JPH06321852A - Production of 1,3-cyclohexanedicarboxylic acid - Google Patents

Abstract

PURPOSE:To facilitate actualization of economic hydrogenation reaction by greatly suppressing redaction in activity of an expensive palladium catalyst and to obtain extremely high-purity 1,3-CHDA by simple procedure by bringing a solution containing the hydrogenation reaction product into contact with steam. CONSTITUTION:In producing 1,3-cyclohexanedicarboxylic acid, two processes wherein the first process is carried out by hydrogenating an isophthalic acid- containing solution in the presence of a palladium catalyst in an acid-resistant container or a container lined with an acid-resistant substance and the second process is done by bringing a 1,3-cyclohexanedicarboxylic acid-containing solution obtained by the first process into contact with steam and removing the impurities transferred to the steam side are successively conducted to provide a characteristic production method of 1,3-cyclohexanedicarboxylic acid. By using the high-purity 1,3-CHDA, a resin having excellent weather resistance and mechanical strength and a high-purity medicine can be produced.

Description

Detailed Description of the Invention

[0001]

[Industrial applications]

The present invention is 1,3-cyclohexanedicarboxylic acid (hereinafter sometimes referred to as 1,3-CHDA).
Manufacturing method.

[0003]

[Prior art]

1,3-CHDA is a drug or synthetic resin,
It is useful as a raw material for synthetic fibers, paints and the like, and is particularly used as a raw material for producing resins and fibers having excellent heat resistance, weather resistance and physical strength.

As a method for producing 1,3-CHDA, a highly pure one of isophthalic acid (hereinafter sometimes referred to as IPA) produced as an industrial raw material is used to hydrogenate a benzene ring. A typical method is to obtain it, and some methods have already been reported.

[0006] Some of these methods are roughly divided into
Once the acid part of IPA is changed to a metal salt such as sodium,
A method of reducing the benzene ring after forming various esters,
There is a method to reduce the acid as it is.

The former method is, for example, USP 2,828,
As disclosed in Japanese Patent No. 335, etc., it is said that isophthalic acid is dissolved in sodium hydroxide or the like to give sodium salt of isophthalic acid, which is reduced using ruthenium oxide or the like as a catalyst, and sodium is removed using an acid. But the raw material I
Since it takes extra time to convert PA into a derivative form once and then reduce it back to the acid form, it has been regarded as economical and promising to reduce the acid as it is.

In spite of many attempts, there are relatively few cases where the reduction with acid is successful, but, for example, Journal of Organic Chemistry (Journal of O
rganic Chemistry), 31 (10) p3438-9 (1)
966), IPA was hydrogenated in a water solvent in the presence of a rhodium-alumina catalyst under the conditions of 60 to 70 ° C. and a hydrogen pressure of 3 atm or less to obtain the desired 1,3-CHDA (melting point: 112).
A method for obtaining (-134 ° C.) at a ratio of cis isomer: trans isomer = 60: 40 with a yield of about 96% is introduced.

[0009]

[Problems to be Solved by the Invention]

Recently, in the field of resins and the like using 1,3-CHDA as a raw material, as products having international competitiveness and advanced functions are required, the raw materials also have international price competitiveness. Products with extremely few impurities, such as high-purity products with 1,3-CHDA purity of about 99.9% by weight, products with few inorganic substances such as chlorine, products with few impurities such as cyclohexanecarboxylic acid analogs, etc. Is required to be offered at a price that is not much different from conventional products.

However, the 1,3-CHDA obtained by the conventional production method is not so high in purity as to meet the present demands for high quality, and even if some production method is considered, it is extremely complicated. However, an expensive process was required, and there was a problem that it was not practical.

[0012] For example, regarding the above-mentioned method of reducing isophthalic acid to a sodium salt and then reducing it, when an additional trial is actually attempted, there is a problem that the activity of the catalyst is drastically lowered and the cost of the catalyst required for the reduction becomes extremely high. There was.

In addition to the above, 4-by-products formed during the reaction
Cyclohexanecarboxylic acid analogs such as methylcyclohexanecarboxylic acid, sodium sulfate, sodium chloride, etc. generated from the acid used when recovering 1,3-CHDA from the alkali or hydrogenation reaction product used for dissolving the raw material IPA There is also a fatal problem that impurities of inorganic salts cannot be avoided from being mixed in 1,3-CHDA.

Therefore, 1,3 obtained by this method
-In the polymerization reaction of a resin or the like using CHDA as a raw material, the unevenness of the reaction may occur due to the presence of impurities in the raw material, and the heat resistance, physical strength, and weather resistance of the obtained resin or other product. There are drawbacks such as the fact that the properties and the like are remarkably impaired by impurities in the raw material, and improvement of these drawbacks has been left as an issue.

Further, regarding the method for directly reducing the isophthalic acid, for example, although the rhodium used as a catalyst is about 10 times as expensive as palladium or ruthenium, it is very expensive, but the catalyst is not so expensive. The life is not long, the purity of the target product in the reaction product is as low as about 96%, and avoids contamination of 1,3-CHDA with impurities such as cyclohexanecarboxylic acid analogs formed as a by-product during the reaction. There was also a problem that they could not do.

As means for solving these problems, 1,
Crystallization of 3-CHDA-containing products is also conceivable, but
Since CHDA and the by-product cyclohexanecarboxylic acid analog have relatively similar structures and properties, it is not so much that the crystallization improves the 96-% 1,3-CHDA purity to 99.9% or more. It's not easy.

In addition, as the use of the catalyst is repeated, a high temperature and a high pressure are required in order not to leave an unreduced substance, but due to the severe temperature condition, the purity of 1,3-CHDA of the reaction product is low. There was also an issue to be answered.

In the method for producing 1,3-CHDA disclosed above, an example in which a new catalyst in which the activity is not lost is used is disclosed, and 1,3 having a relatively high purity on the surface is prepared. Although it seems to be a method of obtaining -CHDA, according to an additional test by the present inventors, almost all the methods produce low-purity 1,3-CHDA when the catalyst is repeatedly used, and are practically used as they are. It became clear that he could not stand.

In many cases, the cause is that impurities are generated, but the impurities are preferentially adsorbed at the adsorption points of activated carbon or the like used as a carrier of the catalyst.
The purity of CHDA only looks high, and the adsorption capacity of activated carbon etc. is small, so after the adsorption capacity is satisfied,
It seems that the originally produced impurities are detected at the rate as they are produced in the reaction.

Further, in the conventional manufacturing method, a pressure resistant container made of stainless steel is adopted, but according to a detailed study by the present inventors, IPA or 1,3 was added to a normal stainless steel container.
When the CHDA solution is put in and brought into contact with the vessel wall at a temperature at which the hydrogenation reaction is carried out, nickel, iron, chromium, molybdenum, etc., which are components of stainless steel, are eluted into the solution and a certain concentration is reached. It was revealed that when the metal is eluted as described above, the metal becomes a catalyst poison and the activity of the catalyst is significantly attenuated.

According to the research conducted by the present inventors, there is no serious effect until the concentration of the eluted metal is about 5 to 10 ppm, but the effect begins to increase from about 20 ppm. It was desired to take measures against the problem of shortening.

Under these circumstances, the conventional method could not be economically produced because the activity of the catalyst deteriorates quickly.
Further, in obtaining 1,3-CHDA, more impurities than are apparent from the conventional reaction are produced, so that the reaction product does not meet the recent high demands, and Since it was also difficult to raise the purity of 1,3-CHDA by the technology, it has been earnestly desired to develop a method for solving the above various problems.

[0023]

[Means for Solving the Problems]

The present inventors have studied the behavior of IPA or its alkali salt for various reactions and the properties of the hydrogenation reaction product, and as a result of earnest studies on a method for realizing the economical process and high purification of the product. It has been found that the cause of the decrease in the activity of the catalyst is nickel, chromium, molybdenum, iron, etc. which have been eluted from the walls of pressure-resistant metal containers such as stainless steel, which have been conventionally used, and a highly acid-resistant container or acid-resistant substance as a reaction container. Succeeded in realizing economical hydrogenation reaction by remarkably suppressing the decrease in catalytic activity by adopting a vessel lined with the above, and further bringing the hydrogenation reaction product-containing liquid into contact with steam. Results in very high purity 1,3-CHD
Succeeded in obtaining A and came to complete the present invention.

The contents of the present invention will be described in detail below.

In the first aspect of the present invention, in producing 1,3-cyclohexanedicarboxylic acid, an IPA-containing solution is hydrogenated in the presence of a palladium catalyst in an acid resistant container or a container lined with an acid resistant material. Sequentially passing through two steps, a first step, a second step of contacting the 1,3-cyclohexanedicarboxylic acid-containing liquid obtained in the first step with water vapor, and removing impurities moved to the water vapor side. Is a method for producing 1,3-cyclohexanedicarboxylic acid.

The invention, secondly, the hydrogenation of the first step 2 kg / cm ² or more, the first, wherein a carried out under a hydrogen pressure of less than 200 kg / cm ² 1, 3
-A method for producing cyclohexanedicarboxylic acid.

The invention, in a third, the hydrogenation of the first step 2 kg / cm ² or more, which comprises carrying out under hydrogen pressure of less than 10 kg / cm ² of the first described 1,3
It is a method for producing cyclohexanedicarboxylic acid.

In the fourth and second steps of the present invention,
While continuously supplying the 1,3-cyclohexanedicarboxylic acid-containing liquid from one side of the packed column, steam is continuously supplied from the opposite direction, and the 1,3-cyclohexanedicarboxylic acid is intermittently or continuously supplied from the other side. Water vapor is discharged in the opposite direction to that of 1,3-cyclohexanedicarboxylic acid and the water vapor is brought into countercurrent contact with the water vapor, and impurities moving to the water vapor side are condensed and removed together with the water vapor, or In the method for producing 1,3-cyclohexanedicarboxylic acid according to any one of the above first to third, characterized in that after removal by passing through an aqueous alkaline solution, steam is heated if necessary and reused. is there.

The quality of IPA used in the present invention is not so high that it is conventionally used as a raw material of 1,3-CHDA, and is slightly lower than that. Even the quality for general industrial use can be advantageously adopted.

The concentration of IPA in carrying out the present invention is preferably 5 to 50% in the first step, and more preferably 10 to 40%.

In practicing the present invention, if the concentration is out of the range of the first step, for example, if it is less than 5%, efficient production cannot be performed for the size of the equipment. Therefore, it is uneconomical because it is uneconomical, and when it exceeds 50%, it is difficult to handle because the crystal tends to precipitate, which is not preferable.

As the hydrogenation reaction catalyst which is advantageously used in the present invention, metallic palladium supported on a carrier can be advantageously adopted, and as the carrier, various activated carbons such as alumina, silica and carbon can be used. The representative carbon is most preferable because it is not easily affected by acid.

Further, the amount of palladium supported which can be advantageously employed in carrying out the present invention is determined by the palladium metal content in the catalyst weight because of the reason that the reaction proceeds sufficiently and is economical. When it is expressed, it is 2 to 20%, but a more preferable supported amount is 5 to 10%.

In carrying out the present invention, various alcohols, water and 1,3 are used as a solvent for adjusting the concentration.
Although there are —CHDA and the like, water is most preferable because it is inert to the reaction and is inexpensive.

The acid-resistant substance and acid-resistant container used in the present invention include metals having strong acid resistance, for example, Hastelloy steel, Inconel steel and molded products thereof, and substances having strong acid resistance other than metals, such as ceramics, enamel and glass. Examples of such glassy materials and molded articles thereof include, in addition to these, a container in which the above-mentioned various acid-resistant substances are lined with iron or stainless steel used for a normal pressure-resistant container is economical and is advantageously used. can do.

Conditions for advantageously carrying out the first step of the present invention are as follows: temperature: 120-160 ° C., hydrogen pressure: 2-200 k
g / cm ² , more preferably 2 kg / cm ² or more and 10 k
The reaction time is less than g / cm ² , and the reaction time is from 30 minutes to 120 minutes, but if it is out of these ranges, the yield and the purity of the product are adversely affected in any case, which is not preferable.

The 1,3-CHD used in the second step
Regarding the concentration of the A-containing reactant, it is most economical to use the filtrate without hydrogenation after the hydrogenation as it is, but the ratio of cis isomer to trans isomer which is usually obtained and economic restrictions, Based on the solubility in water, etc., approximately 2% to 40%
The preferred range is 5% to 30%.
%.

Further, 1,3-CHD used in the second step
There is no particular restriction on the ratio of the cis isomer and the trans isomer contained in the A-containing reaction product, and if the ratio is such that it appears in the reaction product obtained by hydrogenating IPA, the practice of the present invention is hindered. Although it does not occur, the dissolution temperature of the reaction product in water tends to rise as the proportion of the trans form increases, and a cis: trans ratio of about 65:35 may be mentioned as a ratio that is easy to handle in operation.

In the second step of the present invention, steam is used, but the steam is not particularly limited as long as it can realize the temperature conditions necessary for carrying out the present invention. Those generated by a steam generator or the like are sufficient.

In the second step, the method of contacting the 1,3-cyclohexanedicarboxylic acid-containing liquid with steam is as follows:
Although there are a batch method and a continuous method, any method can be adopted in the present invention, and the method of performing continuously is excellent in efficiency.

The method of removing the impurities that have moved to the steam side after the contact between 1,3-CHDA and the steam can be either batch-wise or continuous, and the steam is condensed to remove the impurities and the steam. It is possible to employ a method of removing the mixture as a mixture with the drain, a method of blowing steam into the alkaline aqueous solution, or a method of passing steam through the shower of the alkaline aqueous solution.

As a further preferred embodiment of the second step of the present invention, the 1,3-cyclohexanedicarboxylic acid-containing liquid is brought into contact with steam in countercurrent.

Further, it is optional to reuse the steam in order to reduce the energy loss of the whole process. For example, after the impurities in the steam are removed by the alkaline aqueous solution as described above, the steam may be reused if necessary. It can also be used by heating.

The operations of the second step described above can be employed in any combination, but among these combinations, the 1,3-CHDA-containing liquid is brought into countercurrent contact with water vapor to remove impurities. The most economically advantageous method is to contact the water vapor containing water with an alkali aqueous solution to absorb impurities into the alkali aqueous solution and then reuse the water vapor.

The method using this combination will be described in more detail. A tower (A) and a tower (B) packed with a packing such as Raschig rings are prepared, and the upper part of the tower (A) and the tower (B) are prepared.
The lower part of the column, the lower part of the tower (A) and the upper part of the tower (B) are respectively connected by pipes, and each pipe and the column are provided with a structure such as a jacket so that the temperature can be adjusted to a predetermined temperature. A pump (P) having a function of circulating water vapor is provided in the middle of a pipe connecting the lower part of the column and the upper part of the column (B) such that the column (A) side is the discharge side.

Next, while operating the pump (P) of the apparatus, the heated 1,3-CHDA-containing liquid was continuously introduced from the upper part of the tower (A), withdrawn from the lower part of the tower (A), and At the same time, the heated alkaline aqueous solution is continuously introduced from the upper part of the tower (B) and withdrawn from the lower part of the tower (B).

At this time, 1,3-C supplied to the tower (A)
The preferred concentration of the HDA-containing liquid is 2 to 40%, more preferably 5 to 30%.

The concentration of the alkaline aqueous solution supplied to the tower (B) is preferably 1 to 50%, more preferably 1 to 20%.

The supply rate of the 1,3-CHDA-containing liquid supplied to the tower (A) depends on the concentration, the temperature, the concentration of impurities contained therein, and the like. The amount is preferably 1 to 6 times the capacity / hourly.

At this time, if the feed rate of 1,3-CHDA is less than 1 time / hour, the efficiency is unnecessarily lowered, which is not preferable. If it exceeds 6 times, the removal of impurities is not preferable. It is not preferable because it may be incomplete.

The supply rate of the aqueous alkali solution to the tower (B) is preferably about 1 to 6 times the capacity of the tower (B) per hour, but if it is out of this range, the alkali is wasted in any case. It is not preferable because it may become insufficient or insufficient.

Alkali which can be advantageously used in the present invention includes sodium hydroxide, potassium hydroxide, trisodium phosphate and the like. Among the alkalis, calcium salt often causes scale, and carbonate is gas. Therefore, it is possible to use any of them, but it is not so preferable.

The steam circulation amount of the pump (P) is preferably about 0.1 to 1.6 times the capacity of the column (A) per hour when converted to the amount of water condensed from steam, but this range is preferable. If it is out of the range, none of them has a good influence on the cost or yield of the second step, which is not preferable.

When the second step of the above combination is adopted, it is recommended to keep each column and piping at a temperature in the range of 100 to 150 ° C, more preferably 102 to 130 ° C. ) And the temperature of the tower (B) are different, the 1,3-CHDA-containing liquid supplied is boiled,
This is not preferable because it is difficult to balance the balance of the substances in the column due to the condensation of water vapor, and when the temperature range is less than 100 ° C, the removal of impurities is often insufficient.
If the temperature exceeds 50 ° C., the yield may decrease due to decomposition or the like, which is not preferable.

In the tower (B), since the impurities contained in the water vapor are absorbed and moved to the alkali side at an extremely high speed, the water vapor containing the impurities discharged from the upper part of the tower (A) is showered into an alkali. A method of contacting with an aqueous solution or a method of directly blowing steam into an alkaline aqueous solution can also be adopted.

As described above, by carrying out the present invention, it becomes possible to suppress the activity decrease of the hydrogenation catalyst and to keep the life of the catalyst remarkably long, whereby IPA is directly subjected to the hydrogenation reaction. , 3-CHDA is economically feasible, and further, high quality 1,3-CHDA which can sufficiently meet the present high demands can be produced.

[0058]

【Example】

Hereinafter, the contents of the present invention will be described more specifically with reference to Reference Examples and Examples, but the scope of the present invention is not limited to these examples.

[Example-1] (First step)

30 g of isophthalic acid, 270 g of water and 10 g of 10% palladium-carbon catalyst (manufactured by NE Chemcat) were placed in a glass autoclave having a capacity of 500 ml equipped with a stirring blade made of fluorine resin (Teflon), and the temperature was 130. ° C, hydrogen pressure 8.3 ~ 9.8kg / cm
As a result of hydrogenation at ² , the hydrogen absorption was not observed after 50 minutes and the reaction was completed.

The reaction solution was taken out from the autoclave and
The catalyst was filtered while maintaining at 0 ° C to obtain a filtrate.

As a result of analyzing this filtrate by gas chromatography, the purity of 1,3-CHDA in the solid content was 98.
It was 0%, the amount of unreduced substances was 0.01%, and the types of impurities were only 3-methylcyclohexanecarboxylic acid and cyclohexanecarboxylic acid.

Next, isophthalic acid 30 was added to the recovered catalyst.
g and 270 g of water were added and the same hydrogenation was repeated.

The hydrogenation was repeated up to the 70th time using the recovered catalyst, but there was almost no change in the reaction time, the 1,3-CHDA purity, and the amount of unreduced substances, which are indicators of the hydrogenation activity of the catalyst. I couldn't see it.

The results of repeated hydrogenation are shown in Table 1.

[0067]

[Table 1]

[Comparative Example-1] (First step)

Hydrogenation was repeated up to 20 times in the same manner as in Example-1 except that a stainless steel autoclave was used in place of the glass autoclave of Example-1.

As a result, the reaction time required for hydrogenation was prolonged, so that the subsequent repetition was stopped. The results of repeated hydrogenation are shown in Table 2.

[0071]

[Table 2]

[Example-2] (First step)

10,000 ml of stainless steel (SUS3
06) 1.2k of isophthalic acid was added to an autoclave with glass lining on the inside of the container and the liquid contact part of the stirring blade.
g, 4.8 kg of water and 10% palladium-carbon 240
g, temperature 130 ° C, hydrogen pressure 8.5-9.8 kg /
As a result of hydrogenation under the condition of cm ² , the absorption of hydrogen was not observed 80 minutes after the start of the reaction, and the reaction was completed.

The reaction solution was cooled to 60 ° C., taken out from the autoclave, filtered, and the filtrate was analyzed.
The 1,3-CHDA purity was 97.1%, and the unreduced substance content was 0.02%.

[Example-3] (First step)

600 g of isophthalic acid, 5.4 kg of water, and 120 g of 10% palladium-carbon catalyst were placed in the same autoclave as in Example 2, and hydrogenated at a temperature of 140 ° C. and a hydrogen pressure of 5 to 6 kg / cm ² . As a result, 140 minutes after the start of the reaction, hydrogen absorption was not observed and the reaction was completed.

After cooling the reaction solution, it was heated and filtered in the same manner as in Example-2, cooled, and the filtrate was analyzed.
The 3-CHDA purity was 95.8% and the unreduced matter content was 0.02%.

[Example-4] (First step)

280 g of a 7.5% palladium-carbon catalyst was used as a catalyst, the reaction temperature was 150 ° C., and the hydrogen pressure was 8.5 to 9.8 kg / cm ^2. As a result of hydrogenation, the reaction time was 70 minutes, and the analysis results showed that the purity of 1,3-CHDA was 96.2% and the content of unreduced products was 0.02%.

[Example-5] (First step)

900 g of isophthalic acid, 5.1 kg of water, and 400 g of 5% palladium-carbon catalyst were placed in the same autoclave as in Example 2, and hydrogen was added at a temperature of 130 ° C. and a hydrogen pressure of 8.5 to 9.8 kg / cm ² . As a result, the hydrogen absorption was not observed 80 minutes after the start of the reaction, and the reaction was completed.

As a result of analyzing the filtrate in the same manner as in Example-2, the 1,3-CHDA purity was 97.6% and the unreduced substance content was 0.02%.

[Example-6] (second step)

The stainless steel tower (B) with a jacket and the equipment with a heating jacket shown in FIG. 1 in which the liquid contact parts other than that were glass-lined were prepared, and the piping with a heating jacket was connected as shown in the figure.

The respective dimensions are as follows: the container (1) of the tower (A) (inner diameter 5 cm, length 20 cm), the column (2) (inner diameter 5 c
m, length 200 cm, capacity 3900 ml), liquid receiver (3) (inner diameter 5 cm, length 70 cm), tower (B) container (4) (inner diameter 5 cm, length 20 cm), column (5)
(Inner diameter 5 cm, length 200 cm, capacity 3900 ml),
A liquid receiver (6) (internal diameter 5 cm, length 70 cm) was used. The column (2) was equipped with a porcelain Raschig ring having an inner diameter of 3 mm, an outer diameter of 6 mm and a length of 6 mm, and the column (5) was 5 mm × 12 m.
m wire mesh was filled in each case.

Further, 1,3-CH is provided on the upper part of the container (1).
An inlet (a) for the DA-containing liquid and a steam outlet (b) on the side surface
, A water vapor inlet (c) on the side surface of the liquid receiver (3), a 1,3-CHDA outlet (d) on the lower portion, and an alkaline aqueous solution inlet (e) on the upper portion of the container (4). The water vapor outlet (f) was attached to the side surface, the water vapor inlet (g) was attached to the side surface of the liquid receiver (6), and the aqueous alkaline solution outlet (h) was attached to the lower portion.

First, 4.8 kg / in the jacket of the device.
Apply a vapor pressure of cm ² to adjust the temperature inside the system to 150 ° C, and then turn on the steam circulation pump (9) at 57 ml / min.
By operating at a speed of (amount as water), steam was sent toward the steam inlet (c) to circulate the steam in the system.

Next, the pump (8) was operated to send a 10% aqueous sodium hydroxide solution to the inlet (e) at a rate of 67 ml / min to prepare 1,3-CHDA produced in Example-2.
Contained liquid (concentration 20%, 1,3-CHDA purity 97.1
%) By pump (7) at a rate of 133 ml / min, 1
Each liquid was extracted from the outlet (d) and the outlet (h) of each tower every 0 minutes.

As a result of extracting and analyzing the 1,3-CHDA-containing liquid produced from the outlet (d) of the liquid receiver (3) after 1 hour and 2 hours, no impurities were detected.

[Example-7] (second step)

Processing was carried out by the same method as in Example 6 except for the conditions shown below.

The temperature inside the piping and the apparatus was set to 130 ° C.,
What was obtained under the conditions of Example-5 as a 1,3-CHDA-containing liquid (concentration 15%, 1,3-CHDA purity 97.6%)
The feed rate to the inlet (a) was 133 ml / min, and the feed rate of the 10% aqueous sodium hydroxide solution to the inlet (e) was 67 ml / min.

The steam circulation pump (9) was operated at a supply rate of 71 ml / min of water and the apparatus was operated, and after 1 hour and 2 hours, the liquid was taken out from the discharge port (d) of the liquid receiver (3). As a result of analyzing the solution, no impurities were detected.

[Example-8] (second step)

The temperature inside the apparatus of Example-6 was adjusted to 110 ° C., and the 1,3-CHDA-containing liquid was produced under the conditions of Example-3 (1,3-CHDA purity 95.8%,
(Concentration 10%) and the feed rate to the inlet (a) is 2 per minute
Example-6, in which the feed rate to the inlet (e) was set to 134 ml / min, and the feed rate of the water vapor circulation pump (9) was 71 ml / min in terms of the amount of water. As a result of operating the same operation and analyzing the liquid extracted from the discharge port (d) of the liquid receiver (3) after 1 hour and 2 hours, no impurities were detected.

[Example-9] (second step)

As the tower (B) of Example-6, no packing was contained, the inner diameter was 12 cm, the length was 100 cm, and the volume was 11.
Steam outlet (b) using a 300 ml stainless steel container
A check valve was attached between the water vapor inlet (g) and the water vapor inlet (g) to prevent the liquid from flowing backward, and the water vapor was allowed to flow from the water vapor outlet (b) to the water vapor inlet (g).

5000 ml of potassium hydroxide having a concentration of 20% was added so that the water vapor inlet (g) of the container (B) was below the surface of the alkaline aqueous solution, and the whole system was kept at 130 ° C.

1,3-CH produced under the conditions of Example-5
DA-containing liquid (1,3-CHDA purity 97.6%, concentration 1
5%) at a rate of 67 ml / min from the inlet (a),
As a result of analyzing the liquid extracted from the outlet (d) at the 1st hour and the 2nd hour by operating the apparatus in the same manner as in Example 6 except that the alkali was not continuously supplied and extracted, impurities were found. Not detected.

[Example-10] (second step)

Using only the tower (A) of Example 6, a pipe was connected to the steam inlet (c) so that the steam having the same vapor pressure as the outer jacket could enter, and a throttle valve was connected to the steam outlet (b). A cooler was attached so that the discharged water vapor was condensed.

2.0 kg / in jacket of equipment and piping
A steam pressure of cm ² was applied to maintain the temperature at 120 ° C., a steam inlet (c) valve was opened to introduce steam into the apparatus, and a steam outlet (b) valve was opened to be cooled and discharged. The amount of incoming condensed water was adjusted to 57 ml per minute.

Next, 1, which was produced under the conditions of Example-4,
3-CHDA-containing liquid (1,3-CHDA purity 96.2
%, Concentration 10%) is supplied to the inlet (a) by the pump (7) at a rate of 100 ml / min, and the valve of the steam inlet (c) is adjusted to be discharged from the outlet (d). 1,3-C
The concentration of the HDA-containing solution was adjusted to 10%.

The liquid is discharged from the discharge port (d) every 10 minutes,
Impurities were not detected as a result of analyzing the extracted liquids at 1 hour and 2 hours.

[Example-11] (second step)

As shown in FIG. 2, the tower of Example-6 (B)
Instead of the tower with jacket (C) (material, SUS31
6) is prepared, and the structure of the tower (C) is the same as the tower (B) from the top, and the container (10) (inner diameter 12 cm, length 20 c
m), an alkaline shower device (11) (inner diameter 12 cm,
Length 50 cm, volume 22600 ml), and liquid receiver (1
2) (Inner diameter 12 cm, length 50 cm, volume 11300 m
l).

An alkaline liquid inlet (i) is provided in the upper part of the container (10), and an alkaline liquid is introduced from the alkaline liquid inlet (i) by attaching a distributor to the tip of the alkali pipe inside the container. In the structure (11), the water was uniformly dispersed in a shower, the water vapor outlet (j) was attached to the side surface of the container (10), and the throttle valve and the cooler were attached to the outside thereof.

At the bottom of the liquid receiver (12) is the liquid outlet (k).
A steam inlet (m) and a valve are attached to the side surface, and a pump (13) is attached between the alkaline liquid inlet (i) and the outlet (k) to circulate the liquid in the direction of the alkaline liquid inlet (i). I made it possible.

Further, the water vapor outlet (b) and the water vapor inlet (m), and the water vapor inlet (c) and the water vapor outlet (j) are respectively connected by pipes so that the water vapor inlet (c) and the water vapor outlet (j) are connected. A water vapor circulation pump (9) was put in to allow water vapor to circulate in the direction of the water vapor inlet (c).

First, 10% was added to the container (10) of the tower (C).
Add 5000 ml of sodium hydroxide aqueous solution, apply steam pressure of 2 kg / cm ² to each jacket and raise the temperature to 120 ° C.
After that, the pump (13) was circulated at a rate of 6000 ml / min, and the steam circulation pump (9) was operated at a rate of 71 ml / min (as water), and the production was carried out under the conditions of Example-5 1 , 3-CHDA-containing liquid was supplied to the inlet (a) of the tower (A) at a rate of 177 ml / min, and the 1,3-CHDA-containing liquid was withdrawn every 10 minutes from the outlet (d).

As a result of analyzing the quality of the liquid withdrawn from the outlet (d) at the first hour and the second hour, no impurities were detected.

[0112]

【The invention's effect】

By carrying out the present invention, it becomes possible to remarkably suppress the activity decrease of the expensive palladium catalyst and realize an economical hydrogenation reaction. It is possible to obtain 1,3-CHDA having a very high purity by a simple operation by contacting with a resin, and by using this high-purity 1,3-CHDA, a resin excellent in weather resistance, physical strength, etc. And high-purity pharmaceuticals can be manufactured.

[Brief description of drawings]

FIG. 1 is a schematic view of a first example of an equipment device with a heating jacket used for carrying out the present invention.

FIG. 2 is a schematic view of a second example of the equipment device with a heating jacket used for carrying out the present invention.

[Explanation of symbols]

 A tower B tower C tower a inlet b steam outlet c steam inlet d steam outlet e inlet f steam outlet g steam inlet h discharge outlet i alkali liquid inlet j steam outlet k outlet m steam inlet 1 container 2 column 3 liquid receiver 4 container 5 Column 6 Liquid Receiver 7 Pump 8 Pump 9 Water Vapor Circulation Pump 10 Container 11 Alkaline Shower 12 Liquid Receiver 13 Pump

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Naoki Okamoto 4-61-17 Minamihanajima, Matsudo City, Chiba Prefecture (72) Inventor Kazuaki Kato 477 Nakasone, Yoshikawa-cho, Kitakatsushika-gun, Saitama Prefecture

Claims (4)

[Claims] 1. A first step of producing 1,3-cyclohexanedicarboxylic acid, wherein an isophthalic acid-containing liquid is hydrogenated in the presence of a palladium catalyst in an acid-resistant container or a container lined with an acid-resistant substance, 1. A 1,3-cyclohexanedicarboxylic acid-containing liquid obtained in one step is brought into contact with water vapor, and a second step of removing impurities that have moved to the water vapor side is sequentially performed. , 3-
Method for producing cyclohexanedicarboxylic acid. 2. The method for producing 1,3-cyclohexanedicarboxylic acid according to claim 1, wherein the hydrogenation in the first step is carried out under a hydrogen pressure of ² kg / cm ² or more and less than 200 kg / cm ^2. . 3. The method for producing 1,3-cyclohexanedicarboxylic acid according to claim 1, wherein the hydrogenation in the first step is carried out under a hydrogen pressure of ² kg / cm ² or more and less than 10 kg / cm ^2. . 4. In the second step, 1,3-cyclohexanedicarboxylic acid-containing liquid is continuously supplied from one side of the packed column, while steam is continuously supplied from the opposite direction to the other side, and 1 is supplied from the other side. , 3-Cyclohexanedicarboxylic acid is discharged intermittently or continuously, and steam is discharged from the opposite direction to bring 1,3-cyclohexanedicarboxylic acid and steam into countercurrent contact with each other, and the impurities are moved to the steam side. Is condensed with water vapor to be removed, or is passed through an aqueous alkali solution to be removed, and then the water vapor is heated if necessary and reused. A method for producing 1,3-cyclohexanedicarboxylic acid.