CN114436772A - Preparation method of 1, 4-cyclohexanedimethanol - Google Patents
Preparation method of 1, 4-cyclohexanedimethanol Download PDFInfo
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- CN114436772A CN114436772A CN202210110215.3A CN202210110215A CN114436772A CN 114436772 A CN114436772 A CN 114436772A CN 202210110215 A CN202210110215 A CN 202210110215A CN 114436772 A CN114436772 A CN 114436772A
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention provides a preparation method of 1, 4-cyclohexanedimethanol, which comprises the steps of preparing 1, 4-cyclohexanedimethanol through hydrogenation reaction of 1, 4-cyclohexanedicarboxylic acid, wherein the reaction is carried out on a fixed bed reactor, the 1, 4-cyclohexanedimethanol and water are heated and dissolved in a high-pressure reaction kettle, and are conveyed into the fixed bed reactor through a high-temperature pump, and the product 1, 4-cyclohexanedimethanol is obtained through hydrogenation under the action of a catalyst; the catalyst comprises an active component Ru, an auxiliary agent Pd and Sn, and a carrier which is one of a carbon nano tube and a carbon nano fiber. The conversion rate of the raw material 1, 4-cyclohexanedicarboxylic acid reaches more than 99.5 percent, and the yield of the product 1, 4-cyclohexanedimethanol can stably reach more than 98.5 percent. In addition, the service life of the catalyst is long, the one-way operation life of the catalyst is more than 2000h, and the method has good industrial application prospect.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a method for preparing 1, 4-cyclohexanedimethanol through continuous hydrogenation.
Background
1, 4-cyclohexane dimethanol (CHDM) is an important polyester production raw material, and polyethylene terephthalate (PET) resin modified by CHDM copolymerization has a low crystallization rate and good processing and physical properties, particularly, polyester modified by trans-CHDM has a high glass transition temperature and a high softening temperature, and has good chemical resistance and environmental adaptability, and a wide application range. At present, the main process for industrially producing CHDM is to use dimethyl terephthalate as a raw material, firstly hydrogenate benzene rings to generate 1, 4-cyclohexane dimethyl phthalate, and then further hydrogenate the 1, 4-cyclohexane dimethyl phthalate to prepare CHDM. In contrast, terephthalic acid (PTA) has a lower cost and a richer source of raw materials than dimethyl terephthalate, and thus has become a new trend in recent years.
The CHDM prepared by hydrogenation of terephthalic acid (PTA) mostly adopts a two-step method, wherein PTA benzene skeleton is hydrogenated under the action of a catalyst to generate CHDA, and the generated CHDA is continuously subjected to carboxyl hydrogenation under the action of the catalyst to generate CHDM. The reaction for generating CHDA by PTA hydrogenation generally adopts Pd/C as a catalyst, and the CHDA yield is higher than 95%. The CHDM reaction prepared by CHDA hydrogenation has higher requirements on the catalyst. U.S. Pat. No. 8, 6495730 uses Ru-Sn-Re/C catalyst, and reacts in an autoclave reactor at 230 deg.C and 9.0MPa for about 3.5 hours, the CHDA conversion rate is 98%, and the CHDM yield is 75%. Patent CN1911884 adopts Ru-Sn/Al in autoclave reactor2O3The catalyst reacts for about 4 hours at 230 ℃ and 10MPa, the CHDM yield is 97.9 percent, and the catalyst can be recycled for 5 times. Patent CN101982236 uses Ru-Sn/Al in an autoclave reactor2O3The catalyst reacts at 230 ℃ and 8.0MPa until hydrogen absorption is finished, and the CHDM yield is 94.1%.
For the reaction of CHDM prepared by CHDA hydrogenation, RuSn/C is generally used as a catalyst, and because the activated carbon carrier has rich microporous pore channel structures, the interior of the catalyst has serious internal diffusion resistance. Due to the limitation of mass transfer resistance, a reactant CHDA cannot be diffused into a catalyst pore channel quickly, so that the concentration of the reactant in the catalyst is low, and the reaction speed is reduced remarkably; more importantly, if CHDM generated by the reaction cannot be diffused out of the catalyst pore channel rapidly, side reactions such as decarboxylation and esterification are easy to occur, so that the selectivity of a target product is greatly reduced.
Therefore, a more suitable catalyst or a better hydrogenation process is needed for the CHDA hydrogenation to CHDM reaction.
Disclosure of Invention
The Carbon Nanotubes (CNTs) and the Carbon Nanofibers (CNFs) are mutually wound together, have abundant macropores and large specific surface area, and can greatly reduce the mass transfer resistance in the pore channel. Generally speaking, the diameter of the carbon nanofiber is about 50 to 200nm, and the total specific surface area is 150 to 300m2(g) the external specific surface area is 120-250 m2(ii)/g, the average pore diameter is 8-12 nm. Therefore, the invention discloses a hydrogenation catalyst taking carbon nano tubes or carbon nano fibers as a carrier, and the catalyst can be well applied to the hydrogenation of 1, 4-cyclohexanedicarboxylic acid to prepare 1, 4-cyclohexanedimethanol.
The invention provides a preparation method of 1, 4-cyclohexanedimethanol, which comprises the steps of preparing 1, 4-cyclohexanedimethanol through hydrogenation reaction of 1, 4-cyclohexanedicarboxylic acid, wherein the reaction is carried out on a fixed bed reactor, the 1, 4-cyclohexanedicarboxylic acid and water are heated and dissolved in a high-pressure reaction kettle and are conveyed into the fixed bed reactor through a high-temperature pump, and the 1, 4-cyclohexanedicarboxylic acid is hydrogenated under the action of a catalyst to obtain a product 1, 4-cyclohexanedimethanol; the active component of the catalyst is Ru, the auxiliary agent is Pd and Sn, and the carrier is one of a carbon nano tube and carbon nano fiber; the catalyst is prepared by adopting an impregnation method, and specifically comprises the steps of impregnating precursors of active metal ruthenium and auxiliary agent metal palladium and tin on a carrier, drying and reducing to obtain the catalyst, and reducing by using sodium borohydride in the preparation process of the catalyst.
In a specific embodiment, the mass feed ratio of water to 1, 4-cyclohexanedicarboxylic acid is 3 to 200:1, preferably 4 to 100: 1.
In a specific embodiment, the mass fraction of Ru in the catalyst is 1-8 wt%, preferably 3-6 wt%; the mass fraction of the assistant Pd is 0.01-0.8 wt%, preferably 0.1-0.5 wt%; the mass fraction of the auxiliary Sn is 1.0-10.0 wt%, preferably 3-5 wt%.
In a specific embodiment, the dissolving temperature of the 1, 4-cyclohexanedicarboxylic acid and pure water when the raw material liquid is formed by heating and dissolving in the high-pressure reaction kettle is 100 to 200 ℃, preferably 120 to 170 ℃, and nitrogen is filled into the high-pressure reaction kettle during dissolving to increase the pressure so that the water is not vaporized at the dissolving temperature, and the pressure after the nitrogen is filled into the high-pressure reaction kettle is lower than the hydrogenation reaction pressure in the subsequent fixed bed reactor, preferably 1 to 5MPa after the nitrogen is filled into the high-pressure reaction kettle.
In a specific embodiment, the hydrogenation pressure is 6.0-15.0 MPa, preferably 8.0-10.0 MPa, the reaction temperature is 160-260 ℃, preferably 220-250 ℃, more preferably 220-240 ℃, and the feeding mass space velocity of CHDA is 0.1-1.0 h-1Preferably 0.3 to 0.5h-1The molar ratio of hydrogen to CHDA is 10.0-40.0.
The CHDM preparation method by CHDA hydrogenation adopted by the invention has the following advantages:
1) the invention adopts macroporous carbon nano-tubes or carbon nano-fibers as carriers to promote the diffusion of raw materials and products; and the PdSnRu alloy catalyst is synthesized, the CHDA hydrogenation rate is high, the CHDM yield is high, the CHDA conversion rate reaches over 99.5 percent, and the CHDM yield of the product reaches over 99.0 percent.
2) The catalyst used in the invention has high activity, good selectivity and long service life, and can stably run for more than 2000 h.
In general, the conversion rate of the raw material 1, 4-cyclohexanedicarboxylic acid of the invention reaches more than 99.5 percent, and the yield of the product 1, 4-cyclohexanedimethanol can stably reach more than 98.5 percent. In addition, the catalyst has long service life, the one-way operation life of the catalyst is more than 2000h, and the catalyst has good industrial application prospect.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Preparation of the catalyst:
example a 1: weighing certain mass of stannous chloride, palladium chloride and chlorineDissolving ruthenium in hydrochloric acid, and soaking a certain amount of carbon nanotubes in the solution. Soaking for 24h, drying at 120 deg.C for 4h, and adopting NaBH4And (3) reduction, wherein the loading amount of the metal Ru is 5.0%, the loading amount of the metal Pd is 0.5%, and the loading amount of the Sn is 4.0%, so as to obtain the catalyst 1.
Example a 2: catalyst 2 was obtained in the same manner as in example A1 except that the carrier was carbon nanofibers.
Comparative example a 3: catalyst 3 was obtained by supporting the metals Ru, Pd and Re, with the amount of the metal Ru supported 5.0%, the amount of the metal Pd supported 0.5% and the amount of the metal Re supported 4.0%, as in example A1.
Comparative example a 4: the same procedure as in example A1 was repeated except that metals Ru, Pd and La were supported, the amount of supported metal Ru was 5.0%, the amount of supported metal Pd was 0.5% and the amount of supported metal La was 4.0%, to obtain catalyst 4.
Comparative example a 5: catalyst 5 was obtained by formaldehyde reduction otherwise as in example A1.
Comparative example a 6: catalyst 6 was obtained by reduction with hydrogen at 300 ℃ for 4 hours as in example A1.
Comparative example a 7: catalyst 7 was obtained by supporting metals Ru, Ni and Sn, wherein the supporting amount of metal Ru was 5.0%, the supporting amount of metal Ni was 0.5% and the supporting amount of Sn was 4.0%, in the same manner as in example a 1.
Comparative example A8: catalyst 8 was obtained by supporting metals Ru, Cu and Sn, wherein the supporting amount of metal Ru was 5.0%, the supporting amount of metal Cu was 0.5% and the supporting amount of Sn was 4.0%, as in example a 1.
Comparative example a 9: the support was activated carbon, otherwise as in example A1, giving catalyst 9.
The catalyst evaluation was carried out in a fixed bed reactor, and 20.0g of the catalyst was charged in a reaction tube having an inner diameter of 13 mm. CHDA is dissolved in a high-pressure dissolution kettle to obtain a 20 wt% CHDA aqueous solution, and the CHDA solution is pumped into the fixed bed through a high-temperature pump. Catalyst evaluation conditions: the reaction temperature is 230 ℃, the reaction pressure is 8.0MPa, and the feeding mass space velocity of CHDA is 0.5h-1The molar ratio of hydrogen to CHDA was 20.0. The evaluation results are shown in Table 1:
TABLE 1
| Catalyst number | Characteristics of catalyst preparation | CHDA conversion/%) | CHDM yield/% | |
| Example A1 | Catalyst 1 | Ru、Pd、Sn | 99.5 | 99.0 |
| Example A2 | Catalyst 2 | The carrier is carbon nano-fiber | 99.5 | 98.7 |
| Comparative example A3 | Catalyst 3 | Ru、Pd、Re | 92.2 | 91.5 |
| Comparative example A4 | Catalyst 4 | Ru、Pd、La | 85.5 | 88.3 |
| Comparative example A5 | Catalyst 5 | Formaldehyde reduction | 96.2 | 93.4 |
| Comparative example A6 | Catalyst 6 | Reduction of hydrogen | 93.6 | 93.2 |
| Comparative example A7 | Catalyst 7 | Ru、Ni、Sn | 80.8 | 83.2 |
| Comparative example A8 | Catalyst 8 | Ru、Cu、Sn | 82.8 | 85.6 |
| Comparative example A9 | Catalyst 9 | The carrier is active carbon | 79.2 | 82.3 |
Examples A1, A2 and comparison from Table 1Example A9 shows that for CHDM prepared by hydrogenation of CHDA, the conversion of CHDA and the yield of CHDM are both significantly better than those of catalysts prepared with activated carbon as the support, using carbon nanotubes or carbon nanofibers as the support. The main reason is that the reaction for preparing CHDM by CHDA hydrogenation is influenced by diffusion, when a carbon nano tube or carbon nano fiber with large pore diameter is used as a carrier, the CHDA serving as a raw material can be smoothly diffused into a carrier pore channel and reacts on metal loaded in the pore channel, and the generated product CHDM is quickly diffused into a solution from the pore channel, so that the generation of side reactions is inhibited. Compared with the comparative example A1, the comparative example A3 and the comparative example A4, the accelerating effect of the auxiliary Sn is better than that of Re and La; comparing example A1, comparative example A5, comparative example A6, it was found that the reduction mode during the catalyst preparation process had some effect on the catalyst performance as NaBH4Reducing to the best; in comparative example A1, comparative example A7 and comparative example A8, the improvement of the catalyst performance of the auxiliary agent Pd is obviously higher than that of Ni and Cu.
Optimizing a reaction process:
example B1
The reaction process conditions were optimized in a fixed bed reactor, and 20.0g of catalyst 1 was charged in a reaction tube having an inner diameter of 13 mm. The CHDA was dissolved in a high-pressure dissolution vessel to obtain a 20 wt% aqueous solution of CHDA, and the CHDA solution was pumped into the fixed bed by a high-temperature pump. Catalyst evaluation conditions: the reaction temperature is 230 ℃, the reaction pressure is 8.0MPa, and the feeding mass space velocity of CHDA is 0.5h-1The molar ratio of hydrogen to CHDA was 20.0. The evaluation results are shown in Table 2. Examples B2 to B8 the results are shown in Table 2, with corresponding changes in the reaction conditions.
TABLE 2
As can be seen from the comparison of examples B1-B3 in Table 2, the catalyst has a better hydrogenation effect at a hydrogenation reaction temperature of 230 ℃, and when the hydrogenation reaction temperature is as low as 210 ℃, part of CHDA does not participate in the reaction, and the reaction is incomplete, so the hydrogenation effect is poor; when the reaction temperature is up to 250 ℃, more byproducts are generated due to overhigh temperature. As can be seen from examples B1, B4, B5 and B6, the hydrogenation pressure is greater than 8.0MPa, the hydrogenation effect is good, the CHDA conversion rate is greater than 99.5%, and the CHDM yield is greater than 99.0%. As can be seen from examples B1, B7, and B8 of Table 2, the CHDA feed mass space velocity affects the CHDA conversion, with the CHDA feed mass space velocity not exceeding 0.50h-1It is preferable.
The life evaluation test of catalyst 1 was carried out under the same reaction process conditions as in example B1. The product after hydrogenation was analyzed and the results are shown in Table 3.
TABLE 3
As can be seen from the data in Table 3, catalyst 1 has good stability, and after the catalyst runs for 2000 hours, the CHDA conversion rate is still maintained at 99.3%, and the CHDM yield is as high as 98.7%. The catalyst used in the invention can catalyze CHDA hydrogenation to generate CHDM with the yield stably reaching more than 98.5%, and meanwhile, the catalyst can stably run for more than 2000 hours without obvious inactivation, which shows that the catalyst has good industrial application prospect when being used for CHDA hydrogenation to generate CHDM.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions and substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (5)
1. The preparation method of the 1, 4-cyclohexanedimethanol is characterized by comprising the steps of preparing the 1, 4-cyclohexanedimethanol through a1, 4-cyclohexanedicarboxylic acid hydrogenation reaction, wherein the reaction is carried out on a fixed bed reactor, the 1, 4-cyclohexanedimethanol and water are heated and dissolved in a high-pressure reaction kettle and are conveyed into the fixed bed reactor through a high-temperature pump, and the 1, 4-cyclohexanedicarboxylic acid is hydrogenated under the action of a catalyst to obtain a product 1, 4-cyclohexanedimethanol; the active component of the catalyst is Ru, the auxiliary agent is Pd and Sn, and the carrier is one of a carbon nano tube and carbon nano fiber; the catalyst is prepared by adopting an impregnation method, and specifically comprises the steps of impregnating precursors of active metal ruthenium and auxiliary agent metal palladium and tin on a carrier, drying and reducing to obtain the catalyst, and reducing by using sodium borohydride in the preparation process of the catalyst.
2. The process according to claim 1, wherein the mass feed ratio of water to 1, 4-cyclohexanedicarboxylic acid is from 3 to 200:1, preferably from 4 to 100: 1.
3. The process according to claim 1, wherein the mass fraction of Ru in the catalyst is 1 to 8 wt%, preferably 3 to 6 wt%; the mass fraction of the assistant Pd is 0.01-0.8 wt%, preferably 0.1-0.5 wt%; the mass fraction of the auxiliary Sn is 1.0-10.0 wt%, preferably 3-5 wt%.
4. The method according to claim 1, wherein the dissolution temperature of 1, 4-cyclohexanedicarboxylic acid and pure water in the high-pressure reaction vessel when heated and dissolved to form the raw material liquid is 100 to 200 ℃, preferably 120 to 170 ℃, and the high-pressure reaction vessel is filled with nitrogen gas during dissolution to increase the pressure so that water is not vaporized at the dissolution temperature, and the pressure after the high-pressure reaction vessel is filled with nitrogen gas is lower than the hydrogenation reaction pressure in the subsequent fixed bed reactor, preferably 1 to 5MPa after the high-pressure reaction vessel is filled with nitrogen gas.
5. The process according to any one of claims 1 to 4, wherein the hydrogenation pressure is 6.0 to 15.0MPa, preferably 8.0 to 10.0MPa, the reaction temperature is 160 to 260 ℃, preferably 220 to 250 ℃, more preferably 220 to 240 ℃, and the CHDA feed mass space velocity is 0.1 to 1.0h-1Preferably 0.3 to 0.5h-1The molar ratio of hydrogen to CHDA is 10.0-40.0.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024140390A1 (en) * | 2022-12-28 | 2024-07-04 | 中国石油天然气集团有限公司 | 1,4-cyclohexanedimethanol production system and method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911884A (en) * | 2005-08-09 | 2007-02-14 | 中国石化上海石油化工股份有限公司 | Method of preparing 1,4-cyclohexane dimethanol by hydrogenation of 1,4-cyclohexane diformic acid |
| CN103664524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid |
| CN103877991A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method for trans-1,4-cyclohexanedimethanol, and catalyst used therefor |
| US20170107164A1 (en) * | 2014-04-07 | 2017-04-20 | Lotte Chemical Corporation | Composite metal catalyst composition, and method and apparatus for preparing 1,4-cyclohexanedimethanol using same |
| WO2021133138A1 (en) * | 2019-12-27 | 2021-07-01 | 한화솔루션 주식회사 | Method for preparation of 1, 4-cyclohexanedimethanol |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911884A (en) * | 2005-08-09 | 2007-02-14 | 中国石化上海石油化工股份有限公司 | Method of preparing 1,4-cyclohexane dimethanol by hydrogenation of 1,4-cyclohexane diformic acid |
| CN103664524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid |
| CN103877991A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method for trans-1,4-cyclohexanedimethanol, and catalyst used therefor |
| US20170107164A1 (en) * | 2014-04-07 | 2017-04-20 | Lotte Chemical Corporation | Composite metal catalyst composition, and method and apparatus for preparing 1,4-cyclohexanedimethanol using same |
| WO2021133138A1 (en) * | 2019-12-27 | 2021-07-01 | 한화솔루션 주식회사 | Method for preparation of 1, 4-cyclohexanedimethanol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024140390A1 (en) * | 2022-12-28 | 2024-07-04 | 中国石油天然气集团有限公司 | 1,4-cyclohexanedimethanol production system and method |
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