阅读说明：本技术 具有高反式含量的环己烷二甲醇的制备方法以及由此制备的环己烷二甲醇 (Process for the preparation of cyclohexanedimethanol having high trans content and cyclohexanedimethanol prepared thereby ) 是由 李钟权 金杞暾 金恩廷 韩柱熙 南浩成 于 2018-12-21 设计创作，主要内容包括：本发明涉及在环己烷二羧酸(Cyclohexane dicarboxylic acid,CHDA)氢化反应过程中通过调整特定条件、添加剂的投入或者反应物的添加而具有高反式含量的环己烷二甲醇的制备方法以及由此制备的环己烷二甲醇(Cyclohexane dimethanol,CHDM)。(The present invention relates to a method for preparing cyclohexanedimethanol having a high trans content by adjusting specific conditions, input of additives, or addition of reactants during a hydrogenation reaction of cyclohexanedicarboxylic acid (CHDA), and Cyclohexanedimethanol (CHDM) prepared thereby.)

1. A process for producing Cyclohexanedimethanol (CHDM),

the catalyst is prepared by performing hydrogenation reaction of a catalyst and cyclohexanedicarboxylic acid (CHDA), and the weight ratio of the catalyst to the cyclohexanedicarboxylic acid is 1: 1-5.

2. The method for producing cyclohexanedimethanol according to claim 1,

the hydrogenation reaction further comprises at least one selected from a homogeneous additive and a heterogeneous additive.

3. The method for producing cyclohexanedimethanol according to claim 2,

the homogeneous additive comprises a compound selected from Ammonium Bicarbonate (NH)₄HCO₃) Sodium hydroxide (NaOH), Potassium carbonate (K)₂CO₃) And sodium borohydride (NaBH)₄) Comprises at least one selected from the group consisting of zirconium dioxide, titanium dioxide, cerium dioxide, silicon dioxide and magnesium oxide.

4. The method for producing cyclohexanedimethanol according to claim 2,

the weight ratio of the catalyst to the homogeneous additive is 1: 0.05 to 1.

5. The method for producing cyclohexanedimethanol according to claim 2,

the weight ratio of the catalyst to the heterogeneous additive is 1:0.5 to 3.

6. The method for producing cyclohexanedimethanol according to claim 1,

the temperature of the hydrogenation reaction of the cyclohexane dicarboxylic acid is within the range of 200-280 ℃.

7. The method for producing cyclohexanedimethanol according to claim 1,

the pressure of the hydrogenation reaction of the cyclohexanedicarboxylic acid is in the range of 50 to 150 bar.

8. The method for producing cyclohexanedimethanol according to claim 1,

the hydrogenation reaction time of the cyclohexanedicarboxylic acid is 1-8 hours.

9. The method for producing cyclohexanedimethanol according to claim 1,

as reactants, the cyclohexanedicarboxylic acid is used in a form selected from the group consisting of cis, trans and mixtures thereof.

10. The method for producing cyclohexanedimethanol according to claim 1,

the yield of cyclohexanedimethanol is in the range of 85% to 99%.

11. The method for producing cyclohexanedimethanol according to claim 1,

the catalyst contains at least one selected from ruthenium (Ru), palladium (Pd), rhodium (Rh), platinum (Pt), tin (Sn), and nickel (Ni).

12. The method for producing cyclohexanedimethanol according to claim 1,

the catalyst comprises at least one support selected from the group consisting of silica, alumina, titania, zeolite, zinc oxide, starch, and synthetic polymers.

13. A process for producing cyclohexanedimethanol,

the method for producing cyclohexanedimethanol according to claim 1, wherein said method comprises an isomerization reaction of cyclohexanedicarboxylic acid (CHDA).

14. A cyclohexanedimethanol characterized in that it comprises a cyclohexanedimethanol,

prepared by the process for the preparation of cyclohexanedimethanol according to any one of claims 1 to 13.

15. Cyclohexanedimethanol according to claim 14,

the trans-proportion of the cyclohexanedimethanol is within the range of 60-95%.

Technical Field

The present invention relates to a method for producing cyclohexanedimethanol having a high trans content and Cyclohexanedimethanol (CHDM) produced thereby, and more particularly, to a method for producing cyclohexanedimethanol having a high trans content by adjusting specific conditions, input of additives, or addition of reactants during hydrogenation of cyclohexanedicarboxylic acid (CHDA), and cyclohexanedimethanol produced thereby.

Background

Cyclohexanedimethanol (CHDM, 1, 4-cyclohexenedimethanol) is a basic raw material for producing polyester or polyamide resins, and is currently commercially produced in asia by SK chemistry, Mitsubishi (Mitsubishi) business, and SK NJC, a joint venture of shin nippon Rika, and occupies the entire market worldwide by Indorama (formerly Eastman) company. The demand for high value-added polyester resins is on the increase trend in the cyclohexanedimethanol market and is expected to increase in the future, so that supply and demand are required to be stable. It is known that, at present, the yield of cyclohexanedimethanol is kept at 100KTA scale by Indorama and at 20KTA scale by SK NJC, and SK NJC plans to increase production to 60KTA by 18 years, and recently, one production line has been added on the basis of the existing two production lines.

It is known from the literature that Purified Terephthalic Acid (PTA) is used for the preparation of cyclohexanedicarboxylic acidThere are roughly three methods for methanol. The first method is a method in which purified terephthalic acid of Sumitomo Seika chemical is ionized in an aqueous solution with NaOH to form a Salt (Salt) to increase the solubility of purified terephthalic acid and subjected to hydrogenation. The synthesis method has the advantage that the hydrogenation reaction temperature can be reduced (40-130 ℃) along with the increase of the solubility of purified terephthalic acid at low temperature, but the reaction is neutralized by HCl after the reaction to recover Na⁺Indispensable process of ion, residual Na⁺The Salt (Salt) not only affects the polymerization of PETG after the reaction, but also causes the waste water treatment cost of the Brine (Brine) solution containing NaCl to be excessively high, thereby adversely affecting the economy of the production process. The second method, which is a preparation method adopted by Indorama and SKNJC, is a process of preparing cyclohexanedimethanol from purified terephthalic acid through Dimethyl terephthalate (DMT) after preparing DMT from purified terephthalic acid through esterification (esterification). This process is relatively inexpensive in terms of catalyst price because a Cu or Cr based catalyst is used when cyclohexanedimethanol is produced from dimethyl cyclohexanedicarboxylate, but is disadvantageous in terms of process because it is a three-step (PTA → DMT → DMCD → CHDM) production process as a whole. In contrast, as a third method, a process for producing cyclohexanedimethanol from purified terephthalic acid via cyclohexanedicarboxylic acid, in which ruthenium, a noble metal, is used as an active metal at the time of hydrogenation of cyclohexanedicarboxylic acid, is disadvantageous in terms of the price of the catalyst, but cyclohexanedimethanol, which is a final product, can be obtained through a two-step process (PTA → CHDA → CHDM), and is therefore advantageous in terms of economy, as long as the product cost is reduced by reducing the number of steps and the competitiveness of the process technology is ensured.

However, even when cyclohexanedimethanol is produced by these conventional hydrogenation reactions of cyclohexanedicarboxylic acid, there is no disclosure of a method for obtaining cyclohexanedimethanol having a high trans content, and there is still a need for such.

Disclosure of Invention

Technical problem

The present invention is directed to solving the above-mentioned problems of the prior art and the technical problems that have been conventionally proposed.

An object of the present invention is to provide a method for preparing cyclohexanedimethanol having a high trans content, which can improve heat resistance of a crystalline polymer when used as a polymerization raw material, by a method for preparing cyclohexanedimethanol using reaction conditions, additives or various trans content reactants during hydrogenation of cyclohexanedicarboxylic acid (CHDA), and to provide cyclohexanedimethanol prepared thereby.

Technical scheme

The method for producing Cyclohexanedimethanol (CHDM) according to the present invention for achieving the above objects can be produced by performing a hydrogenation reaction of a catalyst and cyclohexanedicarboxylic acid (CHDA), wherein the weight ratio of the catalyst to the cyclohexanedicarboxylic acid is 1:1 to 5.

In a preferred embodiment of the present invention, the hydrogenation reaction may further include at least one selected from a homogeneous additive and a heterogeneous additive.

In a preferred embodiment of the present invention, the homogeneous additive may comprise one or more additives selected from ammonium bicarbonate (NH)₄HCO₃) Sodium hydroxide (NaOH), potassium carbonate (K)₂CO₃) And Sodium borohydride (NaBH)₄) May comprise at least one selected from the group consisting of zirconium dioxide, titanium dioxide, cerium dioxide, silicon dioxide and magnesium oxide.

In a preferred embodiment of the present invention, the weight ratio of the catalyst to the homogeneous additive may be 1: 0.05 to 1.

In a preferred embodiment of the present invention, the weight ratio of the catalyst to the heterogeneous additive may be 1:0.5 to 3.

In a preferred embodiment of the present invention, the temperature of the hydrogenation reaction of cyclohexanedicarboxylic acid may be in the range of 200 to 280 ℃.

In a preferred embodiment of the present invention, the pressure of the hydrogenation reaction of cyclohexanedicarboxylic acid may be in the range of 50 to 150 bar.

In a preferred embodiment of the present invention, the hydrogenation reaction time of the cyclohexanedicarboxylic acid may be 1 to 8 hours.

In a preferred embodiment of the present invention, the cyclohexanedicarboxylic acid selected from the group consisting of cis-form, trans-form and a mixture thereof is used as a reactant.

In a preferred embodiment of the present invention, the yield of cyclohexanedimethanol may be in the range of 85% to 99%.

In a preferred embodiment of the present invention, the catalyst may include at least one selected from ruthenium (Ru), palladium (Pd), rhodium (Rh), platinum (Pt), tin (Sn), and nickel (Ni).

In a preferred embodiment of the present invention, the method for producing cyclohexanedimethanol may include a process of isomerization of cyclohexanedicarboxylic acid.

In another aspect, the present invention provides a cyclohexanedimethanol prepared by a process for the preparation of a cyclohexanedimethanol.

In a preferred embodiment of the present invention, the trans ratio of cyclohexanedimethanol may be in the range of 60% to 95%.

Effects of the invention

As described above, a cyclohexanedimethanol having a high trans content, which is capable of improving heat resistance of a crystalline polymer when used as a polymerization raw material, is obtained by a cyclohexanedimethanol production method using reaction conditions, additives, or various trans content reactants during hydrogenation reaction of cyclohexanedicarboxylic acid (CHDA).

Drawings

FIG. 1 is a graph showing the hydrogenation activity of cyclohexanedicarboxylic acid as a function of reaction temperature in the production of the cyclohexanedimethanol of the present invention.

FIG. 2 is a graph showing the hydrogenation activity of cyclohexanedicarboxylic acid with NH in the production of cyclohexanedimethanol according to the present invention₄HCO₃Graph of (a).

FIG. 3 is a graph showing the activity of hydrogenation of cyclohexanedicarboxylic acid with the introduction of zirconium dioxide and titanium dioxide in the process for producing a cyclohexanedimethanol of the present invention.

FIGS. 4 to 5 are graphs showing that the results of hydrogenation of cyclohexanedicarboxylic acid in the production process of a cyclohexanedimethanol of the present invention vary with the introduction of zirconium dioxide.

FIGS. 6 to 7 are graphs showing the results of hydrogenation reactions using cyclohexanedicarboxylic acid of various trans contents in the process for producing a cyclohexanedimethanol of the present invention.

Detailed Description

The invention is described below with reference to specific examples capable of carrying out the invention. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. The various embodiments of the invention are distinct from each other but are understood not to be necessarily mutually exclusive. For example, a particular shape, structure, and characteristic described in connection with one embodiment of the present invention may be implemented within other embodiments without departing from the technical spirit and scope of the present invention.

The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims and equivalents thereof, as appropriately interpreted.

In addition, in the present specification, unless otherwise specified, "substituted" or "substituted" means that one or more hydrogen atoms in the functional group of the present invention are substituted with at least one substituent selected from the group consisting of a halogen atom (-F, -Cl, -Br, or-I), a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, an ester group, a ketone group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group, which may also be linked to each other to form a ring.

In the present invention, unless otherwise specified, the term "substituted" means that a hydrogen atom is substituted with a substituent such as a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or the like.

In addition, unless otherwise specified, the "hydrocarbon group" means a saturated or unsaturated hydrocarbon group of a linear, branched or cyclic type, and the alkyl group, alkenyl group, alkynyl group and the like may be of a linear, branched or cyclic type.

In addition, in the present specification, unless otherwise specified, "alkyl" means an alkyl group of C1 to C30, and "aryl" means an aryl group of C6 to C30. The term "heterocyclic group" as used herein refers to a group containing 1 to 3 heteroatoms selected from O, S, N, P, Si and combinations thereof in one ring, and includes, but is not limited to, pyridine, thiophene, pyrazine and the like.

Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention.

As described above, the conventional technology for hydrogenation of cyclohexanedicarboxylic acid (CHDA) has a limitation in producing Cyclohexanedimethanol (CHDM) having a high trans content.

In contrast, the present invention provides a method for producing cyclohexanedimethanol, which comprises hydrogenating a cyclohexanedicarboxylic acid with a catalyst in a weight ratio of 1:1 to 5.

According to the present invention, the kind of the catalyst is not particularly limited, and preferably, a ruthenium-based catalyst may be used.

In general, a carrier on which ruthenium is supported as an active component is a solid which stably supports and holds a substance having a catalytic function after being dispersed, and is generally porous or large in area in order to highly disperse and support the catalytic function substance so that the exposed surface becomes large. Such a carrier needs to be stable mechanically, thermally and chemically, but is not limited to the kind of the carrier, and includes all carriers generally used as a carrier, for example, silica, alumina, titania, zeolite, zinc oxide, starch, synthetic polymer, etc., preferably silica, but is not limited thereto.

In addition, as the active component, the hydrogenation catalyst may include a group 8 transition metal, and preferably, may include at least one selected from ruthenium (Ru), nickel (Ni), palladium (Pd), rhodium (Rh), platinum (Pt), tin (Sn), and the like.

Specifically, according to the present invention, when the hydrogenation reaction is performed under specific reaction conditions, at least one selected from a homogeneous additive and a heterogeneous additive may be included to prepare cyclohexanedimethanol, or cyclohexanedimethanol containing a trans ratio in the range of 60% to 95% may be prepared by a method of adding reactants having a trans content in a specific ratio, and preferably cyclohexanedimethanol containing a trans ratio in the range of 65% to 85% may be prepared.

First, according to the present invention, the specific reaction conditions in the hydrogenation reaction include a hydrogenation temperature in the range of 200 to 280 ℃, a reaction pressure in the range of 50 to 150bar, and a reaction time in the range of 1 to 8 hours.

The type of reactor for carrying out these hydrogenation reactions is not particularly limited, and any batch reactor or continuous reactor may be used as long as it can be used in the technical field to which the present invention pertains. In addition, the reactor may comprise a heat removal device for removing heat generated in the reaction.

In the present invention, the hydrogenation reaction temperature may be in the range of 200 to 280 ℃, preferably 210 to 270 ℃, and more preferably 230 to 250 ℃. In particular, when the reaction temperature is less than 200 ℃, the hydrogenation reaction of cyclohexanedicarboxylic acid is not sufficiently activated, and there is a problem that the selectivity and yield of cyclohexanedimethanol are insufficient, and when the temperature is more than 280 ℃, the yield of cyclohexanedimethanol is decreased by a side reaction, and therefore the above range is preferable.

The hydrogenation reaction pressure can be in the range of 50-150 bar, preferably 70-120 bar, and more preferably 90-120 bar. In particular, when the reaction pressure is less than 50bar, hydrogen participating in the reaction may not be sufficiently present in the solvent, which may cause a problem of activity reduction, and when the reaction pressure is more than 150bar, a problem of process stability may occur, so that the above range is preferable.

The hydrogenation reaction time may be 1 to 8 hours, preferably 1 to 6 hours. In particular, when the reaction time is less than 1 hour, there is a possibility that the reaction does not sufficiently proceed and there is a problem in obtaining cyclohexanedimethanol, and when the reaction time is more than 8 hours, there is a possibility that reduction of cyclohexanedimethanol and a problem in reaction efficiency are caused by additional side reactions, and thus the above range is preferable.

Secondly, the hydrogenation reaction of the present invention may include the homogeneous additive and/or the heterogeneous additive.

According to the invention, the homogeneous additive, as a substance dissolved in the solvent, may be chosen from Ammonium bicarbonates (NH)₄HCO₃) Sodium hydroxide (NaOH), Potassium carbonate (K)₂CO₃) And Sodium borohydride (NaBH)₄) Preferably Ammonium Bicarbonate (NH)₄HCO₃)。

Wherein, when the homogeneous additive is Ammonium Bicarbonate (NH)₄HCO₃) Wherein the weight ratio of the catalyst to the ammonium bicarbonate is 1: 0.05 to 1. Particularly, when the ammonium bicarbonate is contained in an amount of less than 0.05 weight ratio as compared with the catalyst, it may be difficult to obtain cyclohexanedimethanol having a desired yield or selectivity, and when the ammonium bicarbonate is contained in an amount of more than 1 weight ratio as compared with the catalyst, there may occur a problem that a reaction rate is lowered, so that the above range is preferable.

Also, the heterogeneous additive may include at least one metal oxide selected from zirconium dioxide, titanium dioxide, cerium dioxide, silicon dioxide, and magnesium oxide as an additive that is not dissolved in a solvent, and preferably, may be zirconium dioxide or titanium dioxide.

Wherein when it is usedThe heterogeneous additive is zirconium dioxide (ZrO)₂) When the catalyst is mixed with the zirconium dioxide (ZrO)₂) The weight ratio of (A) to (B) may be 1:0.5 to 3. In particular, when the zirconium dioxide is contained in an amount of less than 0.5 weight ratio as compared with the catalyst, it may be difficult to obtain Cyclohexanedimethanol (CHDM) having a desired yield or selectivity, and when it is contained in an amount of more than 1 weight ratio as compared with the catalyst, there may be a problem that a reaction rate is lowered, and thus the above range is preferable.

Finally, the hydrogenation reaction of the present invention may include the reactants, either alone or in admixture.

According to the present invention, the reactant may be selected from the group consisting of cis, trans and a mixture thereof, and preferably, the cyclohexane dicarboxylic acid having a high trans content may be contained.

Wherein, especially the cyclohexane dicarboxylic acid can have a trans content in the range of 5 to 99. Preferably, the trans content of the cyclohexanedicarboxylic acid may be 50 to 99, and more preferably, the trans content of the cyclohexanedicarboxylic acid may be 60 to 95.

Depending on the circumstances, reactants may be included that isomerize cyclohexanedicarboxylic acid containing relatively low trans content.