CN112174777A - Preparation method of 2,2' -di (4-hydroxycyclohexyl) propane - Google Patents
Preparation method of 2,2' -di (4-hydroxycyclohexyl) propane Download PDFInfo
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- CN112174777A CN112174777A CN202011233336.4A CN202011233336A CN112174777A CN 112174777 A CN112174777 A CN 112174777A CN 202011233336 A CN202011233336 A CN 202011233336A CN 112174777 A CN112174777 A CN 112174777A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a non-condensed ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane, which comprises the following specific operation steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, then fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor, wherein the step two is as follows: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: the catalyst comprises 20-50% of Pt, 0.5-1% of an auxiliary agent and the balance of a catalyst carrier, wherein the catalyst carrier is alumina. According to the invention, the reaction process is controllable through the noble metal supported catalyst consisting of 35% by mass of Pt, 1% by mass of an auxiliary agent and the balance of a catalyst carrier, the continuous preparation of 2,2' -bis (4-hydroxycyclohexyl) propane can be realized, the dosage content of the catalyst is 0.8% to the minimum, and the conversion rate is 97.1% to the maximum.
Description
Technical Field
The invention relates to the technical field of hydrogenated bisphenol A, and particularly relates to a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane.
Background
Hydrogenated bisphenol A, 2' -bis (4-hydroxycyclohexyl) propane, is a very useful substance in the preparation of polymers, and is an important raw material for producing synthetic materials such as special epoxy resins, phenolic resins, unsaturated resins, polyacrylic resins and the like, and has the advantages of thermal stability, light stability, chemical stability, weather resistance and the like. The hydrogenated bisphenol A can improve the weather resistance of the epoxy resin, can be applied to most outdoor and special environments, belongs to aromatic compound hydrogenation, belongs to the field of benzene ring hydrogenation, mainly comprises the following three catalysts, namely a metal framework type catalyst, a noble metal supported type catalyst and a homogeneous catalyst, has the general reaction condition of 50-250 ℃ and the hydrogen pressure of 1-30 MPa, and can adopt an intermittent or continuous hydrogenation process flow.
However, in the actual use thereof, patent CN 104220404a relates to a purification process after bisphenol compound hydrogenation, in which the product after bisphenol compound catalytic hydrogenation is washed with an aromatic hydrocarbon as a poor solvent, separated and recovered, and the purity is as high as 95% to 100%, but the bisphenol a hydrogenation catalyst provided in the above method is too expensive, or there is a problem that the conversion rate of the raw material and the product purity cannot be compatible when the catalyst catalyzes the hydrogenation of bisphenol a.
Therefore, it is necessary to develop a process for producing 2,2' -bis (4-hydroxycyclohexyl) propane to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of 2,2 '-bis (4-hydroxycyclohexyl) propane, which is characterized in that a noble metal supported catalyst consisting of 35% by mass of Pt, 1% by mass of an auxiliary agent and the balance of a catalyst carrier is used as a catalyst for the reaction of bisphenol A and hydrogen, so that the reaction process is controllable, the production cost is low, the 2,2' -bis (4-hydroxycyclohexyl) propane can be continuously prepared, the catalyst dosage content reaches the lowest 0.8%, the conversion rate reaches the highest 97.1%, the conversion rate of raw materials and the purity of products can be considered simultaneously, and the defects in the technology are overcome.
In order to achieve the above purpose, the invention provides the following technical scheme: a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane comprises the following specific operation steps:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: the catalyst comprises 20-50% by mass of Pt, 0.5-1% by mass of an auxiliary agent and the balance of a catalyst carrier, wherein the catalyst carrier is alumina;
step three: immersing an alumina carrier into a salt solution, immersing for 3-5 h at 60-80 ℃, then drying at 300-600 ℃, immersing an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 2-4 h, and then drying at 400-500 ℃;
step four: and conveying the gas-liquid mixed product into a condenser for cooling for 5-10 min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 3-5 min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
Preferably, the auxiliary agent is aluminum powder.
Preferably, the solvent is methanol or ethanol.
Preferably, the salt solution is prepared by platinum nitrate and ammonium water according to a ratio of 1: 1.5.
Preferably, the technological conditions of the hydrogenation reaction of the bisphenol A are that the reaction temperature is 100-180 ℃, the reaction pressure is 5-10 MPa, the feed concentration is 15-30%, the liquid space velocity is 1-3 h < -1 >, and the molar ratio of hydrogen to BPA is 18-46.
Preferably, the mass ratio of the bisphenol A to the noble metal supported catalyst is 200: 3.
In the technical scheme, the invention provides the following technical effects and advantages:
the noble metal supported catalyst consisting of 35% by mass of Pt, 1% by mass of an auxiliary agent and the balance of a catalyst carrier is used for the catalyst for the reaction of bisphenol A and hydrogen, so that the reaction process is controllable, the production cost is low, the continuous preparation of 2,2' -bis (4-hydroxycyclohexyl) propane can be realized, the dosage content of the catalyst reaches the lowest level, the conversion rate reaches the highest level of 97.1%, and the conversion rate of raw materials and the purity of products can be considered simultaneously.
Detailed Description
The present invention will be described in further detail below in order to enable those skilled in the art to better understand the technical solution of the present invention.
The invention provides a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane, which comprises the following specific operation steps:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: the catalyst comprises 20-50% by mass of Pt, 0.5-1% by mass of an auxiliary agent and the balance of a catalyst carrier, wherein the catalyst carrier is alumina;
step three: immersing an alumina carrier into a salt solution, immersing for 3-5 h at 60-80 ℃, then drying at 300-600 ℃, immersing an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 2-4 h, and then drying at 400-500 ℃;
step four: and conveying the gas-liquid mixed product into a condenser for cooling for 5-10 min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 3-5 min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
Further, in the above technical scheme, the auxiliary agent is aluminum powder.
Further, in the above technical solution, the solvent is methanol or ethanol.
Further, in the above technical solution, the salt solution is prepared by platinum nitrate and ammonium water according to a ratio of 1: 1.5.
Further, in the technical scheme, the hydrogenation reaction of the bisphenol A is carried out under the process conditions of the reaction temperature of 100-180 ℃, the reaction pressure of 5-10 MPa, the feed concentration of 15-30%, the liquid space velocity of 1-3 h < -1 >, and the molar ratio of hydrogen to BPA of 18-46.
Further, in the above technical solution, the mass ratio of the bisphenol a to the noble metal supported catalyst is 200: 3.
Example 1:
the invention provides a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane, which comprises the following specific operation steps:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: the catalyst comprises 20% of Pt, 0.5% of auxiliary agent and the balance of a catalyst carrier, wherein the catalyst carrier is alumina;
step three: soaking an alumina carrier in a salt solution for 4 hours at 70 ℃, then drying at 450 ℃, soaking an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 3 hours, and then drying at 450 ℃;
step four: and (3) conveying the gas-liquid mixed product into a condenser for cooling for 8min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 4min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
Further, in the above technical scheme, the auxiliary agent is aluminum powder.
Further, in the above technical solution, the solvent is methanol or ethanol.
Further, in the above technical solution, the salt solution is prepared by platinum nitrate and ammonium water according to a ratio of 1: 1.5.
Further, in the above technical scheme, the process conditions of the hydrogenation reaction of bisphenol a are that the reaction temperature is 140 ℃, the reaction pressure is 8MPa, the feed concentration is 20%, the liquid space velocity is 1.5h-1, and the molar ratio of hydrogen to BPA is 35.
Further, in the above technical solution, the mass ratio of the bisphenol a to the noble metal supported catalyst is 200: 3.
In the embodiment, the mass content of the catalyst Pt is less, the mass content of the auxiliary agent is moderate, the reaction process is controllable, the dosage content of the catalyst is 1.5 percent, and the conversion rate is 95.4 percent
Example 2:
the invention provides a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane, which comprises the following specific operation steps:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: the catalyst comprises 20% of Pt, 1% of auxiliary agent and the balance of catalyst carrier, wherein the catalyst carrier is alumina;
step three: soaking an alumina carrier in a salt solution for 4 hours at 70 ℃, then drying at 450 ℃, soaking an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 3 hours, and then drying at 450 ℃;
step four: and (3) conveying the gas-liquid mixed product into a condenser for cooling for 8min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 4min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
Further, in the above technical scheme, the auxiliary agent is aluminum powder.
Further, in the above technical solution, the solvent is methanol or ethanol.
Further, in the above technical solution, the salt solution is prepared by platinum nitrate and ammonium water according to a ratio of 1: 1.5.
Further, in the above technical scheme, the process conditions of the hydrogenation reaction of bisphenol a are that the reaction temperature is 140 ℃, the reaction pressure is 8MPa, the feed concentration is 20%, the liquid space velocity is 1.5h-1, and the molar ratio of hydrogen to BPA is 35.
Further, in the above technical solution, the mass ratio of the bisphenol a to the noble metal supported catalyst is 200: 3.
Further, in the above technical solution, the mass ratio of the bisphenol a to the noble metal supported catalyst is 200: 3. Compared with the example 1, in the example, the mass content of the catalyst Pt is less, the mass content proportion of the auxiliary agent is moderate, the reaction process is controllable, the catalyst dosage content is 1.3%, and the conversion rate is 96.2%.
Example 3:
the invention provides a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane, which comprises the following specific operation steps:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: 35% of Pt, 0.5% of auxiliary agent and the balance of catalyst carrier, wherein the catalyst carrier is alumina;
step three: soaking an alumina carrier in a salt solution for 4 hours at 70 ℃, then drying at 450 ℃, soaking an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 3 hours, and then drying at 450 ℃;
step four: and (3) conveying the gas-liquid mixed product into a condenser for cooling for 8min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 4min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
Further, in the above technical scheme, the auxiliary agent is aluminum powder.
Further, in the above technical solution, the solvent is methanol or ethanol.
Further, in the above technical solution, the salt solution is prepared by platinum nitrate and ammonium water according to a ratio of 1: 1.5.
Further, in the above technical scheme, the process conditions of the hydrogenation reaction of bisphenol a are that the reaction temperature is 140 ℃, the reaction pressure is 8MPa, the feed concentration is 20%, the liquid space velocity is 1.5h-1, and the molar ratio of hydrogen to BPA is 35.
Further, in the above technical solution, the mass ratio of the bisphenol a to the noble metal supported catalyst is 200: 3.
Comparing examples 1 and 2, in the present example, the mass content of the catalyst Pt is moderate, the mass content of the auxiliary agent is moderate, the reaction process is controllable, and the catalyst dosage content is 0.9%, and the conversion rate is 96.7%.
Example 4:
the invention provides a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane, which comprises the following specific operation steps:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: 35% of Pt, 1% of auxiliary agent and the balance of catalyst carrier, wherein the catalyst carrier is alumina;
step three: soaking an alumina carrier in a salt solution for 4 hours at 70 ℃, then drying at 450 ℃, soaking an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 3 hours, and then drying at 450 ℃;
step four: and (3) conveying the gas-liquid mixed product into a condenser for cooling for 8min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 4min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
Further, in the above technical scheme, the auxiliary agent is aluminum powder.
Further, in the above technical solution, the solvent is methanol or ethanol.
Further, in the above technical solution, the salt solution is prepared by platinum nitrate and ammonium water according to a ratio of 1: 1.5.
Further, in the above technical scheme, the process conditions of the hydrogenation reaction of bisphenol a are that the reaction temperature is 140 ℃, the reaction pressure is 8MPa, the feed concentration is 20%, the liquid space velocity is 1.5h-1, and the molar ratio of hydrogen to BPA is 35.
Further, in the above technical solution, the mass ratio of the bisphenol a to the noble metal supported catalyst is 200: 3.
Compared with the examples 1-3, the mass content of the catalyst Pt in the example is moderate, the mass content of the auxiliary agent is moderate, the reaction process is controllable, the catalyst dosage content is the lowest 0.8%, and the conversion rate is the highest 97.1%.
Example 5:
the invention provides a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane, which comprises the following specific operation steps:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: the catalyst comprises 50% of Pt, 0.5% of auxiliary agent and the balance of a catalyst carrier, wherein the catalyst carrier is alumina;
step three: soaking an alumina carrier in a salt solution for 4 hours at 70 ℃, then drying at 450 ℃, soaking an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 3 hours, and then drying at 450 ℃;
step four: and (3) conveying the gas-liquid mixed product into a condenser for cooling for 8min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 4min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
Further, in the above technical scheme, the auxiliary agent is aluminum powder.
Further, in the above technical solution, the solvent is methanol or ethanol.
Further, in the above technical solution, the salt solution is prepared by platinum nitrate and ammonium water according to a ratio of 1: 1.5.
Further, in the above technical scheme, the process conditions of the hydrogenation reaction of bisphenol a are that the reaction temperature is 140 ℃, the reaction pressure is 8MPa, the feed concentration is 20%, the liquid space velocity is 1.5h-1, and the molar ratio of hydrogen to BPA is 35.
Further, in the above technical solution, the mass ratio of the bisphenol a to the noble metal supported catalyst is 200: 3.
Compared with the examples 1 to 4, in the example, the mass content of the catalyst Pt is relatively high, the mass content proportion of the auxiliary agent is moderate, the reaction process is controllable, the dosage content of the catalyst is 1.1%, and the conversion rate is 96.7.
Example 6:
the invention provides a preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane, which comprises the following specific operation steps:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: the catalyst comprises 50% of Pt, 1% of auxiliary agent and the balance of catalyst carrier, wherein the catalyst carrier is alumina;
step three: soaking an alumina carrier in a salt solution for 4 hours at 70 ℃, then drying at 450 ℃, soaking an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 3 hours, and then drying at 450 ℃;
step four: and (3) conveying the gas-liquid mixed product into a condenser for cooling for 8min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 4min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
Further, in the above technical scheme, the auxiliary agent is aluminum powder.
Further, in the above technical solution, the solvent is methanol or ethanol.
Further, in the above technical solution, the salt solution is prepared by platinum nitrate and ammonium water according to a ratio of 1: 1.5.
Further, in the above technical scheme, the process conditions of the hydrogenation reaction of bisphenol a are that the reaction temperature is 140 ℃, the reaction pressure is 8MPa, the feed concentration is 20%, the liquid space velocity is 1.5h-1, and the molar ratio of hydrogen to BPA is 35.
Further, in the technical scheme, the mass ratio of the bisphenol A to the noble metal supported catalyst is 200:3
Compared with the examples 1-5, in the example, the mass content of the catalyst Pt is more, the mass content proportion of the auxiliary agent is moderate, the reaction process is controllable, the catalyst dosage content is 1.3%, and the conversion rate is 96.2%.
The following table is derived from examples 1 to 6:
as can be seen from the above table, in example 4, the mass content of the catalyst Pt is moderate, the mass content of the auxiliary agent is moderate, the reaction process is controllable, the continuous preparation of 2,2' -bis (4-hydroxycyclohexyl) propane can be realized, the catalyst dosage content reaches the lowest 0.8%, and the conversion rate reaches the highest 97.1%.
While certain exemplary embodiments of the present invention have been described above by way of illustration only, it will be apparent to those of ordinary skill in the art that the described embodiments may be modified in various different ways without departing from the spirit and scope of the invention. Therefore, the above description is illustrative in nature and should not be construed as limiting the scope of the invention, which is defined by the appended claims, and any modifications, equivalents, improvements and the like, which come within the spirit and scope of the invention are intended to be embraced therein.
Claims (6)
1. A preparation method of 2,2' -bis (4-hydroxycyclohexyl) propane is characterized by comprising the following steps: the specific operation steps are as follows:
the method comprises the following steps: metering and pressurizing the prepared bisphenol A raw material solution by a metering pump, fully mixing the bisphenol A raw material solution with hydrogen, and preheating the mixture by a reactor;
step two: adding a noble metal supported catalyst and a solvent in sequence for hydrogenation reaction, wherein the noble metal supported catalyst comprises the following components: the catalyst comprises 20-50% by mass of Pt, 0.5-1% by mass of an auxiliary agent and the balance of a catalyst carrier, wherein the catalyst carrier is alumina;
step three: immersing an alumina carrier into a salt solution, immersing for 3-5 h at 60-80 ℃, then drying at 300-600 ℃, immersing an equivalent amount of an auxiliary agent solution on the dried alumina carrier for 2-4 h, and then drying at 400-500 ℃;
step four: and conveying the gas-liquid mixed product into a condenser for cooling for 5-10 min, conveying the cooled gas-liquid mixed product into a high-pressure buffer tank for buffering for 3-5 min, conveying the gas-liquid mixed product into high-pressure gas-liquid separation equipment for gas-liquid separation, metering and discharging the gas through a flowmeter, and discharging the 2,2' -bis (4-hydroxycyclohexyl) propane mixed product from a discharge hole of the high-pressure gas-liquid separation equipment.
2. The process according to claim 1, wherein the reaction mixture comprises at least one of the following components: the auxiliary agent is aluminum powder.
3. The process according to claim 1, wherein the reaction mixture comprises at least one of the following components: the solvent is methanol or ethanol.
4. The process according to claim 1, wherein the reaction mixture comprises at least one of the following components: the salt solution is prepared by platinum nitrate and ammonium water according to the proportion of 1: 1.5.
5. The process according to claim 1, wherein the reaction mixture comprises at least one of the following components: the technological conditions of the hydrogenation reaction of the bisphenol A are that the reaction temperature is 100-180 ℃, the reaction pressure is 5-10 MPa, the feeding concentration is 15-30%, the liquid space velocity is 1-3 h < -1 >, and the molar ratio of hydrogen to BPA is 18-46.
6. The process according to claim 1, wherein the reaction mixture comprises at least one of the following components: the mass ratio of the bisphenol A to the noble metal supported catalyst is 200: 3.
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| JP2023073943A (en) * | 2021-11-16 | 2023-05-26 | 中國石油化學工業開發股▲分▼有限公司 | Method for preparing 2,2-bis(4-hydroxycyclohexyl)propane |
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