアルキレングリコールの少なくとも一部を蒸留分離し、更に、該蒸留分離において析出する固体を分離するものであり、前記触媒循環工程が更に、該蒸留分離において析出する固体を分離した残液から、さらに触媒を分離回収した後に、回収した触媒を前記反応工程に循環させることを特徴とする(1)に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(4)前記析出する固体の分離を、80℃以上で行うことを特徴とする(2)または(3)に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(5)前記反応工程が、触媒及びアルカリ金属の炭酸塩の存在下に、アルキレンオキシドと二酸化炭素とを反応させて、アルキレンカーボネートを生成させるカーボネート化工程、及びカーボネート化工程の反応液中のアルキレンカーボネートを加水分解してアルキレングリコールを生成させる加水分解工程を含み、
前記アルカリ金属塩化物由来の塩素イオンの除去工程が、
カーボネート化工程及び/又は加水分解工程で放出される二酸化炭素を含むガスを冷却する凝縮工程と、触媒循環工程で反応工程へ循環させる触媒液のアルカリ度が触媒濃度に対して0.03mol/mol以上となるように前記凝縮工程で得られた凝縮液を排出する工程を含む、(1)に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(6)前記塩素イオン除去工程において、前記凝縮液をさらに脱水蒸留して中に含まれる水及び有機クロル化合物を除去した後、残りの液を前記反応工程へ循環させる、(5)に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(7)前記有機クロル化合物がエチレンクロルヒドリンである(6)に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(8)前記凝縮液を循環させる場所が、前記加水分解工程で得られる加水分解反応液に含まれる水を蒸留分離する蒸留塔の加水分解反応液供給段またはそれより上の段である(5)~(7)のいずれかに記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(9)前記反応工程に、前記アルカリ金属の炭酸塩を追加添加することを特徴とする(1)~(8)のいずれかに記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
(10)アルキレンカーボネートがエチレンカーボネートであり、アルキレングリコールがエチレングリコールである(1)~(9)のいずれかに記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法、
に存する。
カーボネート化工程の触媒(本明細書中では、これを「カーボネート化触媒」と称することがある)としては、アルカリ金属の臭化物またはヨウ化物、アルカリ土類金属のハロゲン化物、アルキルアミン、第4級アンモニウム塩、有機スズまたはゲルマニウム若しくはテルル化合物、ハロゲン化有機ホスホニウム塩等の公知のものの中から適宜選択して用いれば良い。なかでも、4級ホスホニウムヨーダイド又はブロマイドが好ましく用いられる。具体的には、トリフェニルメチルホスホニウムヨーダイド、トリフェニルプロピルホスホニウムヨーダイド、トリフェニルベンジルホスホニウムヨーダイド、トリブチルメチルホスホニウムヨーダイド等が挙げられる。このようなカーボネート化触媒は、アルキレンオキシドに対して0.001~0.05倍モルとなるように反応系に供給するのが好ましい。
加水分解反応は高温で行う方が反応速度の点で有利であるが、高温にし過ぎるとアルキレングリコールの品質が低下する恐れがあるので、通常は100~180℃で行うのが好ましい。反応圧力は液の沸点までの範囲であれば任意であるが、通常は、常圧~2.1MPaで行うのが好ましく、また、加水分解が進行するにつれて反応温度を高くしたり、反応圧力を低くしたりして、加水分解を促進させるのも好ましい。
加水分解工程で使用される触媒は、カーボネート化工程で使用した触媒をそのまま使用することができる。加水分解速度が不十分な場合は、触媒を加水分解工程で追加してもよい。
加水分解により生成したアルキレングリコールは、公知の方法により反応液中から分離取得することができる。通常は、まず蒸留設備において蒸留、好ましくは減圧蒸留して水を分離する脱水工程を経て、アルキレングリコール、ジアルキレングリコール、その他の高沸点成分及びカーボネート化触媒等からなる粗アルキレングリコールを取得する。
本発明の反応工程において触媒を含む液は、触媒を適当な方法で分離した後に、反応工程のいずれかへ循環させる。ここで、触媒を分離する工程を触媒分離工程、また、触媒分離工程により得られた触媒を含む液を反応工程へ循環させる工程を触媒循環工程という。
触媒分離工程に供される触媒を含む液とは、カーボネート化工程より後の反応工程から取得されるものである。
具体的な触媒分離及び循環工程としては、上記加水分解工程で得られる触媒を含む液を用いる場合、(3)に記載のとおり加水分解工程の反応液を脱水した後、フラッシング槽に供給してアルキレングリコール及びジアルキレングリコール等の高沸点物のほとんどを気化させて分離し、残留したアルキレングリコール、ジアルキレングリコール、高沸点物及び触媒を含む液を回収して、触媒液として反応工程へ循環させる。ここでの触媒液は、カーボネート化工程に循環することが好ましい。上記触媒分離はアルキレングリコール及びジアルキレングリコール等の蒸発を促進する為に減圧下で行われることが好ましい。蒸発装置としてはリボイラーを備えたものを用いて蒸発に必要なエネルギーを補給し且つ蒸発量を制御する。
本発明においては、加水分解触媒として存在させていたアルカリ金属の炭酸塩が中和されて塩化物になったもの(本明細書中では、「アルカリ金属塩化物」と称することがある)を取り除く工程を含むことを特徴とする。上記アルカリ金属の炭酸塩由来のアルカリ金属塩化物の除去方法としては、反応系に存在する上記アルカリ金属塩化物が除去し得る方法であればいずれのものでもよいが、好ましくは、本発明の反応工程のいずれかの反応液を抜き出して、該反応液中に含まれるアルカリ金属塩化物を取り除いた後に、本発明の反応工程のいずれかへ循環させる方法がとられる。なお、本発明の方法においては、カーボネート化触媒由来の塩化物を除去するために無機臭化物または無機ヨウ化物を加えてもよいし、加えなくともよい。
本発明においては、加水分解触媒として存在させていたアルカリ金属の炭酸塩が中和されたアルカリ金属塩化物由来の塩素イオンも反応系から除去する工程を含むことを第2の特徴とする。上記アルカリ金属塩化物由来の塩素イオンの除去方法としては、反応系に存在する当該塩素イオンが除去し得る方法であればいずれのものでもよいが、好ましくは、反応工程へ循環させる触媒液のアルカリ度(触媒液中に含まれる加水分解触媒のOH基の濃度)が、触媒濃度に対して0.03mol/mol以上となるように下述する凝縮液を系外へ排出することを特徴とする方法である。触媒液のアルカリ度が、触媒濃度に対して0.03mol/mol以下となると、加水分解速度が低下して、工業的に有利なアルキレンカーボネート及び/又はアルキレングリコールの製造方法とは言い難い。上記触媒液のアルカリ度は、触媒濃度に対して0.03mol/mol以上に調整するが、更に好ましくは、触媒濃度に対して0.05mol/mol以上に調整される。
上記アルカリ度は、公知の方法により測定することができる。具体的には、触媒液について、酸により滴定することにより行うことができる。
また、上記凝縮液を系外に排出する指標として、上記触媒液に含まれる塩素イオンが、含有するアルカリ金属に対し、モル比で3未満となることも用いることができる。
モル比が上記範囲となる凝縮液の排出量が経験値としてわかる場合には、循環させる触媒液中の塩素イオン濃度を監視しなくとも当該量を排出する方法をとることもできる。
カーボネート化工程で塩素イオンを除去する場合は、反応器の気相部を冷却して凝縮液を回収し、これを抜き出して排出する。排出量は、全量でも良いし、上記反応工程へ循環させる触媒液中のアルカリ度が触媒濃度に対して0.03mol/mol以上となるのに十分な量であればよい。凝縮液中には塩素イオン(有機クロル化合物)の他に原料のアルキレンオキシドが含まれる為に、必要があればアルキレンオキシドを回収した後に、塩素イオン(有機クロル化合物)を含む溶液として排出する。
本発明の反応工程においては、より加水分解反応速度を保ったまま運転を継続するために、最初に加水分解触媒として存在させるアルカリ金属の炭酸塩を反応工程に添加することもできる。添加するアルカリ金属の炭酸塩、好ましくは炭酸カリウムは、4級ホスホニウムヨーダイド等の前記カーボネート化触媒に対して、モル比で0.01~1.0となる濃度を維持する程度とすることが好ましい。炭酸塩の添加方法としては、直接固体を投入してもかまわないが、水に溶かして添加する、あるいは、アルキレングリコールに溶解して添加する方法が取り扱いの点で有効である。アルカリ金属の炭酸塩の添加は連続的に添加してもかまわないが、加水分解反応の状況を監視しながら、反応速度が低下してきた時に適量を追加する方法で問題なく運転を継続できる。
かくして生成、回収された粗アルキレンカーボネート及び/又は粗アルキレングリコールは、それ自体公知の通常用いられる方法により必要に応じて精製することができる。
(1)カーボネート化工程
二酸化炭素で2.0MPaで加圧された滞留時間1時間、100℃のカーボネート化反応器を含むカーボネート化反応部分にトリブチルメチルホスホニウムヨーダイド5重量部/Hr、炭酸カリウム0.8重量部/Hr、原料エチレンオキシド水溶液(60重量%)78重量部/Hrを供給することによりエチレンカーボネート及びエチレングリコール(EG)を含むカーボネート化工程反応液を得た。
カーボネート化工程から得られた反応液を滞留時間2時間、圧力0.5MPa、温度150℃の加水分解反応器を含む加水分解反応部に移して、含有されるエチレンカーボネートを加水分解して、触媒及びエチレングリコールを含む加水分解工程反応液87.5重量部/Hrを得た。
加水分解工程から得られた反応液を、塔底140℃、80torrの減圧蒸留塔により蒸留して、塔底から脱水された液を得、これを更に140℃、60torrで操作される減圧蒸発器によりエチレングリコールの大部分を蒸発させ、蒸発器底部より触媒が濃縮された触媒液を13重量部/Hrを回収した。回収した触媒液は触媒としてカーボネート化反応器へ循環使用した。
運転を継続したところ、加水分解反応が不十分になったので、炭酸カリウムを添加しながら運転を継続した。
3ヶ月運転を継続した加水分解工程から反応液を抜き出し、ガラス製エバポレーターに該反応液100部仕込み、エチレングリコールの蒸留分離操作を行った。圧力を30torrとし、加熱はオイルバスを170℃に加熱して行った。
実施例1において、触媒液から塩化カリウムを除去しないこと以外、実施例1と同様に運転を継続したところ、触媒液に塩化カリウムが析出して触媒液の循環が困難になり運転を停止した。
(1)カーボネート化工程
二酸化炭素で2.0MPaで加圧された滞留時間1時間、100℃のカーボネート化反応器を含むカーボネート化反応部分にトリブチルメチルホスホニウムヨーダイド5重量部/Hr、炭酸カリウム0.8重量部/Hr、原料エチレンオキシド水溶液(60重量%)78重量部/Hrを供給することによりエチレンカーボネート及びエチレングリコール(EG)を含むカーボネート化工程反応液を得た。
カーボネート化工程から得られた反応液を、まず、圧力1.8MPa、温度150℃の第1加水分解反応器でエチレンカーボネートの加水分解反応を行い、引き続き 圧力0.2MPa,温度150℃の第2加水分解反応器で残りのエチレンカーボネートを加水分解して、触媒及びエチレングリコールを含む加水分解工程反応液87.5重量部/Hrを得た。加水分解に伴い発生する炭酸ガスは、熱交換器で冷却し、炭酸ガスに同伴した水分は凝縮した後、加水分解反応器に戻して反応を継続した。
加水分解工程から得られた反応液を、塔底140℃、80torrの減圧蒸留塔により脱水蒸留して、塔底から脱水された液を得、これを更に140℃、60torrで操作される減圧蒸発器によりエチレングリコールの大部分を蒸発させ、蒸発器底部より触媒が濃縮された触媒液を13重量部/Hrを回収した。回収した触媒液は触媒として第1加水分解反応器へ循環使用した。
上記実施例2で抜出した凝縮液と加水分解反応液と共に理論段8段の蒸留塔で蒸留を行い、エチレンクロルヒドリン及びクロルメチルジオキソランを水分とともに塔頂から留出させ、蒸留塔の塔底から有機クロル化合物を含まないエチレングリコールを回収した。
第1加水分解反応器で発生した炭酸ガスを冷却して得られた炭酸ガスに同伴される水蒸気の凝縮液をそのまま加水分解工程に供給した以外は、実施例2と同様にエチレングリコールの生成を行った。230日間運転を継続し、カーボネート化工程へ循環させる触媒液中の加水分解触媒のアルカリ度を実施例2と同様に測定した。この結果を図3に示す。図3から明らかなように、上記加水分解触媒のアルカリ度は減少し加水分解反応の反応速度が次第に遅くなりエチレンカーボネートの転化率が99.9%以上であったものが、98.8%まで低下した。
Claims (10)
- 触媒及びアルカリ金属の炭酸塩の存在下に、アルキレンオキシド、水及び二酸化炭素を反応させて、アルキレンカーボネート及び/又はアルキレングリコールを生成させる反応工程と、該反応工程で得られる反応液からアルキレンカーボネート及び/又はアルキレングリコールを回収する工程と、触媒を含む触媒液を反応工程へ循環させる触媒循環工程とを備えるアルキレンカーボネート及び/又はアルキレングリコールの製造方法において、
反応液中の前記アルカリ金属の炭酸塩由来のアルカリ金属塩化物、又は該アルカリ金属塩化物由来の塩素イオンを除去する工程を含むことを特徴とするアルキレンカーボネート及び/又はアルキレングリコールの製造方法。 - 反応液中の前記アルカリ金属の炭酸塩由来のアルカリ金属塩化物を除去する工程が、前記反応工程中の触媒を含む反応液の一部又は全量を取得して該反応液に含まれるアルキレングリコールの少なくとも一部を蒸留分離し、更に、該蒸留分離において析出する固体を分離するものであり、前記触媒循環工程が該蒸留分離において析出する固体を分離した残液を反応工程へ循環させるものである請求項1に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。
- 反応液中の前記アルカリ金属の炭酸塩由来のアルカリ金属塩化物を除去する工程が、前記反応工程中の触媒を含む反応液の一部又は全量を取得して該反応液に含まれるアルキレングリコールの少なくとも一部を蒸留分離し、更に、該蒸留分離において析出する固体を分離するものであり、前記触媒循環工程が該蒸留分離において析出する固体を分離した残液から、さらに触媒を分離回収した後に、回収した触媒を前記反応工程に循環させることを特徴とする請求項1に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。
- 前記析出する固体の分離を、80℃以上で行うことを特徴とする請求項2または3に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。
- 前記反応工程が、触媒及びアルカリ金属の炭酸塩の存在下に、アルキレンオキシドと二酸化炭素とを反応させて、アルキレンカーボネートを生成させるカーボネート化工程、及びカーボネート化工程の反応液中のアルキレンカーボネートを加水分解してアルキレングリコールを生成させる加水分解工程を含み、
前記アルカリ金属塩化物由来の塩素イオンの除去工程が、
カーボネート化工程及び/又は加水分解工程で放出される二酸化炭素を含むガスを冷却する凝縮工程と、触媒循環工程で反応工程へ循環させる触媒液のアルカリ度が触媒濃度に対して0.03mol/mol以上となるように前記凝縮工程で得られた凝縮液を排出する工程を含む、請求項1に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。 - 前記塩素イオン除去工程において、前記凝縮液をさらに脱水蒸留して中に含まれる水及び有機クロル化合物を除去した後、残りの液を前記反応工程へ循環させる、請求項5に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。
- 前記有機クロル化合物がエチレンクロルヒドリンである請求項6に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。
- 前記凝縮液を循環させる場所が、前記加水分解工程で得られる加水分解反応液に含まれる水を蒸留分離する蒸留塔の加水分解反応液供給段またはそれより上の段である請求項5~7のいずれか一項に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。
- 前記反応工程に、前記アルカリ金属の炭酸塩を追加添加することを特徴とする請求項1~8のいずれか一項に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。
- アルキレンカーボネートがエチレンカーボネートであり、アルキレングリコールがエチレングリコールである請求項1~9のいずれか一項に記載のアルキレンカーボネート及び/又はアルキレングリコールの製造方法。
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CN201180021036.2A CN102858727B (zh) | 2010-04-28 | 2011-04-21 | 碳酸亚烷基酯及/或亚烷基二醇的制造方法 |
KR1020167008016A KR101671155B1 (ko) | 2010-04-28 | 2011-04-21 | 알킬렌카보네이트 및/또는 알킬렌글리콜의 제조 방법 |
BR112012027617-4A BR112012027617B1 (pt) | 2010-04-28 | 2011-04-21 | Método para produção de alquileno glicol |
SG2012079554A SG185059A1 (en) | 2010-04-28 | 2011-04-21 | Method for producing alkylene carbonate and/or alkylene glycol |
KR1020127030331A KR101663347B1 (ko) | 2010-04-28 | 2011-04-21 | 알킬렌카보네이트 및/또는 알킬렌글리콜의 제조 방법 |
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CN109867654B (zh) * | 2019-02-19 | 2021-06-29 | 胜华新能源科技(东营)有限公司 | 一种用于环氧烷烃和二氧化碳制备碳酸亚烷基酯的方法 |
KR102150240B1 (ko) * | 2019-10-14 | 2020-09-01 | 그린케미칼 주식회사 | 알킬렌카보네이트 제조 장치 및 그를 이용한 제조 방법 |
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