CN107954832B - Preparation method of hydrogenated bisphenol A - Google Patents
Preparation method of hydrogenated bisphenol A Download PDFInfo
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- CN107954832B CN107954832B CN201711114635.4A CN201711114635A CN107954832B CN 107954832 B CN107954832 B CN 107954832B CN 201711114635 A CN201711114635 A CN 201711114635A CN 107954832 B CN107954832 B CN 107954832B
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- bisphenol
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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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- 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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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of hydrogenated bisphenol A, wherein the temperature of bisphenol A is 100-200 ℃, the hydrogen pressure is 3-5 MPa,The dioxane is used as a solvent and is hydrogenated in the presence of a graphene supported ruthenium catalyst to generate the hydrogenated bisphenol A, and the reaction equation is as follows:
Description
Technical Field
The invention relates to the field of organic matter hydrogenation, in particular to a preparation method of hydrogenated bisphenol A.
Background
Hydrogenated bisphenol A (HBPA) with the chemical name of 2, 2-bis (4-hydroxycyclohexyl) propane, the structural formula of which is shown as formula (2), and saturated alicyclic dihydric alcohol obtained by hydrogenating two benzene rings in bisphenol A molecules with the structure shown as formula (1). Compared with bisphenol A, hydrogenated bisphenol A has higher thermal stability, chemical stability and weather resistance, is more suitable for outdoor engineering, and is more beneficial to the health of human bodies. At present, the product is mainly used for manufacturing polycarbonate, epoxy resin, polyacrylic resin and the like, and can also be used for producing fine chemical products such as rubber anti-aging agents, plasticizers, flame retardants, antioxidants, coatings and the like.
Hydrogenated bisphenol A is obtained by using bisphenol A as a raw material and hydrogenating under the catalytic action of a catalyst. The preparation of hydrogenated bisphenol a is similar to the hydrogenation of benzene rings and the key to its preparation lies in the choice of hydrogenation catalyst. The catalyst used in industrial production of benzene ring catalytic hydrogenation reaction mostly uses metal catalyst as catalytic active component, mainly contains metals of Ni, Pt, Pd, Ru and Rh, etc.
The pioneer of the bisphenol a catalytic hydrogenation process, Terada, proposed the use of metallic nickel as a catalyst for catalytic hydrogenation and proposed the relevant catalytic mechanism. Patent CN1375484 uses silica as carrier and supported metal ruthenium as active component to carry out hydrogenation reaction of bisphenol a. However, the catalyst has high acidity of the carrier, which can cause dehydroxylation of the product and affect the selectivity of the product. The active component of the catalyst used in patent US 6255530 is colloid of metallic Pd, Ni, and the hydrogenated bisphenol a is prepared batchwise by means of an autoclave. The catalyst is not suitable for industrial production because of complex preparation. The catalyst for preparing hydrogenated bisphenol A reported in patent CN102921440A of Wangchun is prepared by loading noble metals such as Ru, Rh and the like on modified compound alumina, taking isopropanol as a solvent at the reaction temperature of 165-170 ℃ and the pressure of 7.8MPa, and adopting a fixed bed continuous hydrogenation process flow. The corresponding suitable temperature and pressure of the catalyst are limited.
Tomohiro Maegawa et al explored Rh/C, Ru/C catalysts for the catalytic hydrogenation of different aromatic ring hydrocarbons under mild conditions. For the preparation of hydrogenated bisphenol A, the catalytic hydrogenation reaction is completed in isopropanol solution at 60 ℃ for 7h by adopting the reaction of a catalyst Rh/C under the condition that the hydrogen pressure is 5 MPa; and the catalytic hydrogenation reaction of bisphenol A is completed by using a catalyst Ru/C for 12h under the pressure of 10 MPa. Therefore, the conclusion is drawn that the catalytic effect of Rh is stronger than that of Ru under the condition, but the price of Rh is much higher than that of Ru, so that the Ru catalyst with good catalytic effect is prepared according to the economic principle of industrial production, and is more suitable for industrial production. Patent CN 104220404a relates to a purification process of bisphenol compounds after hydrogenation, which uses aromatic hydrocarbon as poor solvent to wash, separate and recover the product after catalytic hydrogenation of bisphenol compounds, and the purity is as high as 95-100%.
The bisphenol A hydrogenation catalyst provided by the method has high cost, or the conversion rate of raw materials and the selectivity and purity of products cannot be considered when the catalyst catalyzes the hydrogenation of bisphenol A. In addition, the prior art has conducted only simple vacuum concentration of the hydrogenated bisphenol a obtained after catalytic hydrogenation or washing and purification thereof with aromatic hydrocarbons, resulting in limitation of the purity of the hydrogenated bisphenol a or excessive loss of the product in the purification step. Accordingly, there is a need in the art to develop a bisphenol a hydrogenation process with better overall results in terms of conversion, selectivity, and purity, and a catalyst for bisphenol a hydrogenation that is inexpensive and readily available.
In view of the above, patent CN 106083529 a discloses a method for preparing hydrogenated bisphenol a and a catalyst for bisphenol a hydrogenation, the method comprises hydrogenating bisphenol a at 50-100 ℃, 5-10 MPa hydrogen pressure, isopropanol as solvent and in the presence of ruthenium catalyst to obtain the hydrogenated bisphenol a, wherein the ruthenium catalyst is Ru-Zn-Ni/TiO2CdO catalysts, i.e. ruthenium catalysts in which zinc and nickel are co-active componentsTitanium dioxide and cadmium oxide are used as composite carriers; the conversion rate of the bisphenol A in the invention can reach 100%, the selectivity of the hydrogenated bisphenol A can be more than 97%, and the purity of the hydrogenated bisphenol A can be more than 99.5%. During the preparation process, the selection of the catalyst is crucial to the selectivity of bisphenol A.
Therefore, there is a need to find a suitable catalyst to further increase the selectivity of hydrogenated bisphenol a.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of hydrogenated bisphenol A, and the selectivity of hydrogenated bisphenol A is further improved by selecting a proper catalyst graphene supported ruthenium catalyst.
In order to solve the technical problems, the technical scheme of the invention is as follows: the preparation method of hydrogenated bisphenol A has the innovation points that: hydrogenating bisphenol A at the temperature of 100-200 ℃, the hydrogen pressure of 3-5 MPa, dioxane as a solvent and the presence of a graphene supported ruthenium catalyst to generate hydrogenated bisphenol A, wherein the reaction equation is as follows:
furthermore, the loading amount of ruthenium in the graphene-loaded ruthenium catalyst is 0.5-1.5 wt%.
Furthermore, the dosage of the dioxane is two milliliters of dioxane added into each gram of bisphenol A, and the mass ratio of the bisphenol A to the graphene supported ruthenium catalyst is 100: 1.
The invention has the advantages that: according to the invention, the graphene-supported ruthenium catalyst is selected, so that the catalytic efficiency is high, the dosage of the catalyst is greatly reduced, the conversion rate of bisphenol A can reach 100%, the selectivity of hydrogenated bisphenol A can be more than 99%, and the purity of hydrogenated bisphenol A can be more than 99.5%.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
Example 1
Adding 150 g of bisphenol A into A1L high-pressure kettle, adding 300ml of dioxane and 1.5 g of graphene-supported ruthenium catalyst, wherein the content of ruthenium is 0.5 wt%, charging 5 kg of nitrogen, discharging gas under the pressure of 5 kg, charging 5 kg of hydrogen, discharging gas for three times, then hydrogenating at 100 ℃ and 3MPa until hydrogen is not absorbed, cooling, discharging, performing suction filtration, washing dioxane, and recovering the solvent to obtain the product, wherein the conversion rate is 100%, the selectivity is 99.3%, and the purity is 99.6%.
Example 2
Adding 150 g of bisphenol A into A1L high-pressure kettle, adding 300ml of dioxane and 1.5 g of graphene-supported ruthenium catalyst, wherein the content of ruthenium is 1.5 wt%, charging 5 kg of nitrogen, discharging gas under the pressure of 5 kg, charging 5 kg of hydrogen, discharging gas for three times, then hydrogenating at 200 ℃ and 5MPa until hydrogen is not absorbed, cooling, discharging, performing suction filtration, washing dioxane, and recovering the solvent to obtain the product, wherein the conversion rate is 100%, the selectivity is 99.2%, and the purity is 99.5%.
Example 3
Adding 150 g of bisphenol A into A1L high-pressure kettle, adding 300ml of dioxane and 1.5 g of graphene-supported ruthenium catalyst, wherein the content of ruthenium is 1 wt%, charging 5 kg of nitrogen, discharging gas under the pressure of 5 kg, charging 5 kg of hydrogen, discharging gas for three times, then hydrogenating at 150 ℃ and 4MPa until hydrogen is not absorbed, cooling, discharging, performing suction filtration, washing the dioxane, and recovering the solvent to obtain the product, wherein the conversion rate is 100%, the selectivity is 99.5%, and the purity is 99.7%.
It can be seen from the above examples that the conversion rate of bisphenol a can reach 100%, the selectivity of hydrogenated bisphenol a can be greater than 99%, and the purity of hydrogenated bisphenol a can be more than 99.5% by the catalysis of the graphene supported ruthenium catalyst of the present invention; in addition, comparing examples 1 to 3 with each other, the catalytic effect of example 3 is the best, and thus the loading amount of ruthenium in the graphene supported ruthenium catalyst is the best 1 wt%, the best reaction temperature is 150 ℃, and the hydrogen pressure is 4 MPa.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (1)
1. A process for producing hydrogenated bisphenol A, characterized by comprising: adding 150 g of bisphenol A into A1L high-pressure kettle, adding 300ml of dioxane and 1.5 g of graphene-supported ruthenium catalyst, wherein the content of ruthenium is 0.5 wt%, charging 5 kg of nitrogen, discharging gas under the pressure of 5 kg, charging 5 kg of hydrogen, discharging gas for three times, then hydrogenating at 100 ℃ and 3MPa until hydrogen is not absorbed, cooling, discharging, performing suction filtration, washing dioxane, and recovering the solvent to obtain the product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113336623B (en) * | 2020-03-03 | 2023-05-30 | 台湾中油股份有限公司 | Method for producing dihydric alcohol containing dicycloaliphatic |
| CN111454124A (en) * | 2020-05-13 | 2020-07-28 | 惠泽化学科技(濮阳)有限公司 | Method for preparing hydrogenated bisphenol AF through catalytic hydrogenation |
| CN113045384B (en) * | 2020-11-24 | 2023-01-13 | 上海徽迪皓新材料科技有限公司 | Continuous preparation method of hydrogenated bisphenol A |
| CN113117743B (en) * | 2021-04-06 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method of hydrogenation catalyst and method for preparing hydrogenated bisphenol A |
| CN115197048B (en) * | 2021-04-12 | 2023-08-11 | 万华化学集团股份有限公司 | Preparation method of hydrogenated bisphenol A |
| CN116023234B (en) * | 2022-09-14 | 2024-05-17 | 中国石油集团工程股份有限公司 | Continuous production process of hydrogenated bisphenol A |
| CN115739116B (en) * | 2022-11-29 | 2024-06-21 | 本源精化环保科技有限公司 | Catalyst, preparation and regeneration method thereof and hydrogenated bisphenol A production method |
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| JPS53119855A (en) * | 1977-03-29 | 1978-10-19 | Takeda Chem Ind Ltd | Preparation of 4,4'-isopropylydenedicyclohexanol |
| CN102211979A (en) * | 2010-04-02 | 2011-10-12 | 盘锦和运新材料有限公司 | Method for preparing 2,2-bis(4-hydroxy cyclohexyl) propane |
| CN102921440A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Catalyst for preparation of hydrogenated bisphenol A |
| DE102015219729A1 (en) * | 2014-10-16 | 2016-04-21 | Basf Se | Process for the hydrogenation of dihydroxydiphenylalkanes |
| CN104815650B (en) * | 2015-04-17 | 2017-03-22 | 郑州大学 | Preparation method and application of graphene loaded Ru catalyst |
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