KR101431123B1 - Method for regenerating catalysts used in the production of alkylene carbonate and/or alkylene glycol and preparation method of alkylene carbonate and/or alkylene glycol - Google Patents
Method for regenerating catalysts used in the production of alkylene carbonate and/or alkylene glycol and preparation method of alkylene carbonate and/or alkylene glycol Download PDFInfo
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- KR101431123B1 KR101431123B1 KR1020120092890A KR20120092890A KR101431123B1 KR 101431123 B1 KR101431123 B1 KR 101431123B1 KR 1020120092890 A KR1020120092890 A KR 1020120092890A KR 20120092890 A KR20120092890 A KR 20120092890A KR 101431123 B1 KR101431123 B1 KR 101431123B1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
According to the present invention, there is provided a process for producing a polyimide precursor, comprising the steps of: reacting an alkylene oxide with carbon dioxide in the presence of a catalyst of a quaternary phosphonium iodide compound and / or a quaternary phosphonium bromide compound; And reacting the concentrate with a salt of iodide and / or a salt of bromide, and a process for producing an alkylene carbonate and / or an alkylene glycol capable of regenerating a catalyst having low activity .
Description
The present invention relates to a process for regenerating a catalyst for synthesizing an alkylene carbonate and / or an alkylene glycol, and a process for producing an alkylene carbonate and / or an alkylene glycol. More particularly, The present invention relates to a method for regenerating a catalyst used for the synthesis of an alkylene carbonate and / or an alkylene glycol, and to a process for producing an alkylene carbonate and / or an alkylene glycol which can regenerate a catalyst having a low activity.
Previously, a method of hydrolyzing ethylene oxide to synthesize ethylene glycol was used. According to this method, however, a large amount of by-products such as diethylene glycol or triethylene glycol were produced. In order to synthesize and purify ethylene glycol, There was a problem that energy had to be input. Recently, a method for producing ethylene glycol by hydrolyzing ethylene carbonate (EC, ethylene-carbonate) has been widely used commercially.
Specifically, in the method of producing ethylene glycol by hydrolysis of ethylene carbonate, ethylene oxide (EO, ethylene oxide) is synthesized by reacting ethylene and oxygen, and carbon dioxide is reacted with the ethylene oxide to synthesize ethylene carbonate. The carbonate is hydrolyzed to synthesize high purity ethylene glycol. In the synthesis of ethylene oxide, a silver catalyst is generally used, and a quaternary phosphonium iodide compound or a quaternary phosphonium bromide compound is generally used for the synthesis of ethylene carbonate.
Ethylene dichloride (EDC) is used as a reaction modifier in the production of ethylene oxide. Part of the chloride component of the compound partially remains in the product, and the quaternary phosphonium iodine Compound or a quaternary phosphonium bromide compound is chlorinated, thereby lowering the reaction efficiency of ethylene carbonate and ethylene glycol.
Korean Patent No. 0880135 discloses a process for decompressing ethylene carbonate and ethylene glycol synthesized in order to regenerate a chlorinated catalyst and adding iodide salt and / or bromide salt thereto. In particular, the vacuum distillation is applied to remove the ethylene carbonate or ethylene glycol from the reaction product to increase the catalyst regeneration efficiency. However, in the case of concentrating the reaction product by applying the reduced pressure distillation, it usually takes 20 hours or more, and it is not easy to secure the efficiency of removing ethylene carbonate or ethylene glycol or the regeneration efficiency of the catalyst to a certain level or more there was.
The present invention aims at providing a method capable of reducing the processing time and cost and more effectively regenerating the catalyst used in the synthesis of alkylene carbonate and / or alkylene glycol.
The present invention also relates to a process for producing an alkylene carbonate and / or an alkylene glycol which can be used by regenerating a catalyst whose activity is reduced.
The present invention relates to a process for producing an organic electroluminescence device, which comprises reacting carbon dioxide with an alkylene oxide having 2 to 6 carbon atoms in the presence of at least one catalyst selected from the group consisting of a quaternary phosphonium iodine compound and a quaternary phosphonium bromide compound, ≪ / RTI > And reacting the concentrate with at least one halogenated salt compound selected from the group consisting of a iodide salt and a bromide salt.
Also, the present invention provides a method for producing carbon dioxide, comprising: reacting carbon dioxide with an alkylene oxide having 2 to 6 carbon atoms in the presence of at least one catalyst selected from the group consisting of a phosphonium iodide compound and a phosphonium bromide compound; And regenerating the used catalyst by the method of
A method of regenerating a catalyst according to a specific embodiment of the present invention and a method for producing at least one compound selected from the group consisting of an alkylene carbonate having 2 to 6 carbon atoms and an alkylene glycol having 2 to 6 carbon atoms will be described in detail do.
According to one embodiment of the present invention, the result obtained by reacting carbon dioxide with an alkylene oxide having 2 to 6 carbon atoms in the presence of at least one catalyst selected from the group consisting of a quaternary phosphonium iodine compound and a quaternary phosphonium bromide compound, Concentrating using a thin film evaporator; And reacting the concentrate with at least one halide salt compound selected from the group consisting of iodide salt and bromide salt.
As a result of research conducted by the present inventors, it has been found that the result obtained by reacting an alkylene oxide having 2 to 6 carbon atoms and carbon dioxide in the presence of at least one catalyst selected from the group consisting of a quaternary phosphonium iodine compound and a quaternary phosphonium bromide compound, , It is possible to efficiently remove the alkylene carbonate or the alkylene glycol contained in the resulting product in a shorter time and to effectively remove the catalyst used for the synthesis of the alkylene carbonate and / It was confirmed that it can be reproduced.
Particularly, in the step of concentrating the reaction product using the thin film evaporator, the reaction product between the resulting alkylene oxide and carbon dioxide is heated for a relatively short time, for example, within 8 hours, preferably 30 minutes to 5 hours . In this concentration process, the alkylene carbonate or alkylene glycol contained in the reaction product can be removed at a high efficiency, for example, 95% or more, preferably 97% or more. Further, according to the catalyst regeneration method, it is possible to regenerate the catalyst (or the catalyst deformation product) that has lost activity in the reaction process, that is, the quaternary phosphonium chloride compound in a yield of 93% or more, preferably 95% have. This regeneration yield (%) can be obtained from the formula [regenerated amount of catalyst * 100 / amount of catalyst in concentration object].
As a thin film evaporator that can be used in the concentration step, a reaction product of alkylene oxide and carbon dioxide may be formed on the heat transfer surface or the heating surface in the form of a thin film (for example, a column, a tube, Etc.) can be used without limitation. Examples of such a thin film evaporator include a thin tube evaporator, a descending evaporator, a plate evaporator or a centrifugal evaporator, but the present invention is not limited thereto.
The thin-film evaporator may include a rotor, which is a part for rotating and rotating the reactant, a reactant supply part, and a heating part capable of heating the supplied reactant. Further, the thin film evaporator may further include one or more shafts And may include a rotation drive motor capable of rotating various types of blades (blades).
An example of such a thin film evaporator is the apparatus illustrated in FIG. As shown in FIG. 1, the thin film evaporator includes a
In the thin-film evaporator, the resulting product obtained by reacting carbon dioxide with an alkylene oxide having 2 to 6 carbon atoms in the presence of the above-mentioned specific catalyst is allowed to stand at a rate of 20 to 100 kg / hr relative to the above- . The retention rate can be adjusted by changing the injection amount of the resultant or the speed of an apparatus used for injection, for example, an injection motor. The heat transfer surface or the heating surface can be appropriately adjusted in accordance with the actual application process or the conditions such as the thin film evaporator.
Meanwhile, the concentration step using the thin film evaporator may be performed at a pressure of 10 -3 torr to 100 torr, preferably 10 -2 torr to 10 torr. If the pressure in the concentration step is too low, the alkylene carbonate or alkylene glycol, which is an evaporation product in the concentration step, as well as the catalyst compound having low activity, can be evaporated together, If the pressure in the concentration step is too high, the alkylene carbonate or the alkylene glycol can not be evaporated sufficiently and can be contained in the remaining concentrate. When the substance to be evaporated remains in the concentrate, And the yield of the whole process may be lowered.
The concentration step using the thin film evaporator may be performed at a temperature of 100 to 150 ° C, preferably 120 to 140 ° C. If the temperature of the concentration step is too high, the evaporated product, such as the alkylene carbonate or the alkylene glycol, as well as the less active catalytic compound may be evaporated, some of the catalysts whose activity is lost in the evaporated product, Or may be denatured. If the temperature of the concentration step is too low, the alkylene carbonate or the alkylene glycol is not sufficiently evaporated and is contained in the remaining concentrate. If the substance to be evaporated remains in the concentrate, And the yield of the whole process may be lowered.
More preferably, the phenomenon that the decomposition of the catalyst due to the high temperature is minimized and the phenomenon that the concentration object or the waste catalyst (activity-reduced catalyst composition) contained therein is solidified to cause a malfunction of each part of the actual process The concentration step using the thin film evaporator may be performed at a temperature ranging from 125 to 130 < 0 > C.
On the other hand, when carbon dioxide is reacted with an alkylene oxide having 2 to 6 carbon atoms in the presence of the catalyst described above, an alkylene carbonate can be produced, and alkylene glycol can be produced by hydrolysis of the alkylene carbonate. As described above, the alkylene oxide contains a certain amount of chloride component due to the cause of the reaction modifier and the like added at the time of production. Accordingly, in the reaction between the alkylene oxide having 2 to 6 carbon atoms and carbon dioxide, An iodine compound or a quaternary phosphonium bromide compound is converted into a quaternary phosphonium chloride compound.
Accordingly, the resulting product obtained by reacting the alkylene oxide with carbon dioxide includes at least one compound selected from the group consisting of alkylene glycols having 2 to 6 carbon atoms and alkylene carbonates having 2 to 6 carbon atoms; At least one compound selected from the group consisting of a quaternary phosphonium iodine compound and a quaternary phosphonium bromide compound; Quaternary phosphonium chloride compounds; And water may be present.
The relative proportions of the alkylene glycol and / or alkylene carbonate, the quaternary phosphonium iodide compound and / or the quaternary phosphonium bromide compound, the quaternary phosphonium chloride compound, and water may vary depending on the reaction conditions. For example, the reaction product of the alkylene oxide and the carbon dioxide may include 10 to 90% by weight of at least one compound selected from the group consisting of alkylene glycols having 2 to 6 carbon atoms and alkylene carbonates having 2 to 6 carbon atoms; 1 to 80% by weight of at least one compound selected from the group consisting of a quaternary phosphonium iodine compound and a quaternary phosphonium bromide compound; 0.1 to 80% by weight of a quaternary phosphonium chloride compound; And 0.001 to 50% by weight of water. The reactant of the alkylene oxide and the carbon dioxide may contain 0.1 to 10% by weight of other additives such as potassium carbonate.
On the other hand, the catalyst to be regenerated may be a catalyst used for the reaction of an alkylene oxide having 2 to 6 carbon atoms with carbon dioxide, specifically, a quaternary phosphonium iodide compound, a quaternary phosphonium bromide compound, or a mixture thereof . The quaternary phosphonium iodine compound may be a phosphonium iodide compound having at least four functional groups having at least one functional group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a benzyl group. Specific examples thereof include triphenylmethylphosphonium Iodide, triphenylpropylphosphonium iodide, triphenylbenzylphosphonium iodide, tributylmethylphosphonium iodide, or a mixture thereof. The quaternary phosphonium bromide compound may be a phosphonium bromide compound having at least four functional groups having at least one functional group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a benzyl group. Specific examples thereof include triphenylmethylphosphonium Bromide, triphenylpropylphosphonium bromide, triphenylbenzylphosphonium bromide, tributylmethylphosphonium bromide, or mixtures thereof.
Preferable examples of the alkylene oxide having 2 to 6 carbon atoms include ethylene glycol. Preferred examples of the alkylene carbonate having 2 to 6 carbon atoms include ethylene carbonate, and preferred examples of the alkylene glycol having 2 to 6 carbon atoms include Ethylene glycol.
On the other hand, the thin film evaporator can remove the alkylene carbonate, the alkylene glycol, or the mixture thereof from the reaction product of the alkylene oxide having 2 to 6 carbon atoms with the carbon dioxide, and the remaining reaction solution can be concentrated. More preferably, the thin film evaporator may remove ethylene carbonate, ethylene glycol or a mixture thereof from the reaction product of ethylene glycol and carbon dioxide, thereby allowing the remaining reaction liquid to be concentrated.
As described above, the concentrate thus obtained may have a catalyst that is less active due to its chloride component, i.e., a quaternary phosphonium chloride compound. As such a compound reacts with an iodide salt, a bromide salt, or a mixture thereof, Can be reproduced. Examples of the iodide salt which can be used herein include potassium iodide, calcium iodide, sodium iodide, or a mixture thereof, preferably potassium iodide. The bromide salt may be potassium bromide, silver bromide or a mixture thereof, and potassium bromide may be preferably used.
On the other hand, considering the solubility and reactivity to water, the higher the concentration of the iodide salt or the bromide salt is, the higher the proportion of the chloride can be substituted. However, if the concentration is higher than a certain level, excessive iodide salt or bromide salt is lost . Accordingly, the iodide salt or the bromide salt may be contained in the aqueous solution at a concentration of 1 wt% to 3 wt%.
On the other hand, the reaction ratio of the quaternary phosphonium chloride, which is an inactive catalyst, with the iodide salt or the bromide salt can be changed depending on the concentration of the iodide salt or the bromide salt to be used, but for example, a 2 wt% iodide salt or an aqueous solution of bromide salt A weight ratio of about 1: 1 can be applied.
The step of reacting the concentrate with at least one halogenated salt compound selected from the group consisting of iodide salt and bromide salt may be carried out at 50 to 150 ° C, preferably at 80 to 120 ° C. In the step of reacting the concentrate with at least one halide salt compound selected from the group consisting of iodide salt and bromide salt, the chloride (chlorine) of the quaternary phosphonium chloride compound may be substituted with iodine or bromine, Is too high or low, the substitution rate may be lowered.
Meanwhile, the regeneration method of the catalyst may further include a step of cooling the reaction product of the concentrate and the halogen salt compound to 10 to 30 占 폚. The quaternary phosphonium iodide, the quaternary phosphonium bromide or the quaternary phosphonium chloride compound exist in the form of solid particles in an aqueous solution. To keep the size of the solid particles large or large, Preferably at room temperature. In this cooling process, the effect of controlling the size of the solid particles may be enhanced by adding a high purity catalyst compound such as quaternary phosphonium iodide or quaternary phosphonium bromide to recrystallize.
Specifically, the step of reacting the concentrate with at least one halide salt compound selected from the group consisting of iodide salt and bromide salt may include the steps of: raising the temperature of the concentrate to 80 to 120 ° C; Adding at least one halogenated salt compound selected from the group consisting of a iodide salt and a bromide salt to the heated concentrate; Reacting the reaction solution containing the concentrate and the halogenated salt compound at 80 to 120 캜; And cooling the reacquired reaction solution to 10 to 30 캜.
The temperature may be lowered by adding at least one halogenated salt compound selected from the group consisting of iodide salt and bromide salt to the concentrate which has been heated to 80 to 120 ° C. Accordingly, the chloride (chlorine) of the quaternary phosphonium chloride compound may be lowered, The reaction solution may be re-heated to 80 to 120 ° C after addition of the halogenated salt compound in order to maintain or improve the efficiency of substitution with iodine or bromine.
After the re-warming step, the temperature of the reaction solution is maintained at a constant level. For example, the reaction solution is maintained at a temperature of 80 to 120 ° C for about 1 minute to 3 hours to convert the chloride of the deactivated catalyst to iodine or Bromine. After the temperature of the reaction solution is maintained for a predetermined time, the cooling step described above can be performed.
An example of the temperature control process (temperature profile) of reacting the concentrate with at least one halogenated salt compound selected from the group consisting of iodide salt and bromide salt is shown in FIG. The contents shown in FIG. 2 briefly show the temperature control performed in the regeneration process of the inactive catalyst of the embodiment. However, the respective steps of temperature rise, re-warm-up, temperature maintenance or cooling applicable in the present invention are not limited thereto.
Further, the regeneration method of the catalyst may further include a step of filtering the reactant of the concentrate and the halogen salt compound. As described above, since the catalyst to be regenerated is present in the form of a solid in the form of an aqueous solution, the aqueous solution can be filtered in order to recover them more easily. In this filtration step, any method or apparatus known to be used for filtering solid components or particles can be used without any limitations. For example, the reactant may be filtered using a filter having a size of 10 um or less, or centrifuged .
As described above, the catalyst may be one used for synthesis of at least one compound selected from the group consisting of alkylene carbonates having 2 to 6 carbon atoms and alkylene glycols having 2 to 6 carbon atoms.
According to another embodiment of the present invention, there is provided a process for producing an organic electroluminescent device, comprising: reacting carbon dioxide with an alkylene oxide having 2 to 6 carbon atoms in the presence of at least one catalyst selected from the group consisting of a phosphonium iodide compound and a phosphonium bromide compound; And regenerating the used catalyst by the method of
As described above, according to the catalyst regeneration method, it is possible to effectively regenerate a catalyst having a low activity in a short period of time. Accordingly, in the production method according to another embodiment of the present invention, And the reaction yield can be increased by establishing a continuous process.
The details of the step of regenerating the used catalyst are as described above. The specific contents of the iodinated phosphonium compound and the brominated phosphonium compound are as described above. Preferable examples of the alkylene oxide having 2 to 6 carbon atoms include ethylene glycol. Preferred examples of the alkylene carbonate having 2 to 6 carbon atoms include ethylene carbonate, and preferred examples of the alkylene glycol having 2 to 6 carbon atoms include Ethylene glycol.
The catalyst obtained through the regeneration step may be recycled to the reaction step of the alkylene oxide and carbon dioxide having 2 to 6 carbon atoms.
As described above, according to the catalyst regeneration method, it is possible to regenerate a catalyst having a low activity in the reaction process, that is, a quaternary phosphonium chloride compound at a yield of 93% or more. Therefore, In the above-described production method, the catalyst can be regenerated within a short time, and the amount of consumption can be controlled to a small extent.
On the other hand, as described above, when the alkylene oxide having 2 to 6 carbon atoms reacts with carbon dioxide, an alkylene carbonate may be formed. The alkylene carbonate may be added to water present in the reaction solution, Can be hydrolyzed and converted to an alkylene glycol having 2 to 6 carbon atoms. That is, the production method may further include hydrolyzing the reaction product of the alkylene oxide having 2 to 6 carbon atoms and the carbon dioxide.
According to the present invention, there is provided a method for regenerating a catalyst which can reduce the process time and cost and is more effectively used for the synthesis of an alkylene carbonate and / or an alkylene glycol, and a method for regenerating an alkylene carbonate and / / RTI > and / or a process for the preparation of alkylene glycols may be provided.
Fig. 1 schematically shows a thin-film evaporator used in Example 2. Fig.
Figure 2 is a graph of the activity Which is a schematic representation of the applied temperature profile.
The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
< Example : Regeneration of catalyst>
Example 1 .
1. Concentration of reaction solution using a thin film vaporizer
The reaction product (70 Kg) having the composition shown in the following Table 1 was obtained by reacting ethylene oxide with carbon dioxide in the presence of a tri-butyl-methyl Phosphonium Iodide catalyst.
The reaction product was agitated at 125 rpm and 200 rpm at a pressure of 5 torr using an 8-inch thin film vaporizer (manufactured by VTA, Germany, heat transfer area: 0.40 m 2, 8 inch (20 cm) column, While ethylene glycol was removed, and the reaction product was concentrated. This process was carried out twice for 2 hours to remove 97.7% (39 Kg) of ethylene glycol.
2. Disabled Regeneration of the catalyst (replacing the chloride of the deactivated catalyst with iodine)
The obtained concentrate was heated to 95 캜, and 2% by weight of potassium iodide (KI) was added to the heated concentrate to make the amount of chloride and iodine equal. The reaction solution was reheated to 95 캜, and after the temperature of the reaction solution reached 95 캜, the reaction solution was kept isothermal for 30 minutes and then cooled to 25 캜.
3. Purification of catalyst
The reaction solution obtained in the above-mentioned regeneration step was filtered using a filter having a size of 10 mu m or less. At this time, the residue was collected, and the filtrate was filtered again to collect the residue. Then, the collected residue (regenerated catalyst) was mixed with ethylene glycol separated from the thin film vaporizer, and potassium carbonate was added to complete regeneration of the catalyst.
The composition of the obtained final regenerated catalyst is shown in Table 2 below.
As shown in the compositions of Tables 1 and 2, it can be seen that most of Tri-Butyl-Methyl Phosphonium Chloride was converted into Tri-Butyl-Methyl Phosphonium Iodide through
Example 2 .
1. Concentration of reaction solution using a thin film vaporizer
Ethylene oxide and carbon dioxide were reacted in the presence of a tri-butyl-methylphosphonium iodide catalyst to obtain a reaction product (70.22 Kg, ethylene glycol content: 59.38 wt%) having the composition shown in Table 3 below. The composition of the main elements contained in the reaction product is shown in Table 3 below.
The resulting reaction product was stirred at 120 rpm at a temperature of 135 DEG C at a pressure of 0.03 torr using a 71L thin film vaporizer (UIC GmbH D-63755), and ethylene glycol was removed to concentrate the reaction product. This process was run for about 7 hours to remove about 98.3% (41 Kg) of ethylene glycol.
2. Disabled Regeneration of the catalyst (replacing the chloride of the deactivated catalyst with iodine)
The obtained concentrate was heated to 95 캜, and 2% by weight of potassium iodide (KI) was added to the heated concentrate to make the amount of chloride and iodine equal. The reaction solution was reheated to 95 캜, and after the temperature of the reaction solution reached 95 캜, the reaction solution was kept isothermal for 30 minutes and then cooled to 25 캜.
3. Purification of catalyst
The reaction solution obtained in the above-mentioned regeneration step was filtered using a filter having a size of 10 mu m or less. At this time, the residue was collected, and the filtrate was filtered again to collect the residue. Then, the collected residue (regenerated catalyst) was mixed with ethylene glycol separated from the thin film vaporizer, and potassium carbonate was added to complete regeneration of the catalyst.
The compositions of the major elements contained in the thus-obtained reproduced product are shown in Table 4 below.
As shown in the compositions of Tables 3 and 4, it can be seen that the content of chlorine in the result of the regeneration is significantly reduced compared with the content of chlorine (Cl) contained in the reaction product as the concentrate. That is, it can be seen that the catalyst containing tri-butyl-methyl Phosphonium Iodide, which is inactivated in the step of reacting ethylene oxide with carbon dioxide, was regenerated with high efficiency in a short time through each step of the above example.
< Comparative Example : Regeneration of catalyst>
1. Concentration of the reaction mixture through vacuum distillation
The reaction product (the composition of Table 1) used in the above Example was distilled under reduced pressure at a pressure of 3 torr at a temperature of 128 占 폚 to remove ethylene glycol (see Korean Patent No. 0880135). When this process was run for about 24 hours, about 93% of ethylene glycol was removed.
2. Disabled Regeneration of the catalyst and purification of the catalyst
The catalyst was regenerated and purified in the same manner as in Example 1, except that the concentrated liquid obtained through the above-described vacuum distillation was used. At this time, the time from the concentration step to the final completion step was 43 hours, and the regeneration yield was 91%.
< Example And Comparative example Comparison>
1. Measurement of regeneration yield
The yields of the catalysts regenerated in the above Examples and Comparative Examples were determined using the following general formula (1).
[Formula 1]
Regeneration yield (%) = (regenerated catalyst amount (A) * 100 / catalyst amount (B)
The regenerated catalytic quantity A and the catalytic quantity B of the concentrated object are calculated as follows: [(concentration of each of the target samples * concentration of P * sum of molecular weights of catalyst (inclusive of P)) / .
As shown in the following Table 5, according to the regeneration method of the Example, the reaction liquid containing the deactivated catalyst can be efficiently concentrated by removing ethylene glycol more effectively in a short time, and the regeneration is completed in a relatively short time By implementing a relatively high regeneration yield, the process time and cost can be greatly reduced.
01: Reactant Feed
02: Distillate
03: Residue Residue
04: Heating
05: Cooling
06: Pressure regulator (Vacuum)
Claims (17)
Adjusting the temperature of the concentrate to 80 to 120 캜;
Adding at least one halogenated salt compound selected from the group consisting of a iodide salt and a bromide salt to the concentrate having a temperature controlled at 80 to 120 ° C;
Adjusting the reaction solution containing the concentrate and the halogenated salt compound to 80 to 120 캜; And
And cooling the temperature-regulated reaction solution to 10 to 30 DEG C,
Wherein the resulting product obtained by reacting the alkylene oxide with carbon dioxide is retained at a rate of 20 kg / hr to 100 kg / hr in a thin-film evaporator.
Wherein the concentration step using the thin-film evaporator is performed at a temperature of 125 ° C to 130 ° C.
Wherein the concentration step using the thin film evaporator is performed within 8 hours.
The quaternary phosphonium iodine compound may be at least one selected from the group consisting of triphenylmethylphosphonium iodide, triphenylpropylphosphonium iodide, triphenylbenzylphosphonium iodide, and tributylmethylphosphonium iodide Or more;
The quaternary phosphonium bromide compound is a catalyst for regeneration of a catalyst comprising at least one member selected from the group consisting of triphenylmethylphosphonium bromide, triphenylpropylphosphonium bromide, triphenylbenzylphosphonium bromide and tributylmethylphosphonium bromide. Way.
The resultant product obtained by reacting the alkylene oxide with carbon dioxide in the presence of at least one catalyst selected from the group consisting of a quaternary phosphonium iodine compound and a quaternary phosphonium bromide compound,
At least one compound selected from the group consisting of alkylene glycols having 2 to 6 carbon atoms and alkylene carbonates having 2 to 6 carbon atoms;
At least one compound selected from the group consisting of a quaternary phosphonium iodine compound and a quaternary phosphonium bromide compound;
Quaternary phosphonium chloride compounds; And water.
The iodide salt which reacts with the concentrate includes at least one compound selected from the group consisting of potassium iodide, calcium iodide and sodium iodide,
Wherein the bromide salt to be reacted with the concentrate comprises at least one compound selected from the group consisting of potassium bromide and silver bromide.
And filtering the reactant of the concentrate and the halogen salt compound.
Wherein the catalyst is used in the synthesis of at least one compound selected from the group consisting of an alkylene carbonate having 2 to 6 carbon atoms and an alkylene glycol having 2 to 6 carbon atoms.
Regenerating said used catalyst by the process of claim 1. < RTI ID = 0.0 > 11. < / RTI &
An alkylene carbonate having 2 to 6 carbon atoms, and an alkylene glycol having 2 to 6 carbon atoms.
And circulating the regenerated catalyst to the reaction step of the alkylene oxide and carbon dioxide having 2 to 6 carbon atoms.
Further comprising hydrolyzing the reaction product of the alkylene oxide and carbon dioxide having 2 to 6 carbon atoms.
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| PCT/KR2012/006786 WO2013028039A2 (en) | 2011-08-24 | 2012-08-24 | Method of regenerating a catalyst for synthesis of alkylene carbonate and/or alkylene glycol, and a method for producing alkylene carbonate and/or alkylene glycol |
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| KR100880135B1 (en) * | 2003-02-07 | 2009-01-23 | 미쓰비시 가가꾸 가부시키가이샤 | Method for producing alkylene derivative and method for regenerating catalyst for producing alkylene derivative |
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