CN102921440A - Catalyst for preparation of hydrogenated bisphenol A - Google Patents
Catalyst for preparation of hydrogenated bisphenol A Download PDFInfo
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- CN102921440A CN102921440A CN2012104189278A CN201210418927A CN102921440A CN 102921440 A CN102921440 A CN 102921440A CN 2012104189278 A CN2012104189278 A CN 2012104189278A CN 201210418927 A CN201210418927 A CN 201210418927A CN 102921440 A CN102921440 A CN 102921440A
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Abstract
The invention relates to a catalyst for preparation of hydrogenated bisphenol A. The catalyst comprises: by mass, 100 parts of modified compound alumina carriers and 1 to 3 parts of precious metals as active ingredients. The modified compound alumina carriers comprise: by mass, 30 to 80 parts of pseudo-boehmite, 10 to 40 parts of aluminum hydroxide, 1 to 5 parts of an alkali metal and 1 to 5 parts of phosphorus. The active ingredients comprise two of Pd, Ru and Rh. The modified compound alumina carriers are adopted and are loaded with multiple precious metals to form the catalyst which is a hydrogenation catalyst having high activity, high selectivity and high loading capacity. The catalyst can realize preparation of a high trans-form/trans-form ratio isomer product under the condition of a trace amount of a stabilizer.
Description
Technical field
The present invention relates to the catalyst that the bisphenol-A catalytic hydrogenation prepares hydrogenated bisphenol A, hydrogenated bisphenol A is to be prepared by hydrogenation reaction by bisphenol-A, under certain temperature, Hydrogen Vapor Pressure and catalyst action, after two phenyl ring in the bisphenol-A molecule are carried out saturated hydrogenation, a kind of alicyclic dihydroxylic alcohols that obtains is widely used as fine-chemical intermediate.Prepared catalyst is applicable to the catalytic hydrogenation process of bisphenol-A in the invention, has high load capacity, high selectivity, long-life characteristics, cooperates micro-stabilizing agent in the reaction system, can improve anti-/ trans-isomer content in the product.
Background technology
Hydrogenated bisphenol A (being called for short HBPA) mainly for the manufacture of epoxy resin, unsaturated-resin, Merlon, polyacrylic resin, has the advantages such as heat endurance, chemical stability and weatherability, and application is extensive.Especially at opoxy resin, studies show that, the epoxy-resin systems that does not contain two keys in the molecule segment is more superior than the bisphenol A type epoxy resin weather resistance that contains pair keys, and the performance of improving epoxy resin with hydrogenated bisphenol A becomes the important means of epoxy resin modification.
The preparation of hydrogenated bisphenol A is take bisphenol-A as raw material, carries out hydrogenation reaction under the solution state and generate under the effect of catalyst.The preparation of hydrogenated bisphenol A belongs to the aromatic compound hydrogenation, the category that belongs to benzene ring hydrogenation, its key problem in technology is the selection of activity of hydrocatalyst component and carrier, the material that in theory benzene ring hydrogenation is played catalytic action can be applied to the hydrogenation process of bisphenol-A, characteristics for the bisphenol-A molecular structure, for reaching high activity and high selectivity, will be allowed a choice to active component and carrier.Development through decades, the bisphenol-A hydrogenation mainly contains following three class catalyst, metallic framework type catalyst, noble metal carrier catalyst and homogeneous catalyst, general reaction condition is 50 ~ 250 ℃, Hydrogen Vapor Pressure 1 ~ 30MPa, can adopt intermittence or continously hydrogen adding technological process, product uses rectification under vacuum or recrystallizing technology to carry out separating-purifying.
US Patent No. 2927127 reports were just arranged as far back as the fifties in last century, adopt silica to do carrier in CN 1375484 patents, supported metal ruthenium carries out the hydrogenation reaction of bisphenol-A as active component, but the acidity of carrier is higher, the decarboxylation reaction that can cause product affects the selective of product; Use with nickel-base catalyst and metal oxide the standby hydrogenated bisphenol A of Hydrogenation among JP 2003002853, JP 06128182 and the JP 06329569; Adopt SiO among the WO 2005061106
2Load Ru catalyst carries out the catalytic hydrogenation of bisphenol-A; JP 6279339 adopts Raney nickel, carries out the catalytic hydrogenation of bisphenol-A in representative examples of saturated aliphatic alcohol; JP 2000044503 adopts the catalytic hydrogenation that carries out bisphenol-A under the Ru/ alumina catalyzation in ethylene glycol.US 4001343, US 4271323 and US 4192960 adopts transition organic metal homogeneous catalysts, and course of reaction is to carry out catalytic hydrogenation reaction to prepare hydrogenated bisphenol A in the presence of water and ethanol, increased the separation circuit of catalyst after the reaction; And for example use a kind of active Pd, Ni colloid type catalyst among the patent US6255530, prepare hydrogenated bisphenol A in the autoclave discontinuous, although reactant mixture is easy to separate, the catalyst preparation is complicated, industrial applicability inconvenience.
From existing bisphenol-A hydrogen addition technology, present load type catalyst carrier mainly is aluminium oxide, silica or diatomite, all has higher surface acidity, has increased the weight of the generation of dehydration accessory substance; And metallic framework type catalyst activity is lower, loads low; Inconvenience is used in the homogeneous catalyst preparation, is not suitable for commercial Application.The technology point that the application will solve is to improve catalyst activity, and under the catalyst high load capacity, introduces stabilizing agent in the course of reaction, when keeping high selectivity, obtains the hydrogenated bisphenol A mix products of high trans isomer proportion.
Hydrogenated bisphenol A anti-/ transisomer particularly, more valuable in application, it can produce cooperative effect and better mechanical performance in polymer, such as the softening point of raising polymer.But in the current production technology, anti-/ transisomer ratio is usually 30～45%, for obtaining more at high proportion, generally need to carry out subsequent treatment, in patent US4487979, use chlorine-containing organic compounds to be recrystallized as solvent, just can obtain the product of high trans isomer proportion.Catalyst among the present invention cooperates stabilizing agent, can obtain anti-high/transisomer ratio mixture through disposable hydrogenation reaction.
Summary of the invention
Adopt conventional method to prepare the composite alumina support of macropore, carry out the multicomponent noble-metal-supported, use fixed-bed reactor and carry out the reaction of bisphenol-A continuous catalytic hydrogenation.The present invention is by composite modified to carrier, reduced carrier surface acid, improved catalyst activity and selectivity, simultaneously in use by adding minor amount of water as stabilizing agent, prolonged the life-span of catalyst, this catalyst has the characteristics of high load capacity, high selectivity, uses this catalyst can obtain the mixture of the hydrogenated bisphenol A of high trans ratio.
The applicant has prepared a kind of catalyst of bisphenol-A continuous catalytic hydrogenation reaction by a large amount of experimental studies, on the basis of this catalyst, has found more stable process conditions.Technical method of the present invention is as follows:
A kind of catalyst for the preparation of hydrogenated bisphenol A, its component and mass fraction are:
100 parts of the composite alumina supports of modification,
1～3 part of the noble metal of active component;
Wherein: the composite alumina support of modification is comprised of 30～80 mass parts boehmites, 10～40 mass parts aluminium hydroxides, 1～5 mass parts alkali metal, 1～5 mass parts P elements; Described active component is multicomponent, is selected from two kinds among Pd, Ru, the Rh.
Described catalyst alkali metal is selected from a kind of in the nitrate of Na, K, Mg or Ca.Described phosphorus is selected from phosphoric acid or phosphorous acid.
The amount of described Pd is 0.5～2.0% (wt%) with respect to carrier.The amount of described Ru is 0.5～2.0% (wt%) with respect to carrier.The amount of described Rh is 0.1～1.0% (wt%) with respect to carrier.(take carrier as 100%)
Hydrogenation catalyst of the present invention in catalyst, adds minor amount of water as stabilizing agent during for the preparation of hydrogenated bisphenol A.
The content of described stabilizing agent water in reaction system is preferred 300～500ppm.
When hydrogenation catalyst uses, product be characterised in that in the product composition hydrogenated bisphenol A anti-/ the transisomer ratio is greater than 55%.
The inventor adopts the fixed bed hydrogenation technological process, finds by great many of experiments, uses the catalyst of said method preparation, after simultaneously adding micro-stabilizing agent water in the reaction system, the activity that can keep catalyst improves anti-/ transisomer product, has prolonged the service life of catalyst.By following examples, the catalyst among the present invention is described.
Description of drawings
Fig. 1: product gas chromatographic analysis collection of illustrative plates;
Fig. 2: raw material adds hydrogenation reaction conversion ratio and the selective experimental data figure of 350ppm minor amount of water;
Fig. 3: raw material does not add hydrogenation reaction conversion ratio and the selective experimental data of minor amount of water.
The specific embodiment
Being prepared as follows of composite carrier:
Get commercially available boehmite, aluminium hydroxide powder and be mixed into by a certain percentage uniform powder, take by weighing quantitative rare nitric acid, phosphoric acid and alkali nitrates and be mixed with the aqueous solution, solution with preparation in kneader evenly is sprayed in the powder, behind the aging certain hour, extrusion molding on double screw extruder, dry rear roasting under the pre-set programs temperature control obtains the composite aluminium oxide of strip, crushing screening is got certain granules degree carrier, the composite modified catalyst carrier that obtains using among the present invention.
The load of active component is as follows:
Adopt conventional dipping method to carry out the dip loading of active component, use the chloride mixed aqueous solution of palladium, ruthenium or the rhodium of metering concentration to flood catalyst carrier, under temperature programming control, carry out roasting after dry, reduction activation in reactor before the hydrogenation reaction obtains catalyst described in the present invention.
Can obtain the catalyst of following feature by above-mentioned preparation method, the composite alumina support specific area of modification 90～150m
2/ g, pore volume 0.4～0.6ml/g, the Surface L acid strength is 2～5mmol/g, the B acid strength is 0.1～0.5mmol/g, its mesoporous 60～200
Account for total pore volume more than 50%.The adding of aluminium hydroxide and phosphoric acid is favourable to the formation of secondary pore in the roasting process, and for composite carrier provides larger aperture size, the adding of alkali nitrates has reduced the surface acidity of carrier.The simultaneously application of bi-component active component has improved the anti-caking power of precious metal element crystallite under the hydrogenation conditions, and is provided longer hydrogenation service life.
Catalyst activity and life assessment method:
Bisphenol-A is dissolved in the isopropyl alcohol, forms the material solution of 20%～25%(wt) concentration.The catalyst of packing in the single tube fixed bed reactors, reduction activation under temperature programming in atmosphere of hydrogen passes into material solution and to carry out hydrogenation reaction in the reactor, reaction condition: pressure 7.8Mpa, 165 ℃ of bed temperatures, liquid air speed 6.6h through measuring pump
-1(V), hydrogen gas space velocity 450h
-1(V), after the hydrogenation mix products cooling, obtain containing the mix products of the hydrogenated bisphenol A of solvent, carry out gas chromatographic analysis.
Embodiment 1
Get commercially available boehmite, aluminium hydroxide powder and be mixed into by a certain percentage uniform powder, take by weighing 3% diluted nitric acid aqueous solution (wt%), 85% phosphate aqueous solution (wt%) and alkali metal sodium nitrate and be mixed with the aqueous solution, solution with preparation in kneader evenly is sprayed in the powder, behind the aging certain hour, extrusion molding on double screw extruder, 120 ℃ of dryings 12 hours, in 650 ℃ of roastings 6 hours, obtain the composite aluminium oxide of strip, crushing screening is got certain granules degree particle as carrier, carries out carrier and characterizes.Be prepared as follows 1～7 carrier according to different raw material proportionings:
The preparation and characterization of the composite alumina support of table one
From table one, can find out, carrier 1～5 is composite modified, alkali metallic sodium and P elements have been introduced, carrier 6, the 7th, unmodified conventional aluminium oxide, carrier after alkali metallic sodium and the P elements modification, the surface acidity of carrier descends, and has kept simultaneously the carrier after the roasting also to have larger pore volume, and such carrier is conducive to the carrying out of hydrogenation reaction.
Above-mentioned carrier is used for following examples, carries out the explanation of catalytic activity.
Embodiment 2
Press the powder formulation of carrier 5 in the table one and the carrier preparation method among the embodiment 1, respectively alkali metal is used instead 30g, 60g, 100g potassium nitrate, obtain following carrier 8a, 8b, 8c, specific area corresponds to 132.17m2/g, 128.60m2/g, 130.47m2/g, pore volume corresponds to 0.48ml/g, 0.51ml/g, 0.53ml/g, the L acid strength corresponds to 4.61mmo1/g, 3.52mmol/g, 3.19mmol/g, the B acid strength corresponds to 0.41mmol/g, 0.36mmol/g, 0.32mmol/g, is used for following examples.
Embodiment 3
Press the powder formulation of carrier 5 in the table one and the carrier preparation method among the embodiment 1, respectively alkali metal is used instead 70g, 120g, 200g magnesium nitrate, obtain following carrier 9a, 9b, 9c, specific area corresponds to 131.06m2/g, 135.44m2/g, 132.70m2/g, pore volume corresponds to 0.46ml/g, 0.47ml/g, 0.42ml/g, the L acid strength corresponds to 5.01mmo1/g, 4.20mmol/g, 3.82mmol/g, the B acid strength corresponds to 0.38mmol/g, 0.29mmol/g, 0.26mmol/g, is used for following examples.
Embodiment 4
Press the powder formulation of carrier 5 in the table one and the carrier preparation method among the embodiment 1, respectively alkali metal is used instead 40g, 90g, 160g calcium nitrate, obtain following carrier 10a, 10b, 10c, specific area corresponds to 124.60m2/g, 129.71m2/g, 130.62m2/g, pore volume corresponds to 0.42ml/g, 0.46ml/g, 0.45ml/g, the L acid strength corresponds to 4.57mmo1/g, 3.48mmol/g, 3.29mmol/g, the B acid strength corresponds to 0.46mmol/g, 0.35mmol/g, 0.31mmol/g, is used for following examples.
Embodiment 5
Take by weighing respectively among the embodiment 1 1～7, embodiment 2, embodiment 3 and embodiment 4 carrier 100g, put into respectively the mixed aqueous solution that 125ml contains ruthenic chloride and radium chloride, wherein Ru content 0.002g/ml, Rh content 0.0004g/ml, flooded after 24 hours 120 ℃ of dryings 6 hours, repeat aforesaid operations 4 times, in 400 ℃ of roastings 4 hours, obtain corresponding after dry
H-1, H-2, H-3, H-4, H-5, H-6, H-7, H-8a, H-8b, H-8c, H-9a, H-9b, H-9c, H-10a, H-10b, H-10c catalyst, all load 1%Ru and 0.2%Rh.
The above-mentioned catalyst that obtains carries out the evaluation of catalyst activity in embodiment 6, confirm the performance of composite modified carrier with this.
Embodiment 6
Bisphenol-A is dissolved in the isopropyl alcohol, forms content of bisphenol A 23%(wt) aqueous isopropanol, in wherein, add entry, make water content reach 400ppm, with this as reaction raw materials solution.The catalyst of in the single tube fixed bed reactors, packing into, reduction activation under temperature programming in atmosphere of hydrogen, material solution passed into through measuring pump carry out hydrogenation reaction in the reactor, reaction condition: pressure 7.8Mpa, 165 ℃ of bed temperatures, liquid air speed 6.6h-1 (V), hydrogen gas space velocity 450h-1 (V) after the hydrogenation mix products cooling, obtains containing the mix products of the hydrogenated bisphenol A of solvent, analyze, as follows:
The evaluation of table two catalyst activity
Annotate: BP15～16 expression chromatography go out the accessory substance of peak retention time in the time of 15～16 minutes, and other is analogized.
Can be found out by table two, adopt composite modified aluminium oxide as catalyst H-1, H-2, H-3, H-4, H-5, H-8a, H-8b, H-8c, H-9a, H-9b, H-9c, H-10a, H-10b, the H-10c of the preparation of double A catalyst carrier for hydrgenating, conversion ratio reach or near 100%, selective 96%, and catalyst H-6, the H-7 of unmodified carrier preparation, conversion ratio and selectively be lower than the former illustrates that the catalyst that adopts in the invention can improve anti-/ transisomer ratio in the product.
As shown in Figure 1: expression product gas chromatographic analysis general figure, the arrow indicating positions is that chromatogram goes out the corresponding product of peak retention time, what of the content of corresponding each product of peak area size are in order to the response data in the instruction card two
Embodiment 7
Adopt carrier 5, according to the method for embodiment 5, preparation different activities constituent content catalyst carries out activity rating, and is as follows:
Table three different activities constituent content evaluating catalyst
Catalyst H-11, H-12, H-13 and H-14 are bi-component supported catalyst, anti-/trans ratios is greater than 55% in the hydrogenation products mixed isomers, and H-15, H-16 and H-17 are the one pack system loaded catalyst, and catalyst hydrogenation activity, selective reaching instead/transisomer ratio all are lower than the former.
Embodiment 8
Adopt H-5 catalyst, the material solution of preparing different water contents carries out hydrogenation reaction, and reaction condition is identical with embodiment 6, and response data is as follows:
The impact of table four water content
Illustrate and adopt catalyst of the present invention, add minor amount of water in hydrogenation process, hydrogenation reaction is had considerable influence, micro-water content is when 300～500ppm, and selectivity of product and anti-/ transisomer ratio all are improved.
Embodiment 9
Adopt catalyst H-5 according to the process conditions of embodiment 6, two groups of 1500 hours continously hydrogen addings reaction contrasts have been carried out respectively, carry out the catalyst stability experiment, raw material adopts respectively and adds the 350ppm minor amount of water and do not add the material solution of minor amount of water, following Fig. 2 of hydrogenation reaction data, shown in Figure 3: Fig. 2 is that course of reaction Raw system adds 350ppm water (wt%), the experimental data demonstration of hydrogenation reaction, after catalyst moves 1500 hours continuously, catalyst performance stabilised.Fig. 3 does not add water in the course of reaction Raw system, and the experimental data of hydrogenation reaction shows, catalyst performance descends along with the prolongation in reaction time, and the hydrogenation reaction operation is after 1500 hours, conversion ratio and selectively dropped to 92%, 83%.
In the contrast experiment of embodiment 9, can be seen by contrast experiment's data of Fig. 2 and Fig. 3, use the catalyst that adopts in the invention, by in course of reaction, adding minor amount of water, can improve the stability of catalyst, the service life of extending catalyst.
Claims (9)
1. catalyst for the preparation of hydrogenated bisphenol A is characterized in that component and mass fraction are:
100 parts of the composite alumina supports of modification,
1～3 part of the noble metal of active component;
Wherein: the composite alumina support of modification is comprised of 30～80 mass parts boehmites, 10～40 mass parts aluminium hydroxides, 1～5 mass parts alkali metal, 1～5 mass parts P elements; Described active component is multicomponent, is selected from two kinds among Pd, Ru, the Rh.
2. according to claim 1 hydrogenation catalyst is characterized in that described catalyst alkali metal is selected from a kind of in the nitrate of Na, K, Mg or Ca.
3. according to claim 1 hydrogenation catalyst is characterized in that described phosphorus is selected from phosphoric acid or phosphorous acid.
4. according to claim 3 hydrogenation catalyst is characterized in that take carrier as 100%, and the amount of described Pd is 0.5～2.0% (wt%).
5. according to claim 3 hydrogenation catalyst is characterized in that the amount take carrier as 100% described Ru is 0.5～2.0% (wt%) with respect to carrier.
6. according to claim 3 hydrogenation catalyst is characterized in that the amount take carrier as 100% described Rh is 0.1～1.0% (wt%) with respect to carrier.
7. according to claim 1 hydrogenation catalyst is used, and when its spy is for the preparation of hydrogenated bisphenol A, in catalyst, adds minor amount of water as stabilizing agent.
8. application according to claim 8, its spy is that the content of described stabilizing agent water in reaction system is 300～500ppm.
9. when hydrogenation catalyst uses according to claim 7, product be characterised in that in the product composition hydrogenated bisphenol A anti-/ the transisomer ratio is greater than 55%.
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| US20160158731A1 (en) * | 2014-12-09 | 2016-06-09 | Industrial Technology Research Institute | Catalyst and manufacturing method thereof and method for manufacturing hydrogenated bisphenol a or derivatives thereof using the same |
| CN106563447A (en) * | 2016-10-20 | 2017-04-19 | 中国石油化工股份有限公司 | Preparation method for bisphenol A hydrogenated catalyst |
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| CN107954832A (en) * | 2017-11-13 | 2018-04-24 | 江苏康恒化工有限公司 | A kind of preparation method of hydrogenated bisphenol A |
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| CN112316939A (en) * | 2020-09-28 | 2021-02-05 | 中国石油化工股份有限公司 | Preparation method of high-trans-proportion hydrogenated bisphenol A |
| CN112174777A (en) * | 2020-11-06 | 2021-01-05 | 本源精化环保科技有限公司 | Preparation method of 2,2' -di (4-hydroxycyclohexyl) propane |
| 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 |
| 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 |
| US11905235B2 (en) | 2021-11-16 | 2024-02-20 | China Petrochemical Development Corporation, Taipei (Taiwan) | Method for preparing 2,2-bis(4-hydroxycyclohexyl)propane |
| JP7519398B2 (en) | 2021-11-16 | 2024-07-19 | 中國石油化學工業開發股▲分▼有限公司 | Method for producing 2,2-bis(4-hydroxycyclohexyl)propane |
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