KR20080040935A - Method and apparatus for separating of catalyst ligand oxide by recrystalization in oxo process - Google Patents

Abstract

A method and an apparatus for separating of catalyst ligand oxides by recrystallization in the oxo process are provided to remove effectively catalyst ligand oxides, particularly triphenylphosphine oxide that is a high boiling point material from a catalytic solution of a hydroformylation reaction by recrystallization, and to remove continuously catalyst ligand oxides in the catalytic solution while continuously performing the oxo process without affecting the operation of an existing process at all. An apparatus for removal of catalyst ligand oxides from a catalytic solution that has passed through a hydroformylation reaction comprises: a catalytic solution injection port into which a catalytic solution comprising a catalyst and catalyst ligands that have passed through a hydroformylation reaction is injected; a recrystallization region for recrystallizing catalyst ligand oxides in the catalytic solution that has been injected into the catalytic solution injection port; and a catalytic solution discharge port for discharging residual catalytic solution except the catalyst ligand oxides that have been recrystallized and precipitated. The apparatus further comprises a filtration unit installed between the recrystallization region and the catalytic solution injection port, or between the recrystallization region and the catalytic solution discharge port. The recrystallization region includes an agitator.

Description

Separation method and apparatus of catalytic ligand oxide by recrystallization in oxo process {METHOD AND APPARATUS FOR SEPARATING OF CATALYST LIGAND OXIDE BY RECRYSTALIZATION IN OXO PROCESS}

1 is a diagram illustrating an oxo processing apparatus according to an exemplary embodiment of the present invention.

[Description of Main Code in Drawing]

1: raw material supply line 2: first reactor

3: second reactor 4: upper part of a vaporizer

5: lower part of separation means 6: product transfer line

7: unreacted raw material recovery line 8: catalyst ligand oxide removal means

9: catalyst recovery line

The present invention relates to a method for removing an oxide of a catalyst ligand generated by oxidation of a catalyst ligand of a hydroformylation reaction from a catalyst solution, and more particularly, to remove an oxide of a catalyst ligand from a catalyst solution of a hydroformylation reaction during an oxo process. It relates to a method that can be removed continuously and effectively by the recrystallization process.

In general, oxo (OXO) hydroformylation (hydroformylation) reaction reaction well-known to include various olefin and synthesis gas in the presence of a metal catalyst and catalyst ligand (Synthetic gas, e.g., CO / H ₂₎ is reacted with one or a number of carbon atoms in olefin This refers to the process of generating linear, normal or branched (aldehyde) aldehydes. Various aldehydes synthesized by the oxo reaction can be transformed into aldehyde derivatives, acids and alcohols, by oxidation or reduction. In addition, after the condensation reaction of Aldol (Aldol) it is transformed into various acids and alcohols containing a long alkyl group through oxidation or reduction reaction. Such alcohols and acids are used as solvents, additives, and raw materials for various plasticizers.

In many oxo processes, catalysts include acetylacetonatodicarbonyldium (Rh (AcAc) (CO) ₂ ), acetylacetonatocarbonyltriphenylphosphinedium (Rh (AcAc) (CO) (TPP)) Lidocarbonyltristriphenylphosphinedium (HRh (CO) (TPP) ₃ ) is mainly used and these catalysts are readily available commercially. In case of propene based oxo process, BASF is tetra (carbonyl) cobalt sodium (NaCo (CO) ₄ ), Shell is hydridotricarbonyltributylphosphinecobalt (HCo (CO) ₃ PBu ₃ ), UCC uses hydridocarbonyltritriphenylphosphinedium (HRh (CO) (TPP) ₃ ), and Ruhrchemie-Rhone-Poulence uses rhodium / TPPTS as a catalyst. Rh (AcAc) (CO) ₂ and Rh (AcAc) (CO) (TPP) are both catalytic active species HRh under the reaction condition of syngas and triphenylphosphine (TPP). It is known to convert to (CO) (TPP) ₃ .

In addition to cobalt (Co) and rhodium (Rh), the core metals of the oxo catalyst are iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe) and nickel (Ni). ) Can be applied. However, since the metals are known to exhibit catalytic activity in the order of Rh >> Co> Ir, Ru> Os> Pt> Pd> Fe> Ni, most of the processes and researches are focused on rhodium and cobalt.

The catalytic ligands include phosphine (Phosphine, PR ₃ , R = C ₆ H ₅ , nC ₄ H ₉ ), phosphine oxide (Phosphine Oxide, O = P (C ₆ H ₅ ) ₃ ), phosphite, Amine, Amide, Isonitrile, etc. are applicable, but triphenylphosphine (TPP) is the best in terms of catalyst activity, stability and cost.

By the way, in the case of triphenylphosphine which is widely used as a catalyst ligand of the oxo reaction, it is easily combined with oxygen molecules during the hydroformylation reaction and oxidized to triphenylphosphine oxide. This acts as a high boiling point material in the separation process after the reaction step in the oxo process to cause a high temperature process for separation from the product aldehyde. After the separation process, the catalyst solution is recycled back to the reaction process, and the catalyst in contact with the high temperature in the separation process is affected by its stability. Therefore, the removal of triphenylphosphine oxide, a high boiling point material that causes high temperatures in the separation process, consequently prevents the catalyst solution from contacting the high temperature environment, thereby contributing to the maintenance of stability. In addition, by removing the oxidized triphenylphosphine oxide, the margin of the volume occupied by the triphenylphosphine oxide in the reactor is generated, and as the volume, propene and syngas as raw materials can be further supplied. Since the productivity can be increased, the effective removal of triphenylphosphine oxide is very important not only in terms of catalyst stability but also in reaction productivity.

It is an object of the present invention to provide a method and apparatus capable of continuously and effectively removing an oxide of a catalyst ligand from a catalyst solution of a hydroformylation reaction in an oxo process.

In order to achieve the above technical problem, the present invention provides a method for separating the catalyst ligand oxide by recrystallization from a catalyst solution comprising a catalyst and a catalyst ligand subjected to the hydroformylation reaction.

The present invention also provides a catalyst solution inlet into which a catalyst solution comprising a catalyst and a catalyst ligand subjected to a hydroformylation reaction is introduced, a recrystallization region for recrystallizing the catalyst ligand oxide in the catalyst solution introduced into the catalyst solution inlet, and recrystallization. Provided is a device for removing the catalyst ligand oxide from the catalyst solution subjected to the hydroformylation reaction, comprising a catalyst solution outlet for discharging the remaining catalyst solution except the precipitated catalyst ligand oxide.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by using a recrystallization method to remove the catalyst ligand oxide from a catalyst solution comprising a catalyst and a catalyst ligand undergoing hydroformylation. In this way, not only can the catalyst ligand oxide be easily and effectively removed from the catalyst solution of the hydroformylation reaction, but the catalyst ligand oxide can be removed and the catalyst is removed in the catalyst solution during the oxo process including the hydroformylation step and separation of the product. Since the recycling of the solution can be carried out continuously, the catalyst ligand oxide can be removed continuously and effectively without affecting the operation of the existing process, thereby greatly improving catalyst stability and reaction productivity.

In the present invention, the catalyst in the catalyst solution used in the hydroformylation reaction can be used without particular limitation as long as it is known in the art. For example, transition metal catalysts, specifically cobalt (Co), rhodium (Rh) iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe), nickel (Ni) A catalyst containing a metal such as may be used, and a catalyst containing cobalt, rhodium or iridium is preferable. More specifically, acetylacetonatodicarbonyldium (Rh (AcAc) (CO) ₂ ), acetylacetonatocarbonyltriphenylphosphinedium (Rh (AcAc) (CO) (TPP)), hydridocarbonyl Tri (triphenylphosphine) rhodium (HRh (CO) (TPP) ₃ ), rhodium / tipipthyses (Rh / TPPTS), acetylacetonatodicarbonyliridium (Ir (AcAc) (CO) ₂ ), hidolido Carbonyltri (triphenylphosphine) iridium (Hir (CO) (TPP) ₃ ), tetra (carbonyl) cobalt sodium (NaCo (CO) ₄ ), and hydridotricarbonyltributylphosphinecobalt (HCo ( CO) ₃ PBu ₃ ) and the like can be used, but is not limited to these examples.

The content of the transition metal is preferably 50 to 500 ppm based on the reaction solution. If the content of the transition metal is less than 50 ppm, the hydroformylation reaction rate may be slowed down, and if it is more than 500 ppm, the cost increases and there is no more favorable effect on the reaction rate.

In the present invention, the catalyst ligand in the catalyst solution used for the hydroformylation reaction includes phosphine (Phosphine, PR ₃ , R = C ₆ H ₅ , nC ₄ H ₉ ), amine (Amine), amide (Amide), Isonitrile and the like can be used, with triphenylphosphine (TPP) being most preferred.

The catalyst ligand may be used 0.5 to 150 moles, preferably 1 to 20 moles. If the content of the catalyst ligand is less than 0.5 moles there is a problem in the stability of the catalyst system, if more than 150 moles there is a problem that the cost rises without a particular benefit.

In the present invention, the catalyst solution subjected to the hydroformylation reaction is a high temperature state of about 80 to 120 ℃, removal of the catalyst ligand oxide through recrystallization can be carried out using a temperature difference. In this case, in order to recrystallize the catalyst ligand oxide from the above-described high temperature catalyst solution, it is preferable to maintain the recrystallization temperature at 0 to 50 ° C. The amount of the catalyst ligand oxide that is recrystallized and precipitated decreases as the recrystallization temperature of the catalyst ligand oxide increases, and increases as the recrystallization temperature decreases, but it is more preferable to maintain the recrystallization temperature at 20 to 40 ° C. in the process operation. Do.

 In addition, the amount of catalyst ligand that is recrystallized and precipitates varies depending on the time of maintaining the catalyst solution at the recrystallization temperature of the catalyst ligand oxide. Therefore, it is desirable to maintain the recrystallization of the catalyst ligand oxide for 0.5 to 24 hours after reaching the desired temperature within the above-mentioned temperature range, and more preferably 1 to 16 hours.

In the method for removing the catalyst ligand oxide from the catalyst solution of the hydroformylation reaction according to the present invention, the catalyst solution may be further stirred while recrystallizing the catalyst ligand oxide. Regardless of the agitation, a predetermined amount or more of the catalyst ligand oxide is precipitated, but a difference may occur in the form and amount of the precipitate depending on the presence or absence of the agitation. When accompanied by agitation, the precipitate is in the form of a powder, and a larger amount is precipitated, but in addition to the catalytic ligand oxide to be removed through recrystallization, a small amount of a substance serving as a catalyst ligand may be precipitated. On the other hand, in the absence of stirring, precipitates are formed in the crystalline form, and the amount of precipitation is relatively small, but the catalyst ligand itself is hardly precipitated. Therefore, it is possible to determine whether or not stirring depending on the amount and the situation to be precipitated.

In the present invention, the catalytic ligand oxide precipitated by recrystallization as described above can be removed from the catalyst solution by conventional methods known in the art, such as filtration or the like.

The method for removing the catalyst ligand oxide from the catalyst solution subjected to the hydroformylation reaction according to the present invention can be carried out during an oxo process which is carried out continuously. Specifically, in the oxo process in which the step of hydroformylation and the separation of the catalyst solution and the aldehyde compound from the product are repeatedly performed, the present invention is carried out from at least a portion of the catalyst solution which has been subjected to the step of separating the catalyst solution from the aldehyde compound. The catalyst ligand oxide may be removed by the method according to the above method, and the catalyst solution from which the catalyst ligand oxide is removed may be added to the hydroformylation reaction step.

In the successive oxo process, a catalyst ligand oxide is precipitated and removed from at least a portion of the catalyst solution subjected to hydroformylation by the recrystallization method according to the above-described method of the present invention, and the catalyst ligand oxide is removed. By repeating the process such that the solution continues to circulate the oxo process, the amount of catalytic ligand oxide present in the catalyst solution can be reduced while continuously performing the oxo process. The amount of one-time catalyst solution that undergoes the recrystallization step in the total catalyst solution used in the continuous oxo process is not particularly limited, and even if the amount is very small, the above process is repeated to reduce the catalyst ligand oxide in the catalyst solution. The object of the present invention can be achieved. Those skilled in the art can determine the amount of one-time catalyst solution through step (c) in consideration of process conditions such as the capacity of the catalyst ligand oxide removal device. As described above, by reducing the catalyst ligand oxide in the catalyst solution during the continuous oxo process, the high temperature process due to the presence of the catalyst ligand oxide can be avoided, thereby contributing to the stability of the catalyst and greatly improving the productivity.

The present invention also provides a catalyst solution inlet into which a catalyst solution comprising a catalyst and a catalyst ligand subjected to a hydroformylation reaction is introduced, a recrystallization zone for recrystallizing the catalyst ligand oxide in the catalyst solution introduced into the catalyst solution inlet, and An apparatus for removing a catalyst ligand oxide from a catalyst solution subjected to a hydroformylation reaction, comprising a catalyst solution outlet for discharging the remaining catalyst solution except the precipitated catalyst ligand oxide.

In the apparatus for removing the catalytic ligand oxide, the recrystallization region may be, for example, a jacket-shaped bath. The recrystallization zone is maintained at 0 to 50 ° C., preferably 20 to 40 ° C., so that the catalyst ligand oxide can be recrystallized, and the catalyst solution introduced thereto is maintained at 0.5 to 24 hours, preferably 1 to 16 hours. .

The apparatus for removing the catalytic ligand oxide may include a controller for controlling the amount of the catalyst solution introduced into the apparatus, or a controller capable of adjusting the temperature in the recrystallization zone and the retention time of the catalyst solution. In addition, it is preferable to provide filtering means between the recrystallization zone and the catalyst solution inlet or the recrystallization zone and the catalyst solution outlet in order to prevent the catalyst ligand oxide precipitated and precipitated out of the catalyst solution inlet or catalyst solution outlet. . In addition, the apparatus for removing the catalytic ligand oxide may be further provided with a stirrer as necessary.

The apparatus according to the present invention may be provided as some components of the apparatus for performing the oxo process as illustrated in FIG. 1. 1 illustrates an oxo processing apparatus, which comprises a raw material supply line 1; Hydroformylation reactors 2, 3 having a feed inlet and a reactant outlet connected to a feed line; Separating means (4, 5) connected to the reactant outlet of the hydroformylation reactor and separating the reactant into a product and a catalyst solution; A product conveying line (6) at one end connected to said separating means; A catalyst solution recovery line 9 connected at one end to the separation means and at the other end to the hydroformylation reactor; And a catalyst solution inlet through which at least a portion of the catalyst solution is introduced from an intermediate portion of the catalyst solution recovery line, a recrystallization region for recrystallizing the catalyst ligand oxide in the catalyst solution introduced into the catalyst solution inlet, and a catalyst ligand that is recrystallized and precipitated. And a catalyst ligand oxide removal device (8) comprising a catalyst solution outlet for discharging the remaining catalyst solution except oxide to a position downstream of the catalyst solution inlet in the catalyst solution recovery line. However, FIG. 1 is intended to illustrate the invention and is not intended to limit the scope of the invention thereby.

The raw material supply line 1 allows the olefinic compound, syngas and catalyst solution to be supplied to the reactors 2 and 3 through this.

The hydroformylation reactors 2 and 3 include a raw material inlet and a reactant outlet connected to a raw material supply line, and are divided into two, but the scope of the present invention is not limited to the number of reactors. By controlling the temperature and pressure in these hydroformylation reactors, the raw materials introduced into the raw material feed line participate in the hydroformylation reaction.

The separating means (4, 5) is composed of an evaporator consisting of the upper end (4) and the lower end (5). Due to the action of the evaporator, the upper part 4 collects the products of the reactants discharged from the reactor, and the lower part 5 collects the catalyst solution.

The product collected at the upper end 4 of the separating means is conveyed through the product conveying line 6. This product transfer line can be connected to a separate collection device for accumulating the product resulting from repeated reactions. Further, in order to recover the unreacted raw material in the product passing through the product transfer line 6, the oxo processing apparatus is connected at one end to the product transfer line 6 and the other end of the hydroformylation reactor (2, 3). It may further comprise an unreacted raw material recovery line (7) connected to).

The catalyst solution collected at the lower end 5 of the separation means is fed back to the reactor via a catalyst solution recovery line 9. Here, the oxo processing apparatus includes a catalyst ligand oxide removal device 8 capable of introducing at least a portion of the catalyst solution from the catalyst solution recovery line to remove the catalyst ligand oxide through recrystallization. The oxo process apparatus according to the present invention is equipped with a catalyst ligand oxide removal device 8 connected to the catalyst solution recovery line 9 so as to continuously perform the oxo process without any effect on the operation of the existing process. Can be effectively removed.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by the description of the examples.

Example

Example 1

100 g of a high temperature catalyst solution at 90 ° C. was placed in a jacket-shaped bath maintained at 40 ° C., and then recrystallized without stirring for 1 hour. The resulting precipitate was separated from the catalyst solution from which triphenylphosphine oxide (TPPO) was removed. At this time, as the catalyst solution, 19 wt% of triphenylphosphine, 36 wt% of triphenylphosphine oxide, and 45 wt% of butyl aldehyde were used, and rhodium (Rh) contained 1000 ppm. And the weight of the precipitate separated from the catalyst solution was measured. It was confirmed through GC that the precipitated material was triphenylphosphine oxydra. The form of the precipitate was observed, and the removal rate of triphenylphosphine oxide (TPPO) from the catalyst solution was calculated based on the weight, and the results are shown in Table 1. The triphenylphosphine oxide (TPPO) was confirmed by GC and NMR.

Example 2

100 g of a high temperature catalyst solution at 90 ° C. was carried out in the same manner as in Example 1 except that the bath was placed in a jacket-shaped bath maintained at 20 ° C. The results are shown in Table 1. In this case, the removal rate of triphenylphosphine oxide (TPPO) was higher than in Example 1.

Example 3

It carried out similarly to Example 1 except having maintained the recrystallization time in 16 hours. The results are shown in Table 1. In this case, triphenylphosphine oxide (TPPO) removal rate was similar to that of Example 1.

Example 4

It carried out similarly to Example 1 except having maintained the recrystallization time in a bath at 0.5 hour. The results are shown in Table 1. In this case, the triphenylphosphine oxide (TPPO) removal rate was slightly lower than that in Example 1.

Example 5

The same procedure as in Example 1 was carried out except that the recrystallization process was performed with stirring. The results are shown in Table 1. In this case, the removal rate of triphenylphosphine oxide (TPPO) was slightly higher than that of Example 1, and the form of precipitates was different from that of Example 1.

Precipitation (g) shape TPPO removal rate (%) Example 1 22.0 decision 61.11 Example 2 29.4 decision 81.67 Example 3 22.7 decision 63.06 Example 4 12.8 decision 35.56 Example 5 23.1 powder 64.17

As mentioned above, the present embodiments selectively remove catalyst ligand oxides, especially triphenylphosphine oxide (TPPO), from the hydroformylation reaction catalyst solution through recrystallization to increase catalyst stability and efficiency of the oxo process. It was carried out for the purpose of checking the precipitation tendency of triphenylphosphine oxide (TPPO) according to the temperature, precipitation time and stirring in the recrystallization process.

As a result of Example 2, the triphenylphosphine oxide (TPPO) removal rate was higher when cooling to a low temperature of 20 ℃ at a high temperature of 90 ℃ compared to the low temperature of 40 ℃ of Example 1. This trend indicates that the greater the temperature difference before and after the recrystallization process, the more effective triphenylphosphine oxide (TPPO) removal is.

The results of Example 3 show no significant change when the time required for the recrystallization process lasted for 1 hour or more in the same temperature condition. That is, the recrystallization of triphenylphosphine oxide (TPPO) at the temperature conditions used in the embodiment can be said to be enough for about 1 hour. However, from the results of Example 4, it can be seen that only a part of triphenylphosphine oxide (TPPO) in the initial catalyst solution is recrystallized when the recrystallization process is continued for less than 1 hour.

Example 5 shows the result of the presence or absence of agitation during the recrystallization process under the same conditions. Although there is no significant difference in the removal rate of triphenylphosphine oxide (TPPO), the precipitated triphenylphosphine oxide (TPPO) is formed in a powder form when stirred, and is different from the crystalline form when the mixture is not stirred. Other trends. However, as mentioned above, it does not affect the removal of the original purpose triphenylphosphine oxide (TPPO).

As described above, according to the present invention, the catalyst ligand oxide, particularly high boiling point triphenylphosphine oxide (TPPO), can be effectively removed from the hydroformylation catalyst solution by the recrystallization method. In addition, the method according to the invention can continuously remove the catalyst ligand oxide in the catalyst solution while continuously performing the oxo process without affecting the operation of the existing process.

Although the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and variations are within the scope of the present invention. Of course.

Claims (11)

A method of separating a catalyst ligand oxide by recrystallization from a catalyst solution comprising a catalyst and a catalyst ligand undergoing hydroformylation. The method of claim 1, wherein the recrystallization is performed using a temperature difference. The method of claim 1, wherein the recrystallization is carried out at a temperature of 0 to 50 ° C. The method of claim 1, wherein the recrystallization is performed for 0.5 to 24 hours. The method of claim 1, wherein the catalyst is cobalt (Co), rhodium (Rh) iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe) and nickel (Ni) It is a metal catalyst comprising at least one selected from. The method according to claim 1, wherein the catalytic ligand is selected from phosphine (Phosphine, PR ₃ , R = C ₆ H ₅ , n- C ₄ H ₉ ), amine (Amine), amide (Amide) and isonitrile And at least one. The method of claim 1, further comprising removing the catalyst ligand oxide by filtration after the recrystallization. The method of claim 1 wherein the process is performed during a continuous oxo process. A catalyst solution inlet into which a catalyst solution comprising a catalyst and a catalyst ligand subjected to a hydroformylation reaction is introduced, a recrystallization region for recrystallizing the catalyst ligand oxide in the catalyst solution introduced into the catalyst solution inlet, and a catalyst ligand precipitated by recrystallization An apparatus for removing a catalyst ligand oxide from a catalyst solution subjected to a hydroformylation reaction, comprising a catalyst solution outlet for discharging the remaining catalyst solution except oxides. 10. The apparatus of claim 9, further comprising filtering means between the recrystallization zone and the catalyst solution inlet or between the recrystallization zone and the catalyst solution outlet. 10. The apparatus of claim 9, wherein the recrystallization zone further comprises a stirrer.

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