Method for producing catalyst for selective hydrogenation of cyclododecatriene and catalyst produced by the method

Abstract

The present invention relates to a method for producing a catalyst for the selective hydrogenation reaction of cyclododecatriene and a catalyst produced by the method. The method for producing a catalyst for the selective hydrogenation reaction of cyclododecatriene of the present invention comprises: (S1) reacting ruthenium chloride with formaldehyde to produce a ruthenium complex; and (S2) adding triphenylphosphine to the ruthenium complex and conducting the reaction.

Description

Technical Field

[0001] The present invention relates to a method for producing a catalyst for selective hydrogenation of cyclododecatriene and the catalyst produced by the method. Background Art

[0002] The synthesis of cyclododecene (CDEN) using cyclododecatriene (CDT) as a starting material and selective hydrogenation is well documented in the literature, and a large number of studies have been conducted to improve the yield of cyclododecene.

[0003] For the above-mentioned selective hydrogenation reaction, a metal ligand catalyst known as a Wilkinson catalyst is used, that is, a catalyst in which a ligand such as triphenylphosphine (TPP), CO and a halogen element are combined with a metal such as ruthenium (Ru), rhodium (Rh), cobalt (Co), nickel (Ni).

[0004] Such catalysts play a major role in the selective hydrogenation reaction, i.e., selective hydrogenation reaction, by activating the entire reaction and accelerating the entire reaction without reacting themselves, or by improving the yield of the product. Therefore, various studies on catalysts have been conducted.

[0005] In U.S. authorized patent US the 7838705th, ruthenium chloride (RuCl ), triphenylphosphine (TPP), formaldehyde, acetic acid, ethanol etc. are added in the hydrogenation reactor of cyclododecatriene, and under hydrogenation reaction conditions, synthesize ruthenium composite catalyst by original position (in-situ) mode and use.Such catalyst manufacturing method has manufactured the ruthenium composite catalyst that can improve cyclododecene yield, but has generated byproduct hydrochloric acid in the manufacturing process of catalyst, and reaction residues such as methyl alcohol, water, formaldehyde remain, so shortcoming is, comprises a large amount of impurities in the resultant separated after selective hydrogenation reaction.

[0006] Furthermore, the production of the catalyst involves the use of various solvents, which present difficulties in managing and using the solvents, thus resulting in a drawback of a complex overall process. Summary of the Invention

[0007] The object of the present invention is to provide a method for producing a catalyst for the selective hydrogenation reaction of cyclododecatriene, which can produce a high-purity catalyst through simple steps and has a high catalyst production yield.

[0008] Another object of the present invention is to provide a catalyst for the selective hydrogenation of cyclododecatriene, which, when used in the selective hydrogenation reaction, can produce cyclododecene in a faster time with high selectivity and high yield.

[0009] The method for producing a catalyst for the selective hydrogenation reaction of cyclododecatriene of the present invention comprises: (S1) reacting ruthenium chloride with formaldehyde to produce a ruthenium complex; and (S2) adding triphenylphosphine to the ruthenium complex and then reacting.

[0010] In the method for producing a catalyst for the selective hydrogenation of cyclododecatriene according to one embodiment of the present invention, the step (S1) may be performed at a temperature of 40°C to 80°C.

[0011] In the method for producing a catalyst for the selective hydrogenation of cyclododecatriene according to one embodiment of the present invention, in the step (S1), the molar ratio of ruthenium chloride:formaldehyde may be 1:20 to 400.

[0012] In the method for producing a catalyst for the selective hydrogenation of cyclododecatriene according to one embodiment of the present invention, in the step (S1), a CO ligand may be formed by the reaction of ruthenium chloride with formaldehyde.

[0013] In the method for producing a catalyst for the selective hydrogenation of cyclododecatriene according to one embodiment of the present invention, the reaction in step (S2) may be performed at the gasification temperature of the formaldehyde.

[0014] In the method for manufacturing a catalyst for the selective hydrogenation reaction of cyclododecatriene according to one embodiment of the present invention, in the above-mentioned step (S2), the molar ratio of the above-mentioned ruthenium chloride: the above-mentioned triphenylphosphine can be 1:1 to 300.

[0015] In the method for producing a catalyst for the selective hydrogenation of cyclododecatriene according to one embodiment of the present invention, in the above step (S2), a PPh 3 ligand may be formed by reacting a ruthenium complex with triphenylphosphine.

[0016] The present invention is a catalyst for selective hydrogenation of cyclododecatriene produced by the above method.

[0017] In the catalyst for selective hydrogenation of cyclododecatriene according to one embodiment of the present invention, when performing the selective hydrogenation reaction of cyclododecatriene, the catalyst may be added in an amount of 40 ppm to 200 ppm based on ruthenium relative to cyclododecatriene.

[0018] According to one embodiment of the present invention, the catalyst for the selective hydrogenation reaction of cyclododecatriene may be RuH(PPh3)3COCl.

[0019] The method for producing a catalyst for the selective hydrogenation reaction of cyclododecatriene according to the present invention can produce a high-purity catalyst with a high yield through relatively simple steps without using an additional solvent.

[0020] The catalyst produced by the production method of the present invention has excellent catalytic performance. Therefore, when used in the selective hydrogenation reaction of cyclododecatriene, the selective hydrogenation reaction time of cyclododecatriene can be shortened while cyclododecene can be produced in a high yield. DETAILED DESCRIPTION

[0021] For the technical and scientific terms used in this specification, unless otherwise defined, they have the meanings generally understood by those skilled in the art, and descriptions of well-known functions and structures that may unnecessarily obscure the main purpose of the present invention are omitted in the following description.

[0022] In addition, the singular forms used in this specification are intended to include the plural forms as well, unless otherwise indicated in the context.

[0023] In addition, unless otherwise specified in this specification, the units used are based on weight. As an example, the unit of % or ratio refers to weight % or weight ratio. Unless otherwise defined, weight % means the weight % of any component in the entire composition in the composition.

[0024] In addition, the numerical ranges used in this specification include the lower limit and upper limit, all values ​​within the range, theoretically induced increments from the form and width of the defined range, all values ​​defined therein, and all possible combinations of the upper and lower limits of the numerical range defined in different forms. In the description of the present invention, unless otherwise specified, values ​​outside the numerical range that may occur due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0025] The term "comprising" in this specification is an open-ended description having a meaning equivalent to expressions such as "having", "containing", "having" or "characterized by", and does not exclude elements, materials or processes not further listed.

[0026] In addition, the term "substantially" in this specification means that other elements, materials or processes not listed together with the specific elements, materials or processes can be present in an amount that does not bring about a significant impact to a degree that is not allowed by at least one basic and new technical concept of the invention.

[0027] The present invention relates to a method for producing a catalyst for the selective hydrogenation reaction of cyclododecatriene, comprising: (S1) reacting ruthenium chloride with formaldehyde to produce a ruthenium complex; and (S2) adding triphenylphosphine to the ruthenium complex and then carrying out the reaction.

[0028] In the past, ruthenium chloride (RuCl ), triphenylphosphine (TPP), formaldehyde, acetic acid, ethanol etc. are added to the hydrogenation reactor of cyclododecatriene, and under hydrogenation reaction conditions, the ruthenium composite catalyst is synthesized by in-situ mode and used. The manufacture method of this catalyst generates by-product hydrochloric acid in the process of manufacturing catalyst, and reaction residues such as methanol, water, formaldehyde remain, so the shortcoming is that, comprises a large amount of impurities in the resultant separated after the selective hydrogenation reaction. In addition, when manufacturing catalyst, owing to using various solvents, there is difficulty in the management and use of solvent, therefore has the shortcoming of whole process complexity.

[0029] But the present invention can manufacture the catalyst for the selective hydrogenation reaction of cyclododecatriene (CDT) based on ruthenium chloride, formaldehyde and triphenylphosphine (Triphenylphosphine, TPP) by relatively simple operation, and does not use other solvent.In addition, in the catalyst manufacturing process, by products such as HCl are removed, therefore need not to carry out other separation process in order to obtain highly purified catalyst, can directly be put into the selective hydrogenation reaction of cyclododecatriene after manufacturing.In addition, the present invention can generate catalyst with high yield when manufacturing catalyst, can show excellent process efficiency.

[0030] Furthermore, the catalyst produced by the production method of the present invention has excellent catalytic performance. Therefore, when used in the selective hydrogenation reaction of cyclododecatriene, the selective hydrogenation reaction time of cyclododecatriene can be shortened while producing cyclododecene in high yield.

[0031] Specifically, the present invention first implements the step (S1) of reacting ruthenium chloride with formaldehyde to produce a ruthenium complex. At this time, a CO ligand (carbonyl group) may be formed as ruthenium chloride (RuCl3) reacts with formaldehyde (CH2O). That is, the ruthenium complex may contain the CO ligand and ruthenium.

[0032] The temperature of step (S1) is not limited as long as it is within the range where ruthenium chloride and formaldehyde can react, but it can be preferably carried out at a temperature of 40° C. to 80° C., more preferably 50° C. to 60° C. Within the above range, ruthenium chloride and formaldehyde can react smoothly in a relatively short period of time to form a ruthenium complex.

[0033] In step (S1), the reaction time can be 10 minutes to 1 hour, specifically 20 minutes to 40 minutes, but is not particularly limited as long as it is a time that allows the reaction between ruthenium chloride and formaldehyde to be completed.

[0034] In the step (S1), the molar ratio of ruthenium chloride: formaldehyde can be 1:20 to 400, specifically, 1:80 to 350, more specifically, 1:100 to 150, but is not limited thereto. However, within the above range, the ruthenium complex generated by the reaction of ruthenium chloride and formaldehyde is dissolved in formaldehyde, so that the reaction in the step (S2) described later occurs smoothly. Simultaneously, without consuming relatively high-priced ruthenium chloride, a ruthenium complex can be formed.

[0035] In step (S1), ruthenium chloride may be in the form of dark brown or black powder, and formaldehyde may be pure formaldehyde or a formaldehyde aqueous solution. The formaldehyde aqueous solution may have a concentration of 5 wt % to 40 wt %, but is not limited thereto.

[0036] In step (S1), the formation of CO ligands and the generation of ruthenium complexes can be visually detected by color change. For example, when ruthenium chloride powder is mixed with formaldehyde solution, it will appear reddish brown before the reaction and dark green after the reaction.

[0037] The present invention, after the above-described step (S1), implements the step (S2) of adding triphenylphosphine to the above-described ruthenium complex and reacting the mixture, thereby manufacturing a catalyst for the selective hydrogenation of cyclododecatriene. Accompanying the implementation of step (S2), a PPh3 ligand can be formed by the reaction of the ruthenium complex and triphenylphosphine. That is, the manufactured catalyst can include the above-described CO ligand and PPh3 ligand.

[0038] Specifically, after step (S1), molten triphenylphosphine is added to formaldehyde in which a ruthenium complex is dissolved, thereby obtaining a heterogeneous liquid mixture. The molten triphenylphosphine is melted at a temperature above its melting point of 80°C. The temperature is not particularly limited as long as it can be melted, but preferably, completely melted triphenylphosphine is used. The ruthenium complex and triphenylphosphine are then reacted to produce a catalyst for the selective hydrogenation of cyclododecatriene.

[0039] In step (S2), the reaction can be carried out at the vaporization temperature of formaldehyde. The reaction between the ruthenium complex and triphenylphosphine can be achieved due to the vaporization of formaldehyde. The temperature of implementation is not limited as long as it is within the range of formaldehyde vaporization, but specifically, it can be above the melting point of triphenylphosphine, preferably at a temperature of 80°C to 200°C, more preferably at a temperature of 100°C to 140°C. Within the above range, the residual formaldehyde, moisture, methanol that did not participate in the reaction in step (S1), and HCl generated in step (S1) are vaporized, and the ruthenium complex and triphenylphosphine react smoothly in a relatively short time, thereby generating a ruthenium complex in a short time.

[0040] In addition, in step (S2), the reaction time is not limited as long as it is a time during which all the formaldehyde can be vaporized.

[0041] In step (S2), the amount of triphenylphosphine added can be based on the ruthenium chloride added in step (S1). Specifically, the molar ratio of ruthenium chloride to triphenylphosphine added can be 1:1 to 300, specifically 1:4.5 to 230, but is not limited thereto. However, within the above range, the production of a catalyst having excellent catalytic performance can be achieved.

[0042] Furthermore, the present invention relates to a catalyst produced by the above-mentioned method. Hereinafter, the catalyst produced by the above-mentioned method will be described in detail.

[0043] The catalyst produced by the above method is used for the selective hydrogenation of cyclododecatriene and can be represented by the chemical formula RuH(PPh3)3COCl. Such a catalyst has excellent catalytic performance. Therefore, when used in the selective hydrogenation of cyclododecatriene, the selective hydrogenation reaction time of cyclododecatriene can be shortened while producing cyclododecene in high yield.

[0044] Specifically, in the selective hydrogenation reaction of cyclododecatriene, the catalyst of the present invention can be added in an amount sufficient to allow the reaction of the reactants to proceed fully, without limitation. However, based on ruthenium, the amount added can be 40 ppm to 200 ppm, specifically 50 ppm to 150 ppm, relative to cyclododecatriene. Within this range, the catalyst can exhibit excellent catalytic performance relative to the amount of catalyst added, and cyclododecene (CDEN) can be efficiently produced from cyclododecatriene.

[0045] Meanwhile, the selective hydrogenation reaction of cyclododecatriene using the catalyst of the present invention as described above can be carried out at a temperature of 100 to 200° C. and a pressure of 10 to 80 bar, more preferably at a temperature of 140 to 180° C. and a pressure of 20 to 60 bar, and even more preferably at a temperature of 150 to 175° C. and a pressure of 20 to 40 bar. However, this is only a preferred example for increasing the yield of cyclododecene, and the present invention is not limited thereto.

[0046] The following examples illustrate the method for producing the catalyst for the selective hydrogenation of cyclododecatriene according to the present invention in more detail. However, the following examples are merely a reference for describing the present invention in detail, and the present invention is not limited thereto and can be implemented in various forms.

[0047] Unless otherwise defined, all technical and scientific terms have the same meanings as those commonly understood by one skilled in the art. In this application, descriptive terms are used solely to effectively describe specific embodiments and are not intended to limit the present invention. Furthermore, for additives not specifically mentioned in this specification, the unit of weight percent may be used.

[0048] (Example 1)

[0049] A reaction solution was prepared by dissolving 1.0 g of RuCl₃ in 119.7 g of formaldehyde (37% formaldehyde aqueous solution), followed by reaction at 60°C for 30 minutes. After confirming that the reaction solution had changed from reddish-brown to dark green, 3.27 g of triphenylphosphine (TPP) completely melted at 100°C was added and mixed, and the remaining formaldehyde was evaporated at 100°C to produce a catalyst.

[0050] (Example 2)

[0051] A catalyst was produced by the same method as in Example 1, except that 4.91 g of triphenylphosphine (TPP) was used instead of 3.27 g of triphenylphosphine (TPP).

[0052] (Example 3)

[0053] A catalyst was produced by the same method as in Example 1, except that 205.7 g of triphenylphosphine (TPP) was used instead of 3.27 g of triphenylphosphine (TPP).

[0054] (Experimental example)

[0055] In order to evaluate the performance of the catalyst of the example, the catalyst was added to the selective hydrogenation reaction of cyclododecatriene, and the reaction time, conversion, selectivity of cyclododecene and yield were measured.

[0056] The charging conditions for each example are shown in Table 1 below. In each example, the total amount of TPP used, including the TPP contained in the catalyst, was fixed at 230 times the amount of Ru. The CDT charging amount (mol) for the comparative example was the same as in the examples: 0.08 g of RuCl₃, 9.58 g of formaldehyde (37% formaldehyde aqueous solution), and 20.0 g of TPP were charged in situ.

[0057] [Table 1]

[0058] distinguish Example 1 Example 2 Example 3 Catalyst mixture input amount (Ru:TPP mol ratio) 0.317(1:3) 0.448(1:4.5) 20.1(1:230) TPP (relative to Ru, mol ratio) 19.8(227) 19.7(225.5) 0(0) CDT input amount (mol ratio) 400 400 400

[0059] The reaction solution was stirred under 6 bar of hydrogen and then subjected to a selective hydrogenation reaction for 2 hours at 180°C and 20 bar in a stirred tank reactor equipped with a gas-introducing hollow stirrer. After 1.5 hours of selective hydrogenation, the solution was cooled to below 30°C under nitrogen and recovered.

[0060] The conversion rate was calculated by the following calculation formula 1, the selectivity was calculated by the following calculation formula 2, and the yield was calculated by the following calculation formula 3. The results are shown in Table 2 below.

[0061] [Calculation formula 1]

[0062] Conversion rate (%) = (CDT0-CDT1-CDDN1) / CDT0×100

[0063] In formula 1, CDT0 represents the molar amount of cyclododecatriene fed, CDT1 represents the molar amount of cyclododecatriene after the reaction, and CDDN1 represents the molar amount of cyclododecadiene. Cyclododecadiene (CDDN) is a product resulting from hydrogenation of only one of the three double bonds in cyclododecatriene, leaving two double bonds uncompleted.

[0064] [Calculation formula 2]

[0065] Selectivity (%) = CDEN1 / (CDEN1+CDAN1)×100

[0066] In the above calculation formula 2, CDEN1 is the number of moles of cyclododecene produced, and CDAN1 is the number of moles of cyclododecane, a by-product produced.

[0067] [Calculation formula 3]

[0068] Yield (%) = conversion rate × selectivity

[0069] [Table 2]

[0070]

[0071] With reference to Table 2 above, it was confirmed that the catalyst of the present invention can produce cyclododecene with a high conversion rate and selectivity similar to the method of the comparative example, and that cyclododecene can be produced in a high yield in a shorter reaction time than in the comparative example. As described above, the present invention is described through specific matters and limited examples, but these are provided only to facilitate a more comprehensive understanding of the present invention. The present invention is not limited to the above-described examples, and those skilled in the art will be able to make various modifications and variations based on such descriptions.

[0072] Therefore, the concept of the present invention cannot be limited to the illustrated embodiments, and not only the scope of protection claimed by the present invention described later, but also all scopes that are equal to or have equivalent modifications to the scope claimed by the present invention belong to the scope of the concept of the present invention.

Claims

1. A method for producing a catalyst for the selective hydrogenation of cyclododecatriene, comprising: (S1) a step of reacting ruthenium chloride with formaldehyde to produce a ruthenium complex; as well as (S2) a step of adding triphenylphosphine to the ruthenium complex and then reacting the mixture. wherein the step (S1) is carried out at a temperature of 40° C. to 80° C., and the step (S2) is carried out at the gasification temperature of the formaldehyde. Wherein, in the step (S1), the molar ratio of the ruthenium chloride: the formaldehyde is 1:20 to 400, and in the step (S2), the molar ratio of the ruthenium chloride: the input triphenylphosphine is 1:1 to 300.

2. The method for producing a catalyst for the selective hydrogenation of cyclododecatriene according to claim 1, wherein: In the step (S1), the CO ligand is formed by the reaction of ruthenium chloride and formaldehyde.

3. The method for producing a catalyst for the selective hydrogenation of cyclododecatriene according to claim 1, wherein: In the step (S2), the PPh3 ligand is formed by reacting the ruthenium complex with triphenylphosphine.

4. The method for producing a catalyst for the selective hydrogenation of cyclododecatriene according to claim 1, wherein: The catalyst is RuH(PPh3)3COCl.

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