JP6051980B2 - Method for producing 1,4-cyclohexanedimethanol - Google Patents

Description

  The present invention relates to a process for producing cycloalkanedimethanol by hydrogenating cycloalkanedicarboxylic acid. Specifically, 1,4-cyclohexanedicarboxylic acid (hereinafter sometimes abbreviated as 1,4-CHDA) is used as a catalyst. The present invention relates to a process for producing 1,4-cyclohexanedimethanol (hereinafter sometimes abbreviated as 1,4-CHDM) by hydrogenation in the liquid phase in the presence.

Cycloalkanedimethanol such as 1,4-CHDM is useful as a polyester-based paint, polyester-based synthetic fiber and synthetic resin, and particularly as a raw material for resins and fibers having excellent heat resistance, weather resistance, physical strength, etc. It is used.
Conventionally, as a method for producing 1,4-CHDM, a method for hydrogenating an ester is known. For example, in Patent Document 1, using a catalyst in which dimethyl terephthalate is supported on Ru or Pd on alumina, nuclear hydrogenation is performed to produce dimethyl cyclohexanedicarboxylate, and then the side chain of the obtained ester is Cu-Zn oxidized. A method for producing 1,4-CHDM by hydrogenation in the presence of a product catalyst is described. In Patent Document 2, 1,4-CHDM is produced by hydrogenating a dialkyl terephthalate to obtain 1,4-cyclohexanedimethyl ester, and then hydrogenating a side chain using a catalyst containing Ru and Su. A method is disclosed.

  On the other hand, in addition to the above method, there is also a method of obtaining cycloalkanedimethanol by directly hydrogenating cycloalkanedicarboxylic acid. For example, Patent Document 3 describes a method of obtaining 1,4-CHDM by hydrogenating a carboxyl group of 1,4-CHDA, and a ruthenium catalyst containing tin is described as a catalyst. . Moreover, when hydrogenation is performed in a solution state, purification of 1,4-CHDM from the produced solution can be performed by distillation or extraction.

  1,4-CHDM has a trans isomer and a cis isomer. In the production of 1,4-CHDM on an industrial scale, a method of hydrogenating 1,4-cyclohexanedimethyl ester is used. The resulting 1,4-CHDM is a mixture containing a trans isomer and a cis isomer at a certain ratio regardless of whether it is used or a method in which the carboxyl group of 1,4-CHDA is directly hydrogenated. .

  The cis form of 1,4-CHDM has a melting point of 43 ° C., and the trans form of 1,4-CHDM has a melting point of 67 ° C. As a 1,4-CHDM derivative, when a high melting point polyester or polyester amide is produced, a raw material having a high content of 1,4-CHDM trans isomer is preferably used. At normal temperature, 1,4-CHDM having a trans isomer content of 60 wt% or more is solid, but 1,4-CHDM having a trans isomer content of 55 wt% is in a fluid state.

In a method for producing 1,4-CHDM by a hydrogenation reaction, the hydrogenation reaction and the isomerization reaction proceed simultaneously. Therefore, in the isomerization reaction, the trans isomer content tends to a certain equilibrium value, and the equilibrium value of the 1,4-CHDM trans isomer content is between 72% and 75%. It is known.
In order to produce more 1,4-CHDM with a high trans isomer content, which is also in industrial demand, 1,4-CHDA is hydrogenated even if it is a method of hydrogenating 1,4-cyclohexanedimethyl ester. Even if it is a method to carry out, it is preferred to use as a raw material what has many trans isomers in 1,4-cyclohexane dimethyl ester of raw materials or 1,4-CHDA, and also from a cis isomer of cyclohexanedimethanol. It is necessary to promote isomerization to the trans isomer and suppress isomerization from the trans isomer to the cis isomer.

On the other hand, in order to produce more 1,4-CHDM having a high cis isomer content, it is necessary to suppress isomerization from the cis isomer to the trans isomer by using a raw material having a low trans isomer content as much as possible. .
Patent Document 4 describes that the trans isomer content in 1,4-CHDM obtained is controlled by a method of hydrogenating 1,4-cyclohexanedimethyl ester. In the paragraph, in the hydrogenation of 1,4-cyclohexanedimethyl ester, the yield of 1,4-CHDM and the trans isomer content are substantially synonymous, and the trans isomer content is controlled by the residence time of the reaction. It is described.

JP-T 8-510686 Japanese Patent Laid-Open No. 6-228028 JP 2000-80053 A JP-A-7-196559

  In recent years, with the diversification of needs for 1,4-CHDM, it is required to change the trans isomer content rate while maintaining a constant production amount and continuing operation. In the above Patent Documents 1 to 4, when 1,4-CHDM is produced, the production amount of 1,4-CHDM (conversion rate of raw material) is constant, and the trans isomer content in 1,4-CHDM is set as follows. It does not describe how to control. The method described in Patent Document 4 is a reaction under a gas phase, and it is not described that the production amount of 1,4-CHDM (conversion rate of raw material) and the isomerization rate are independently controlled. In order to obtain 1,4-CHDM having a trans isomer content of 1, the residence time must be changed. As a result, the production amount of 1,4-CHDM also changes at the same time, which is not an industrially preferable method.

  That is, the subject of this invention is providing the manufacturing method of 1, 4-CHDM which can control trans-isomer content rate, maintaining the conversion rate which was not able to be achieved with the prior art.

  As a result of intensive research on the above problems, the present inventors have conducted a hydrogenation step reaction in a method for producing 1,4-CHDM by hydrogenating 1,4-CHDA in the liquid phase in the presence of a catalyst. By manipulating the temperature and the total reaction pressure, it was found that a product 1,4-CHDM having an arbitrary trans isomer content can be produced while maintaining a desired conversion rate, and the present invention has been made. .

That is, the gist of the present invention resides in the following [1] and [2] .
[1] Using 1,4-cyclohexanedicarboxylic acid having a trans isomer content of 10 to 50 wt% as a raw material compound, a hydrogenation reaction is performed in the liquid phase in the presence of a solid catalyst containing at least ruthenium, tin, and platinum. Thus, when obtaining 1,4-cyclohexanedimethanol having a trans isomer content of 30 to 75 wt%, the hydrogenation reaction temperature is in the range of 200 to 240 ° C. while maintaining the conversion rate of the raw material compound. 1 having a desired trans isomer content by controlling the hydrogenation reaction temperature and / or the contact time by setting the total pressure in the range of 7-12 MPa and the contact time in the range of 0.5-1.5 hours. , 4-Cyclohexanedimethanol is obtained, A method for producing 1,4-cyclohexanedimethanol,
[2] The method for producing 1,4-cyclohexanedimethanol according to claim 1, wherein the total pressure of the hydrogenation reaction is further manipulated.
(that's all)

  According to the present invention, when 1,4-CHDM is produced from 1,4-CHDA, the trans content in 1,4-CHDM can be freely controlled. Moreover, it is also possible to produce 1,4-CHDM having a trans content of 30% or less, which was difficult to produce industrially by conventional methods.

It is the figure which expressed the trans content of 1, 4-CHDM as a function of temperature and contact time from the result of the Example of this invention. It is the schematic which shows the apparatus which performs the hydrogenation of 1, 4-CHDA in the Example of this invention.

  In the present invention, the raw material compound used for the production of cycloalkanedimethanol is cycloalkanedicarboxylic acid, and the number of carbon atoms of cycloalkane of cycloalkanedicarboxylic acid is preferably 3-12, more preferably 3-8. It is. Among these, 1,4-CHDA having 6 carbon atoms is particularly preferably used. The trans isomer content in the cycloalkanedicarboxylic acid is not particularly limited, but the trans isomer content is preferably 1 to 99 wt%, more preferably 5 to 80 wt%, and particularly preferably 10 to 10 wt%. 50 wt%. As the trans content of the cycloalkanedicarboxylic acid of the raw material compound increases, the solubility becomes lower, and if it is not heated sufficiently, it will not dissolve and may be clogged with piping or the like.

  The hydrogenation reaction of the present invention is a hydrogenation reaction in a liquid phase and is usually performed in the presence of a solvent. The solvent is not particularly limited as long as it does not react with the raw materials and products in the reaction step, and is not particularly limited as long as it does not adversely affect the reaction such as not poisoning the catalyst, for example, water, methanol, ethanol, etc. Solvents such as alcohols, ethers such as tetrahydrofuran and dioxane, hydrocarbons such as hexane and decalin can be used alone or as a mixed solvent if necessary. Among these, in the present invention, it is preferable to use an aqueous solvent containing water.

In the hydrogenation reaction under the liquid phase of the present invention, the raw material compound such as 1,4-CHDA and a catalyst are present in a solvent and maintained under a predetermined reaction condition, whereby the hydrogenation reaction is performed at a conversion rate close to 100%. The reaction can proceed. The ratio of the raw material compound to the solvent is preferably as high as possible as long as the raw material compound can be dissolved in the solvent.
If this ratio is small, the production efficiency of the reaction apparatus will decrease, and the efficiency of the apparatus and the consumption energy will be reduced when the product 1,4-CHDM is separated and recovered from the product solution such as 1,4-CHDM in the subsequent process. This is not preferable because it causes an increase. Even if this ratio is large, the solvent after separating the product from the product solution can be recycled and used in the hydrogenation step again. For example, when water is used as a solvent, it is preferably used so that the concentration of the raw material compound before the reaction is 5 to 50% by weight, more preferably 10 to 40% by weight.

  The catalyst of the present invention is not particularly limited as long as the side chain of cycloalkanedicarboxylic acid can be directly hydrogenated, but from the viewpoint of separation of the catalyst after the reaction and the product solution, a solid catalyst Are preferably used. The solid catalyst of the present invention is preferably a catalyst in which a metal having catalytic activity is supported on a carrier. Specifically, examples of the carrier include porous carriers such as activated carbon, alumina, silica, diatomaceous earth, titania, and zirconia. These may be used alone or in combination of two or more. A preferred carrier is activated carbon. The catalyst metal includes ruthenium and tin, and may optionally include at least one metal selected from rhodium and platinum, more preferably a catalyst comprising a combination of ruthenium, platinum and tin. It is a metal.

  Moreover, as a ratio which carries a catalyst metal, 0.5-50 weight% is preferable normally with respect to the total value of the weight of all the catalyst active metals, and the support | carrier, and 1-20 weight% is more preferable. From the viewpoint of improving the selectivity of the product, tin is preferably present in the catalyst in an amount of 0.3 to 10 mol times, more preferably 0.5 to 5 mol times relative to ruthenium. Further, platinum or rhodium is preferably present in the catalyst in an amount of 0.05 to 2.5 moles, particularly 0.1 to 0.4 moles, relative to ruthenium from the viewpoint of improving the activity.

  Hereinafter, a method for preparing the catalyst will be described. The catalyst component can be supported on the carrier by any method commonly used for the preparation of a supported catalyst, such as an immersion method, an ion exchange method, and an impregnation method. Among them, the immersion method is particularly simple and preferable. When the immersion method is used, the metal component compound to be supported is dissolved in a solvent, for example, water, to form an aqueous solution of the metal compound, and the carrier is immersed in this aqueous solution to support the metal component on the carrier. There is no particular limitation on the order in which each metal component is supported on the carrier, and all the metal components may be supported simultaneously or each component may be individually supported. It is preferable to carry the metal component simultaneously. Further, if desired, each component may be carried in a plurality of times. In the case of a non-supported catalyst that does not use a carrier, C.I. S. As described in Narasiman; Journal of Catalyst, 121, 1,165 (1990), it can be prepared by a reducing method or a coprecipitation method.

As the compound of each catalytic metal component used for catalyst preparation, although depending on the method for preparing the catalyst, mineral salts such as nitrates, sulfates and hydrochlorides are usually used. In addition to these, organic acid salts such as acetates, hydroxides, oxides, organic metal compounds, complex salts, and the like can be used. Of these, hydrochlorides are particularly preferable. In the case of using the hydrochloride, the chlorine component may be removed by drying the fresh catalyst once and then washing with an aqueous ammonium hydrogen carbonate solution.

  If the metal component is supported on the support, it is dried, and then calcined and reduced as desired to form a catalyst. Drying is usually performed at a temperature of 200 ° C. or lower, preferably 50 to 150, under reduced pressure, or a dry gas such as air may be circulated. In the case where the catalyst metal component is loaded in a plurality of times, it is preferable to dry each time the catalyst metal component is loaded. Firing is usually performed at a temperature of 100 to 600 ° C., preferably 200 to 500 ° C. while aerating air or nitrogen. The reduction may be performed by either liquid phase reduction or gas phase reduction. Usually, gas phase reduction is performed at 100 to 700 ° C., preferably 300 to 600 ° C., using hydrogen or methanol as a reducing gas.

  In the present invention, a cycloalkanedimethanol having a desired trans isomer content is obtained by controlling the hydrogenation reaction temperature and the total hydrogenation reaction pressure while maintaining the conversion rate of the raw material cycloalkanedicarboxylic acid. Can do. Thereby, the trans content of cycloalkanedimethanol can be continuously controlled without lowering the production amount of cycloalkanedimethanol. In the production of cycloalkanedimethanol of the present invention, the trans content of cycloalkanedimethanol obtained as a product is preferably controlled to 1 to 99 wt%, more preferably 5 to 80 wt%, Preferably, it is 30 to 75 wt%. When cycloalkanedimethanol is 1,4-CHDM, if the trans content is about 50 wt%, 1,4-CHDM fluidized at room temperature can be obtained, and the subsequent derivative can be manufactured efficiently. It can be well supplied to subsequent processes. On the other hand, the higher the trans content, the more preferable because it is used as a raw material for obtaining derivatives with much industrial demand. However, since it becomes easier to solidify at room temperature, it is necessary to add heat energy to melt and transport it. There are also cases where there is a concern about blockage in process steps.

  The hydrogenation reaction of the present invention is usually carried out under hydrogen pressure, but the reaction conditions such as the hydrogenation reaction temperature and the total hydrogenation reaction pressure depend on the selected catalyst, solvent, reaction type, or raw material. Therefore, suitable conditions may be determined and operated according to each case, but in the present invention, the hydrogenation reaction temperature is in the range of 50 to 350 ° C. from the viewpoint of reaction rate and suppression of side reactions. It is preferable to operate at 150, more preferably in the range of 150-300 ° C, particularly preferably in the range of 180-270 ° C. If the hydrogenation reaction temperature is too high, by-products such as cyclohexanemethanol and methylcyclohexanemethanol may increase. On the other hand, if the hydrogenation reaction temperature is too low, the reaction rate may decrease. The total hydrogenation reaction pressure is preferably operated in the range of 0.1 to 30 MPa, more preferably in the range of 1 to 25 MPa, and particularly preferably in the range of 7 to 15 MPa. The reaction rate may decrease as the total hydrogenation reaction pressure decreases, and by-product may increase as it increases.

In the present invention, the trans isomer content of cycloalkane dimethanol such as 1,4-CHDM which is a product depends on the trans isomer content of cycloalkane dicarboxylic acid such as 1,4-CHDA which is a raw material compound. If the contact time for achieving the target conversion rate of the raw material compound is determined, the hydrogenation reaction temperature and the total hydrogenation reaction pressure can be controlled.
The contact time in the present invention is synonymous with the residence time in the complete mixing tank reactor, and is the residence time based on the empty volume in the case of a tubular reactor, that is, the reciprocal of the space velocity. In the present invention, the contact time is preferably 0.5 to 3 hours, more preferably 0.7 to 2 hours to achieve the target conversion rate (1 to 100%) of the raw material compound.

  In the present invention, the set value of the total pressure is manipulated within the range of the total hydrogenation reaction pressure described above, but by increasing the set value, the amount of dissolved hydrogen in the reaction liquid in the reactor increases, As a result, the hydrogenation reaction rate increases, so that it is possible to hydrogenate almost the entire amount of the raw material cycloalkanedicarboxylic acid such as 1,4-CHDA to cycloalkanedimethanol such as 1,4-CHDM. In addition, the trans isomer content of the product is maintained. Since this reaction is a hydrogenation reaction under a liquid phase, the density of the reaction liquid hardly changes depending on the set value of the total hydrogenation reaction pressure. If the flow rate is maintained, the contact time does not change and the product output does not change.

Therefore, when it is desired to change only the trans isomer content while maintaining the production of cycloalkanedimethanol such as 1,4-CHDM as the product, the desired trans isomer content can be obtained by appropriately setting the hydrogenation reaction temperature. A product with a rate can be produced. In addition, an appropriate total hydrogenation reaction pressure may be set so as to achieve a desired conversion rate of the raw material compound.
If the desired trans isomer content of the product is to be maintained, such a hydrogenation reaction temperature and contact time can be set, and then by providing an appropriate total pressure to achieve the same conversion rate, It is also possible to manipulate the production volume.

The hydrogenation reaction may be carried out by either a continuous method or a batch method, but the continuous method is preferred from the viewpoint of easy operation and economical efficiency. As the reaction type, either a liquid phase suspension reaction or a fixed bed flow reaction can be employed, but the fixed bed flow reaction is preferred from the viewpoint of ease of catalyst separation.
If necessary, the catalyst is solid-liquid separated from the product solution after the hydrogenation reaction is completed. When a solvent is used in the reaction solution, the mechanism for separating the product and the solvent to finally obtain a pure product of cycloalkanedimethanol such as 1,4-CHDM may be distillation or extraction. In a state where cycloalkanedimethanol such as 1,4-CHDM is not in contact with the hydrogenation catalyst, the trans isomer is converted to the cis isomer or the cis isomer to the trans isomer even under high temperature conditions necessary for the catalytic hydrogenation reaction. The reaction rate of the isomerization reaction is very slow. Therefore, even in a separation process that requires heat, such as distillation purification, the trans isomer content of cycloalkanedimethanol such as 1,4-CHDM is usually small and can be obtained as a solution at the reactor outlet. It is possible to obtain pure cycloalkanedimethanol such as 1,4-CHDM having almost the same trans isomer content as cycloalkanedimethanol such as 1,4-CHDM.

The cycloalkanedimethanol obtained by the method of the present invention is suitably used as a polymerization monomer or copolymerization monomer such as polyester, polyurethane and polycarbonate by a conventional method. Furthermore, the polyester, polyurethane, polycarbonate and the like are used as raw materials for resins and fibers particularly excellent in heat resistance, weather resistance, physical strength and the like.
That is, by the above-described method, it is possible to obtain pure 1,4-CHDM having a desired trans isomer content while maintaining the production amount with a nearly complete conversion rate using the same reactor.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples, unless the summary is exceeded.
[Production example]

<Production (preparation) of hydrogenation reaction catalyst>
The catalyst used in the examples of the present invention was produced as follows with reference to the examples of Japanese Patent Application Laid-Open No. 2000-80053.
Activated charcoal (length: approx. 4 mm x diameter: approx. 1 mmφ) is filtered with a 30% aqueous nitric acid solution at 95 ° C. for 3 hours, washed with water until the pH is 3 and then placed in a 120 ° C. box-type dryer. And dried overnight. An aqueous solution containing RuCl3 · 3H2O, H2PtCl6 · 6H2O and SnCl2 · 2H2O was added to the obtained activated carbon, and the mixture was slowly stirred at room temperature for 3 hours. In this operation, the concentration of the metal raw material is such that the weight ratio of Ru, Pt, and Sn is 6% by weight, 3% by weight, and 7% by weight with respect to the total value of the weight of only the metal in all the metal raw materials and the weight of the activated carbon, respectively. % Was adjusted. Moreover, the amount of water measured the pore volume beforehand, and used the water of the same quantity as the pore volume of all the activated carbon to be used. After impregnation with the metal component, it was kept under reduced pressure at 110 ° C. for about 2 hours and dried.

Subsequently, an aqueous solution (concentration 11%) containing 1.2 times moles of ammonium hydrogen carbonate as the amount of Cl contained in all metal raw materials was prepared, slowly added with stirring at room temperature, and allowed to stand overnight. . Thereafter, the catalyst was washed with water at 70 ° C. (10 times with 18 L of water for 4.5 kg of catalyst), and vacuum-dried at 110 ° C. for 3 hours with a conical dryer.
The obtained metal-impregnated catalyst was reduced at 550 ° C. for 1 hour in a hydrogen stream. Further, the reduced catalyst was slowly oxidized while being stirred with nitrogen gas containing 7% oxygen to obtain 6% Ru-3% Pt-7% Sn / activated carbon catalyst.

<Example 1>
Production of 1,4-CHDM from 1,4-CHDA 1,4-CHDM was produced by hydrogenation of 1,4-CHDA using a flow-through tubular reactor shown in FIG. The catalyst produced in the above preparation example was filled in a tube having an inner diameter of 25 mm so as to have a filling height of 855 mm. The raw material compound was 1,4-CHDA (Tokyo Chemical Industry Co., Ltd., purity 99%, trans isomer content: 25%) and distilled water (Wako Pure Chemical Industries, Ltd., purity 100%) in a dissolution tank. The mixture was heated to 150 ° C., and 1,4-CHDA was completely dissolved in water to prepare an aqueous solution having a concentration of 1,4-CHDA of 20% by weight. While maintaining the temperature of this aqueous solution at 150 ° C., the solution was transferred from a transfer line to a feed tank, and was sent to the reactor at 150 ° C. by a liquid feed pump.

Hydrogen (purity 99.9% or more) used for the hydrogenation reaction was once stored in the pressure accumulator at a pressure higher than the reaction pressure by using a total pressure automatic regulator and a booster from a hydrogen cylinder. The hydrogen pressure accumulated in the pressure accumulator was adjusted while adjusting the hydrogen pressure with an automatic pressure regulator, and was supplied while controlling the flow rate of hydrogen supplied to the reactor by installing a flow rate controller in the supply line. .
The hydrogenation reaction was performed under the reaction conditions shown in Table-1. That is, the reaction temperature is 200 ° C. (a temperature measuring point is installed at a position 250 mm below the uppermost part of the catalyst packed bed in the reactor, and a heat medium is circulated outside the reactor so that this temperature becomes a predetermined temperature. The total pressure in the reactor was 12 MPa, the raw material compound (20 wt% 1,4-CHDA-containing aqueous solution) was supplied to the reactor at 250 mL / hr, and the hydrogen flow rate was 165 NL. / Hr. The contact time at this time is 1.
It was 5 hours. In addition, this contact time is a residence time on a so-called empty base calculated by dividing the catalyst packed bed volume by the 1,4-CHDA aqueous solution flow rate. After 8 hours from the start of the reaction (steady state), 1,4-CHDM-containing liquid as a product is extracted at the outlet of the reactor and analyzed by gas chromatography and liquid chromatography to convert 1,4-CHDA. The rate and the yield of 1,4-CHDM were calculated. The trans isomer content in the product 1,4-CHDM was measured by gas chromatography. The results are shown in Table-1.

<Example 2>
In Example 1, all were carried out in the same manner except that the reaction temperature was 210 ° C., the pressure was 10 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.
<Example 3>
In Example 1, all were carried out in the same manner except that the reaction temperature was 210 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.

<Example 4>
In Example 1, all were carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 110 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.
<Example 5>
In Example 1, all were carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.

<Example 6>
In Example 1, all were carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 220 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.
<Example 7>
In Example 1, all were carried out in the same manner except that the reaction temperature was 230 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.

<Example 8>
In Example 1, all were carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 7 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.
<Example 9>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 8 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.

<Example 10>
In Example 1, all were carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 10 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.
<Example 11>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 1.50 hr. The results are shown in Table-1.
(that's all)

<Example 12>
In Example 1, all were carried out in the same manner except that the reaction temperature was 200 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 13>
In Example 1, all were carried out in the same manner except that the reaction temperature was 210 ° C., the pressure was 10 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.

<Example 14>
In Example 1, all were carried out in the same manner except that the reaction temperature was 210 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 15>
In Example 1, all were carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 8 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.

<Example 16>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 10 MPa, the hydrogen flow rate was 110 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 17>
In Example 1, all were carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 10 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. Table 1 shows the results.
Shown in

<Example 18>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 10 MPa, the hydrogen flow rate was 220 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 19>
In Example 1, all were carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 11 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.

<Example 20>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 110 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 21>
In Example 1, all were carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.

<Example 22>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 220 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 23>
In Example 1, all were carried out in the same manner except that the reaction temperature was 230 ° C., the pressure was 8 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.

<Example 24>
In Example 1, all were carried out in the same manner except that the reaction temperature was 230 ° C., the pressure was 10 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 25>
In Example 1, all were carried out in the same manner except that the reaction temperature was 230 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.

<Example 26>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 6 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 27>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 7 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.

<Example 28>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 8 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 29>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 10 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.

<Example 30>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.75 hr. The results are shown in Table-1.
<Example 31>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 110 NL / hr, and the liquid contact time was 0.50 hr. The results are shown in Table-1.

<Example 32>
In Example 1, all were carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.50 hr. The results are shown in Table-1.
<Example 33>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 220 ° C., the pressure was 12 MPa, the hydrogen flow rate was 220 NL / hr, and the liquid contact time was 0.50 hr. The results are shown in Table-1.

<Example 34>
In Example 1, all were carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 8 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.50 hr. The results are shown in Table-1.
<Example 35>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 10 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.50 hr. The results are shown in Table-1.

<Example 36>
In Example 1, everything was carried out in the same manner except that the reaction temperature was 240 ° C., the pressure was 12 MPa, the hydrogen flow rate was 165 NL / hr, and the liquid contact time was 0.50 hr. The results are shown in Table-1.
[Discussion]
(Dependence of transformer content on gas flow rate)
Examples 4 to 6 are examples in which only the gas flow rate was changed to 110 to 220 NL / hr using the same reactor at a temperature of 220 ° C., a contact time of 1.5 hr, and a total pressure of 12 MPa. In all these examples, the conversion was sufficient. Regardless of the gas flow rate, if the temperature and contact time were kept constant, the trans isomer content did not change with the increase in total pressure. This tendency is a comparison of Examples 16 to 18 using the same reactor (temperature 220 ° C., contact time 0.75 hr, total pressure 10 MPa), and comparison of Examples 20 to 22 (temperature 220 ° C., contact time 1.5 hr). This was the same in the comparison of Examples 31 to 33 (temperature 220 ° C., contact time 0.5 hr, total pressure 12 MPa). That is, the trans isomer content of 1,4-CHDM is determined by manipulating only the contact time and temperature, and does not depend on the gas flow rate.

(Dependence of conversion on total pressure)
Examples 8 to 11 are examples in which the same reactor is used, the temperature is 240 ° C., the contact time is 1.5 hours, the gas flow rate is 165 NL / hr, and only the total pressure is changed to 7 to 12 MPa. The trans isomer content did not change, and the conversion rate did not sufficiently reach when the total pressure was low. When the total pressure was increased, the conversion rate could be almost complete. Since the conversion was constant and the same contact time for the same reactor, the production did not change. This tendency is a comparison between Examples 2 and 3 using the same reactor (temperature 210 ° C., contact time 1.5 hr, total pressure 10 to 12 MPa), and comparison between Examples 13 and 14 (temperature 210 ° C., contact time 0). .75 hr, total pressure 10-12 MPa), comparison of Examples 15-22 (temperature 220 ° C., contact time 0.75 hr, total pressure 8-12 MPa), comparison of Examples 23 and 24 (temperature 230 ° C., contact time 0) .75 hr, total pressure 8-10 MPa), comparison of Examples 26-30 (temperature 240 ° C., contact time 0.75 hr, total pressure 6-12 MPa), comparison of Examples 34-36 (temperature 240 ° C., contact time 0) 0.5 hr, total pressure 8-12 MPa). That is, if an appropriate total pressure is selected, the conversion rate can be increased, and the same reactor is used and the same contact time, that is, the same 1,4-CHDM production amount is maintained while maintaining the trans isomer content. That you can keep.

(Temperature dependence of trans isomer content)
Furthermore, Examples 16 to 22 are examples in which only the total pressure was changed to 8 to 12 MPa at a temperature of 220 ° C. and a contact time of 0.75 hr using the same reactor. If the temperature and the contact time are kept constant, it indicates that the trans isomer content does not change with the increase of the total pressure. This tendency was the same in the comparison of Examples 23 to 25 performed at a temperature of 230 ° C and the comparison of Examples 26 to 30 performed at a temperature of 240 ° C using the same reactor. At all three set temperatures, conversion was not compromised. Moreover, since it was the same contact time with respect to the same reactor, the production amount did not change. That is, if an appropriate total pressure is selected, only the temperature is operated using the same reactor, and only the trans isomer content is maintained while maintaining a high conversion rate while maintaining the production amount of 1,4-CHDM. It can be changed.

(Dependence of trans isomer content on contact time)
Moreover, the example which changed only the contact time at the same temperature is shown. Examples 4 to 6 are examples of a temperature of 220 ° C. and a contact time of 1.5 hours, Examples 20 to 22 are examples of a temperature of 220 ° C. and a contact time of 0.75 hr, Examples 31 to 33 are a temperature of 220 ° C. and a contact time of 0. This is an example of 5 hours. It is shown that if an appropriate total pressure is selected, the trans isomer content can be changed while maintaining the same temperature and operating only the contact time while maintaining a high conversion rate.

(Estimation of trans isomer content from operating conditions)
FIG. 1 is a graph showing the correlation of the resulting 1,4-CHDM trans isomer content for two different combinations of contact time and reaction temperature for the catalyst used in this example. In FIG. 1, the solid line shows the correlation between the reaction temperature at the contact time of 0.5 hr and the trans isomer content, the broken line shows the correlation between the reaction temperature at the contact time of 0.75 hr and the trans isomer content, Indicates a correlation between the reaction temperature at a contact time of 1.5 hr and the trans isomer content. Similar graphs can be created for other contact times. Based on such a graph, it is possible to select an appropriate contact time and reaction temperature necessary for making the trans isomer content substantially constant.

(Example of how to select operating conditions)
An example will be shown in which the same conversion rate is achieved by increasing the flow rate of the liquid having the same composition in the same reactor. When the desired trans isomer content is 40%, it can be achieved by setting the temperature to 204 ° C. and the contact time to 1.5 hr (point A). From this state, if it is desired to increase only the production amount while maintaining the trans isomer content rate at 40%, it is synonymous with the increase in the circulation amount if the contact time is reduced with the same trans isomer content rate. When only the contact time is halved to 0.75 hr and the temperature is 219 ° C. (point B), the output is doubled if the conversion is equal. Since the conversion rate can be increased by increasing the total pressure, it is possible to change only the production volume.

Claims (2)

By performing a hydrogenation reaction in the liquid phase in the presence of a solid catalyst containing at least ruthenium, tin, and platinum, using 1,4-cyclohexanedicarboxylic acid having a trans isomer content of 10 to 50 wt% as a raw material compound, When obtaining 1,4-cyclohexanedimethanol having a trans isomer content of 30 to 75 wt%, the hydrogenation reaction temperature is in the range of 200 to 240 ° C. and the total hydrogenation reaction pressure is maintained while maintaining the conversion rate of the raw material compound. range 7～12MPa, and contact time in the range of 0.5 to 1.5 hours, and by operating the hydrogenation reaction temperature and / or contact time with the desired trans isomer content of 1,4 A method for producing 1,4-cyclohexanedimethanol, comprising obtaining cyclohexanedimethanol . Furthermore, the manufacturing method of the 1, 4- cyclohexane dimethanol of Claim 1 which operates a hydrogenation reaction total pressure.

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