CN107954832A - A kind of preparation method of hydrogenated bisphenol A - Google Patents
A kind of preparation method of hydrogenated bisphenol A Download PDFInfo
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- CN107954832A CN107954832A CN201711114635.4A CN201711114635A CN107954832A CN 107954832 A CN107954832 A CN 107954832A CN 201711114635 A CN201711114635 A CN 201711114635A CN 107954832 A CN107954832 A CN 107954832A
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- bisphenol
- hydrogenated 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of hydrogenated bisphenol A, for bisphenol-A temperature is 100~200 DEG C, hydrogen pressure is 3~5MPa, dioxane is that hydrogenation generates the hydrogenated bisphenol A in the presence of solvent and graphene-supported ruthenium catalyst, its reaction equation is as follows：
Description
Technical field
The present invention relates to organic matter field of hydrogenation, more particularly to a kind of preparation method of hydrogenated bisphenol A.
Background technology
Hydrogenated bisphenol A (HBPA), chemical name 2, double (4- hydroxy-cyclohexyls) propane of 2-, its structural formula such as formula (2) institute
Show, be by two benzene ring hydrogenations obtain in the bisphenol-A molecule of structure as shown in formula (1) saturation cycloaliphatic diols.Compared with bisphenol-A
For, hydrogenated bisphenol A has higher heat endurance, chemical stability and against weather, more suitable for outdoor engineering, to human body
Health it is also more beneficial.At present, which also may be used mainly for the manufacture of makrolon, epoxy resin, polyacrylic resin etc.
For producing the fine chemical products such as rubber antioxidant, plasticizer, fire retardant, antioxidant, coating.
Hydrogenated bisphenol A is using bisphenol-A as raw material, is hydrogenated with and obtains under catalyst effect.The preparation class of hydrogenated bisphenol A
Benzene ring hydrogenation is similar to, its key prepared is the selection of hydrogenation catalyst.Phenyl ring catalytic hydrogenation reaction institute in the industrial production
The catalyst used is more using metallic catalyst as catalytic active component, mainly there is the metals such as Ni, Pt, Pd, Ru, Rh.
The pioneer Terada of bisphenol-A catalytic hydrogenation process proposes the catalyst by the use of metallic nickel as catalytic hydrogenation, and
Propose relevant catalytic mechanism.Patent CN1375484 uses silica as carrier, supported metal ruthenium as active component into
The hydrogenation reaction of row bisphenol-A.But the acidity of carrier is higher in the catalyst, can cause the decarboxylation reaction of product, influence product
Selectivity.The active component of catalyst used in patent US 6255530 is metal Pd, the colloid of Ni, using autoclave
Interval prepares hydrogenated bisphenol A.Because its catalyst preparation is more complicated, industrial production is unsuitable for.Wang Kailin is in patent
The catalyst for preparing hydrogenated bisphenol A reported in CN102921440A is the noble-metal-supporteds such as Ru, Rh in the modified oxidation of compounding three
On two aluminium, 165~170 DEG C of reaction temperature, pressure 7.8MPa, using isopropanol as solvent, using fixed bed continuously hydrogen adding technique stream
Journey.The corresponding preference temperature of the catalyst and pressure are restricted.
Tomohiro Maegawa et al. have probed into Rh/C, Ru/C catalyst in a mild condition to different kinds of aromatic ring hydrocarbon respectively
Catalytic hydrogenation process.Preparation for hydrogenated bisphenol A, all in aqueous isopropanol, temperature is 60 DEG C, using catalyst Rh/C's
Reaction, under the conditions of Hydrogen Vapor Pressure is 5MPa, 7h completes catalytic hydrogenation reaction；And with catalyst Ru/C, under pressure 10MPa,
12h completes the catalytic hydrogenation reaction of bisphenol-A.It follows that the catalytic effect of Rh is better than Ru, but the valency of Rh on this condition
Lattice are far above Ru, with regard to industrial economy principle, prepare the Ru catalyst of excellent catalytic effect, are more suitable for industrial life
Production.Purifying process after bisphenol compound hydrogenation involved in patent CN 104220404A, the patent is by the use of as bad molten
The aromatic hydrocarbon of agent cleans the product after compound bisphenol catalytic hydrogenation and is separated, recycled, and high purity 95%~
100%.
The bisphenol-A hydrogenation catalyst cost provided in the above method is excessive, or raw material during the hydrogenation of catalyst bisphenol-A
Conversion ratio and product selectivity and purity in terms of cannot take into account.In addition, in the prior art to gained after catalytic hydrogenation
Hydrogenated bisphenol A is only simply concentrated in vacuo, or it is cleaned and is purified using aromatic hydrocarbon, causes hydrogenated bisphenol A
Limited purity or purification step in product loss amount it is excessive.Therefore, this area need to develop a kind of conversion ratio, selectivity and
The general effect of purity more preferably bisphenol-A method of hydrotreating and a kind of bisphenol-A catalyst for hydrogenation cheap and easy to get.
For above-mentioned phenomenon, 106083529 A of patent CN disclose a kind of preparation method of hydrogenated bisphenol A and bisphenol-A adds
Catalyst for hydrogen, the preparation method include bisphenol-A temperature be 50~100 DEG C, hydrogen pressure is 5~10MPa, isopropanol is solvent
The hydrogenated bisphenol A is generated with hydrogenation in the presence of ruthenium catalyst, wherein the ruthenium catalyst is Ru-Zn-Ni/TiO2- CdO is catalyzed
Agent, i.e., using zinc and nickel as active component is helped in described ruthenium catalyst, using titanium dioxide and cadmium oxide as complex carrier；In the present invention
The conversion ratio of bisphenol-A is up to 100%, while the selectivity of hydrogenated bisphenol A can be more than 97%, and the purity of hydrogenated bisphenol A can be
More than 99.5%.In preparation process, the selection of catalyst is most important to the selectivity of bisphenol-A.
Therefore, there is an urgent need for seek a kind of suitable catalyst to further improve the selectivity of hydrogenated bisphenol A.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of hydrogenated bisphenol A, is suitably urged by selecting
The graphene-supported ruthenium catalyst of agent, to further improve the selectivity of hydrogenated bisphenol A.
In order to solve the above technical problems, the technical scheme is that：A kind of preparation method of hydrogenated bisphenol A, it is innovated
Point is：Bisphenol-A temperature is 100~200 DEG C, hydrogen pressure is 3~5MPa, dioxane be solvent and graphene-supported ruthenium catalysis
Hydrogenation generates the hydrogenated bisphenol A in the presence of agent, its reaction equation is as follows：
Further, the load capacity of ruthenium is 0.5~1.5wt% in the graphene-supported ruthenium catalyst.
Further, the dosage of the dioxane adds two milliliters of dioxane, bisphenol-A and graphite for every gram of bisphenol-A
The mass ratio of alkene supported ruthenium catalyst is 100:1.
The advantage of the invention is that：In the present invention, by selecting graphene-supported ruthenium catalyst, high catalytic efficiency, significantly
Reduce the dosage of catalyst, while the conversion ratio of bisphenol-A can be made up to 100%, while the selectivity of hydrogenated bisphenol A can be more than
99%, and the purity of hydrogenated bisphenol A can be more than 99.5%.
Embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among the embodiment described scope.
Embodiment 1
Take 150 grams of bisphenol-A to be added in 1L autoclaves, add dioxane 300ml and graphene-supported ruthenium catalyst
1.5 grams, ruthenium content 0.5wt%, 5 kilograms of pressure exhausts of gas are flushed with hydrogen again three times after 5 kilograms of pressure exhausts of inflated with nitrogen, Ran Houyu
100 DEG C, it is hydrogenated with the conditions of 3MPa, untill hydrogen is not inhaled, cooling, discharge, filters, and dioxane washing, recycling design, must produce
Product, conversion ratio 100%, selectivity 99.3%, purity 99.6%.
Embodiment 2
Take 150 grams of bisphenol-A to be added in 1L autoclaves, add dioxane 300ml and graphene-supported ruthenium catalyst
1.5 grams, ruthenium content 1.5wt%, 5 kilograms of pressure exhausts of gas are flushed with hydrogen again three times after 5 kilograms of pressure exhausts of inflated with nitrogen, Ran Houyu
200 DEG C, it is hydrogenated with the conditions of 5MPa, untill hydrogen is not inhaled, cooling, discharge, filters, and dioxane washing, recycling design, must produce
Product, conversion ratio 100%, selectivity 99.2%, purity 99.5%.
Embodiment 3
Take 150 grams of bisphenol-A to be added in 1L autoclaves, add dioxane 300ml and graphene-supported ruthenium catalyst
1.5 grams, ruthenium content 1wt%, 5 kilograms of pressure exhausts of gas are flushed with hydrogen again three times after 5 kilograms of pressure exhausts of inflated with nitrogen, then in 150
DEG C, it is hydrogenated with the conditions of 4MPa, untill hydrogen is not inhaled, cooling, discharge, filters, and dioxane washing, recycling design, obtains product, turns
Rate 100%, selectivity 99.5%, purity 99.7%.
As can be seen from the above-described embodiment, by the catalysis of the graphene-supported ruthenium catalyst of the present invention, turning for bisphenol-A can be made
Rate is up to 100%, while the selectivity of hydrogenated bisphenol A can be more than 99%, and the purity of hydrogenated bisphenol A can be more than 99.5%；
In addition, embodiment 1-3 is compared to each other, the catalytic effect of embodiment 3 is optimal, thus in graphene-supported ruthenium catalyst ruthenium it is negative
Carrying capacity most preferably 1wt%, optimal reaction temperature is 150 DEG C, hydrogen pressure is 4MPa.
The basic principle and main feature and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (3)
- A kind of 1. preparation method of hydrogenated bisphenol A, it is characterised in that：Bisphenol-A temperature be 100~200 DEG C, hydrogen pressure be 3~ 5MPa, dioxane generate the hydrogenated bisphenol A, its reactional equation for hydrogenation in the presence of solvent and graphene-supported ruthenium catalyst Formula is as follows：
- 2. the preparation method of hydrogenated bisphenol A according to claim 1, it is characterised in that：The graphene-supported ruthenium catalysis The load capacity of ruthenium is 0.5~1.5wt% in agent.
- 3. the preparation method of hydrogenated bisphenol A according to claim 1, it is characterised in that：The dosage of the dioxane is The mass ratio of every gram of bisphenol-A two milliliters of dioxane of addition, bisphenol-A and graphene-supported ruthenium catalyst is 100:1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113045384A (en) * | 2020-11-24 | 2021-06-29 | 普氢(上海)新材料科技有限公司 | Continuous preparation method of hydrogenated bisphenol A |
| CN113117743A (en) * | 2021-04-06 | 2021-07-16 | 万华化学集团股份有限公司 | Preparation method of hydrogenation catalyst and method for preparing hydrogenated bisphenol A |
| CN113336623A (en) * | 2020-03-03 | 2021-09-03 | 台湾中油股份有限公司 | Process for producing diol containing double alicyclic group |
| CN115197048A (en) * | 2021-04-12 | 2022-10-18 | 万华化学集团股份有限公司 | Preparation method of hydrogenated bisphenol A |
| CN116023234A (en) * | 2022-09-14 | 2023-04-28 | 中国石油集团工程股份有限公司 | Continuous production process 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 |
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| 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 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336623A (en) * | 2020-03-03 | 2021-09-03 | 台湾中油股份有限公司 | Process for producing diol containing double alicyclic group |
| CN113336623B (en) * | 2020-03-03 | 2023-05-30 | 台湾中油股份有限公司 | Process for producing dialiphatic diol |
| 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 |
| CN113045384A (en) * | 2020-11-24 | 2021-06-29 | 普氢(上海)新材料科技有限公司 | Continuous preparation method of hydrogenated bisphenol A |
| CN113117743A (en) * | 2021-04-06 | 2021-07-16 | 万华化学集团股份有限公司 | Preparation method of hydrogenation catalyst and method for preparing hydrogenated bisphenol A |
| CN115197048A (en) * | 2021-04-12 | 2022-10-18 | 万华化学集团股份有限公司 | Preparation method of 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 |
| CN116023234A (en) * | 2022-09-14 | 2023-04-28 | 中国石油集团工程股份有限公司 | Continuous production process 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 |
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