CN109232188B - Preparation method of hydrogenated bisphenol A - Google Patents

Preparation method of hydrogenated bisphenol A Download PDF

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CN109232188B
CN109232188B CN201811205479.7A CN201811205479A CN109232188B CN 109232188 B CN109232188 B CN 109232188B CN 201811205479 A CN201811205479 A CN 201811205479A CN 109232188 B CN109232188 B CN 109232188B
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CN109232188A (en
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何明阳
钱俊峰
孙中华
孙富安
吴中
陈群
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Changzhou University
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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
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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 hydrogenated bisphenol A, belonging to the field of organic matter hydrogenation. The nickel-based catalyst is Ni/SiO2Or Ni/Al2O3The nickel content of the catalyst is 15-45%, the catalyst is prepared by an impregnation method, the process is simple, and the industrialization is easy to realize. The conversion rate of bisphenol A in the hydrogenation process reaction reaches 100%, the product selectivity is higher than 98.5%, and meanwhile, the continuous preparation can be realized.

Description

Preparation method of hydrogenated bisphenol A
Technical Field
The invention belongs to the field of organic matter hydrogenation, relates to a preparation method of hydrogenated bisphenol A, and further relates to a catalyst for bisphenol A hydrogenation and a preparation method thereof.
Background
Hydrogenated bisphenol A (HBPA for short) is an important production raw material for manufacturing synthetic materials such as epoxy resin, unsaturated resin, polycarbonate, polyacrylic resin and the like, has the advantages of thermal stability, chemical stability, weather resistance and the like, and has wide application fields. Particularly, epoxy resins are important means for modifying epoxy resins.
The hydrogenated bisphenol A is prepared by using bisphenol A as a raw material and carrying out hydrogenation reaction in a solution state under the action of a catalyst. The preparation of hydrogenated bisphenol A belongs to the field of aromatic compound hydrogenation and benzene ring hydrogenation, and the bisphenol A hydrogenation mainly comprises the following three catalysts, namely a metal framework type catalyst, a noble metal supported type catalyst and a homogeneous phase catalyst, wherein the general reaction conditions are 50-250 ℃, the hydrogen pressure is 1-30 MPa, and an intermittent or continuous hydrogenation process flow can be adopted.
For example, in U.S. Pat. No. 4,2118954, a supported nickel-based catalyst is used for liquid-phase kettle-type hydrogenation of bisphenol A to prepare hydrogenated bisphenol A, the reaction temperature is 200 ℃, the pressure is 10-20 MPa, but the reaction time is long, and the product yield is low. U.S. Pat. No. 4,973,323 uses nickel catalyst and kettle hydrogenation method, and the reaction is carried out at 180 deg.C and 3MPa for 4 hours, and the conversion rate of the reaction reaches 99%. U.S. Pat. Nos. 4,193,1343 and 4,960 adopt a nickel-based catalyst and a kettle-type hydrogenation method, the reaction temperature is 120-220 ℃, the pressure is 3MPa, and the conversion rate can reach 97% and the selectivity reaches 99% after 4 hours of reaction. The nickel-based catalyst is basically adopted by a kettle type reaction process, has the defects of high continuous difficulty, difficult catalyst separation and the like, and is not suitable for industrial batch production.
U.S. Pat. No. 4,4885409 discloses a process for hydrogenating bisphenol A by using palladium supported on activated carbon carrier to react bisphenol A in bulk or in solvent with hydrogen, wherein the selectivity of hydrogenated bisphenol A is higher than 99% and the content of trans/trans isomer in the product is higher than 55% by using a kettle type hydrogenation process under the conditions of 140 ℃ of reaction temperature and 10MPa of pressure for 12 hours. Chinese patents CN1095690C and CN1100608C develop a supported ruthenium catalyst which can be used in the hydrogenation process of bisphenol A, and the supported ruthenium catalyst adopts a kettle type hydrogenation process to react for 5 hours under the conditions of the reaction temperature of 150 ℃ and the pressure of 20MPa, and the reaction conversion rate reaches more than 99 percent. Chinese patent CN1375484 discloses a method for preparing hydrogenated bisphenol A in the presence of ruthenium catalyst loaded on silica, which adopts fixed bed hydrogenation process, the hydrogenation reaction is carried out at 50-250 ℃ and 0.5-15 MPa, the molar ratio of hydrogen and bisphenol A is 6: 1-30: 1, the conversion rate is 100% within 40 hours of reaction, and the average selectivity is 96%.
Most of the existing researches on the preparation technology of hydrogenated bisphenol A focus on the development of hydrogenation catalysts, while the catalysts used in fixed bed hydrogenation are mainly noble metals such as Pd, Ru, Rh, etc., while the research reports on nickel-based hydrogenation of bisphenol A mainly focus on batch reactor hydrogenation, and the reports on the use of nickel catalysts in fixed bed reaction are few. Therefore, the catalyst which is suitable for the bisphenol A fixed bed hydrogenation reaction and has relatively low development cost and easy industrialization is of great importance for reducing the production cost of the hydrogenated bisphenol A.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, the invention directly starts with the treatment of the carrier, and the prepared catalyst has the characteristics of high activity, difficult blockage of pore channels, long service life and the like. In order to achieve the above purpose, the invention adopts the following technical scheme.
The preparation method of the nickel-based hydrogenation catalyst comprises the following steps:
(1) and carrying out hydro-thermal treatment on the carrier in a closed reaction kettle at the temperature of 120-180 ℃, and drying to obtain the carrier A.
(2) Preparing a nickel-ammonia solution B by using nickel nitrate and ammonia water, wherein the nickel content in the solution B is 10-20 g/L, and the pH value of the solution B is 8.5-10.
(3) Adding the carrier A into the solution B, dipping for 3-6 hours at the temperature of 60-80 ℃ and under the pressure of-0.08-0.04 MPa, filtering out solids, drying, and roasting for 3-5 hours at the temperature of 350-500 ℃ to obtain a semi-finished catalyst C.
(4) And (3) dipping the auxiliary agent solution onto the catalyst C by adopting an equivalent dipping method, and roasting for 3-5 hours at the temperature of 350-500 ℃.
(5) Activating the catalyst: and reducing the roasted catalyst for 2-4 hours by using hydrogen at the temperature of 400-500 ℃ to obtain the nickel-based hydrogenation catalyst.
The nickel catalyst adopted by the invention comprises 15-45% of nickel by mass, 0.2-2% of auxiliary agent by mass and the balance of carrier. Wherein the auxiliary agent component is one of Mn, Co and Mg, the carrier is spherical or strip-shaped alumina, spherical or strip-shaped silicon dioxide, and the alumina carrier is specific to the surfaceThe area is 70-140 m2The pore volume is 0.15-0.45 mL/g; the specific surface area of the silicon dioxide carrier is 100-300 m2(iv) a pore volume of 0.45 to 1.0 mL/g.
The invention defines the specific surface area and pore volume of the carrier, as this is one of the important factors determining the performance of the catalyst. If the specific surface area is too small, the adsorption capacity of the catalyst to the material is small, which may result in a decrease in the activity of the catalyst, and if the specific surface area is too large, the number of micropores in the catalyst may be large, which may result in a decrease in the selectivity of the product.
The hydrogenation nickel-based catalyst prepared by the method is as follows: Ni/SiO2Or Ni/Al2O3A catalyst.
According to the invention, the carrier is pretreated by a hydrothermal method, so that the proportion of micropores in the carrier can be reduced, the pore volume is increased, and the selectivity of hydrogenated bisphenol A is improved. The method adopts a nickel-ammonia complex solution vacuum impregnation method, utilizes negative pressure to absorb ammonia gas for recycling, simultaneously changes the defects that the prior nickel nitrate impregnation needs complex procedures of multiple impregnation and roasting and the production cost of the catalyst is high, can obtain the required catalyst by one-time impregnation, and has simpler and quicker process.
The synthesis of hydrogenated bisphenol A according to the invention is carried out under the following conditions:
the invention discloses a hydrogenation method for bisphenol A, which is characterized in that the hydrogenation process conditions of bisphenol A are as follows: the temperature is 120-200 ℃ (the preferable reaction temperature is 120-180 ℃), the pressure is 3-5 MPa, the feeding concentration is 10-50%, and the liquid airspeed is 1-2 h-1And hydrogen gas BPA (mol) 3-10, wherein the hydrogenation nickel-based catalyst is Ni/SiO2Or Ni/Al2O3A catalyst.
The solvent adopted by the invention is one of ethanol, isopropanol, n-propanol and butanol. And the mass concentration (feed concentration) of bisphenol A in the mixed solution of bisphenol A and the solvent is 20-50 wt%.
Compared with the prior art, the invention has the beneficial effects that:
(1) the hydrogenation reaction adopts a tower type fixed bed reactor with lower inlet and upper outlet, the materials can effectively absorb the reaction heat generated by the hydrogenation reaction, the reaction temperature is effectively controlled, the aggravation of side reaction caused by overhigh local temperature is avoided, and the selectivity of the hydrogenated bisphenol A of the reaction is improved; meanwhile, the material stays in the catalyst bed for a longer time, the hydrogenation effect is better, the conversion rate of the bisphenol A is improved, the reaction process conditions are optimized, the conversion rate of the bisphenol A in the hydrogenation process reaction can reach 100%, the product selectivity is higher than 98.5%, and meanwhile, the continuous preparation can be realized, the production efficiency is high, the operation is convenient, and the like;
(2) the nickel-based catalyst prepared by adopting a specific process has the advantages of good dispersion degree of active components, more active centers and difficult loss of active components, and simultaneously further reduces the reaction activation energy and improves the conversion rate and the selectivity of the bisphenol A through the synergistic effect with other elements.
Detailed Description
The following examples are given to illustrate the specific embodiments of the silica carrier used in the following examples in which the silica carrier is spherical in shape having a diameter of 2.5mm to 3.5mm and a specific surface of 223.3m2The pore volume is 0.81ml/g, and the average pore diameter is 6.2 nm; the gamma-alumina carrier is in the shape of a strip with the diameter of 3mm and the length of 2-4 mm, and the specific surface area is 118.5m2The pore volume is 0.32ml/g and the average pore diameter is 5.2 nm.
Example 1
Adding 500ml of water and 100g of microsphere silicon dioxide carrier into a 1L high-pressure reaction kettle in sequence, sealing, heating to 160 ℃, keeping for 3 hours, filtering the materials when the temperature is reduced to below 50 ℃, collecting filter cakes, and drying to obtain the required carrier. The preparation of the catalyst is carried out in a closed reaction kettle according to the following steps. Preparing nickel ammonia solution: slowly dripping the ammonia water solution into 500ml of 2M nickel nitrate solution to ensure that the pH value is 8.5, and preparing a clear nickel-ammonia complex solution, wherein the nickel content in the solution is 16%. Dipping: and (3) adding 80g of the carrier into the solution of the nickel-ammonia complex of the step (i), controlling the temperature to 65 ℃, and keeping the impregnation for 4 hours under the condition of stirring pressure of-0.06 MPa to finish the impregnation. Thirdly, separating, drying and roasting for 5 hours at 350 ℃ to obtain a semi-finished catalyst. Fourthly, 100mL of manganese nitrate solution with the concentration of 0.1MUniformly spraying the catalyst on the semi-finished product, drying, and roasting at 500 ℃ for 3 hours. Fifthly, keeping the catalyst for 3 hours at 480 ℃ in a 10 vol% hydrogen/nitrogen atmosphere after roasting to obtain a catalyst finished product A. The mass content of nickel in the catalyst A is 15.5 percent, the content of the auxiliary agent Mn is 0.58 percent, and the specific surface of the catalyst A is 232.5m2Per g, pore volume of 0.72ml/g, and average pore diameter of 5.5 nm.
Example 2
Adding 500ml of water and 100g of microsphere silicon dioxide carrier into a 1L high-pressure reaction kettle in sequence, sealing, heating to 120 ℃, keeping for 4 hours, filtering the materials when the temperature is reduced to below 50 ℃, collecting filter cakes, and drying to obtain the required carrier. The catalyst preparation is carried out in a closed reaction kettle according to the following steps. Preparing nickel ammonia solution: the ammonia solution was slowly added dropwise to 500ml of 4M nickel nitrate solution to a pH of 9.0 to prepare a clear nickel ammonia complex solution with a nickel content of 18%. Dipping: adding 80g of the carrier into the solution of the nickel-ammonia complex of the formula I, controlling the temperature at 80 ℃, keeping the temperature for 6 hours under the stirring pressure of-0.08 MPa, and finishing the impregnation. Thirdly, separating, drying and roasting for 3 hours at 500 ℃ to obtain a semi-finished catalyst. And fourthly, uniformly spraying 0.04M 100mL of manganese nitrate solution on the semi-finished product of the catalyst, drying and roasting for 4.5 hours at 400 ℃. Fifthly, keeping the catalyst for 4 hours at 420 ℃ in a 10 vol% hydrogen/nitrogen atmosphere after roasting to obtain a catalyst finished product B. The nickel content of the catalyst B is 42.8 percent, the content of the auxiliary agent Mn is 0.21 percent, the specific surface of the catalyst is 282.1m2/g, the pore volume is 0.62ml/g, and the average pore diameter is 5.0 nm.
Example 3
Adding 500ml of water and 100g of microsphere silicon dioxide carrier into a 1L high-pressure reaction kettle in sequence, sealing, heating to 180 ℃, keeping for 2 hours, and filtering and drying the material when the temperature is reduced to below 50 ℃ to obtain the required carrier. The catalyst preparation is carried out in a closed reaction kettle according to the following steps. Preparing nickel ammonia solution: the ammonia solution was slowly added dropwise to 500ml of 3M nickel nitrate solution to a pH of 10.0 to prepare a clear nickel ammonia complex solution with a nickel content of 19.8%. Dipping: 80g of the carrier is added into the solution of the nickel-ammonia complex of the formula I, the temperature is controlled at 60 ℃, the solution is kept for 3 hours under the stirring pressure of-0.05 MPa, and the impregnation is finished. ③ separating, drying and roasting for 3 hours at 500 ℃. And fourthly, uniformly spraying 0.4M of 100mL of cobalt nitrate solution on the semi-finished product of the catalyst, drying and roasting for 5 hours at 380 ℃. Keeping the mixture at 500 ℃ for 2 hours in a 10 vol% hydrogen/nitrogen atmosphere to obtain a catalyst finished product C. The content of nickel in the catalyst C is 30.5 percent, the content of the auxiliary agent Co is 1.96 percent, the specific surface of the catalyst is 267.1m2/g, the pore volume is 0.68ml/g, and the average pore diameter is 5.3 nm.
Example 4
Adding 500ml of water and 100g of strip-shaped alumina carrier into a 1L high-pressure reaction kettle in sequence, sealing, heating to 170 ℃, keeping for 3 hours, and filtering and drying the material when the temperature is reduced to below 50 ℃ to obtain the required carrier. The catalyst preparation is carried out in a closed reaction kettle according to the following steps. Preparing nickel ammonia solution: slowly dripping the ammonia water solution into 500ml of 1.5M nickel nitrate solution to ensure that the pH value is 9.0, and preparing a clear nickel-ammonia complex solution with the nickel content of 12.8 percent. Dipping: 80g of the carrier is added into the solution of the nickel-ammonia complex of the formula I, the temperature is controlled at 70 ℃, the solution is kept for 3 hours under the stirring pressure of-0.07 MPa, and the impregnation is finished. ③ separating, drying and roasting for 4 hours at 480 ℃. And fourthly, uniformly spraying 0.5M 100mL of magnesium nitrate solution on the semi-finished product of the catalyst, drying and roasting for 5 hours at 380 ℃. Keeping the reaction product at 500 ℃ for 2 hours in a 10 vol% hydrogen/nitrogen atmosphere to obtain a catalyst finished product D. The nickel content of the catalyst D is 21.3 percent, the content of the auxiliary agent Mg is 1.23 percent, the specific surface area of the catalyst is 105.5m2/g, the pore volume is 0.32ml/g, and the average pore diameter is 5.1 nm.
Example 5
Adding 500ml of water and 100g of strip-shaped alumina carrier into a 1L high-pressure reaction kettle in sequence, sealing, heating to 160 ℃, keeping for 4 hours, and filtering and drying the material when the temperature is reduced to below 50 ℃ to obtain the required carrier. The catalyst preparation is carried out in a closed reaction kettle according to the following steps. Preparing nickel ammonia solution: and slowly dripping the ammonia water solution into 500ml of 2M nickel nitrate solution to ensure that the pH value is 9.5, and preparing a clear nickel-ammonia complex solution with the nickel content of 18.7 percent. Dipping: adding 80g of the carrier into the solution of the nickel-ammonia complex of the formula I, controlling the temperature at 80 ℃, keeping the temperature for 5 hours under the stirring pressure of-0.05 MPa, and finishing the impregnation. ③ separating, drying and roasting for 4 hours at the temperature of 410 ℃. And fourthly, uniformly spraying 0.6M of 100mL of magnesium nitrate solution on the semi-finished product of the catalyst, drying and roasting for 5 hours at 380 ℃. Keeping the temperature at 430 ℃ for 3 hours in a 10 vol% hydrogen/nitrogen atmosphere to obtain a catalyst finished product E. The content of nickel in the catalyst E is 32.6 percent, the content of the auxiliary agent Mg is 1.52 percent, the specific surface of the catalyst E is 94.4m2/g, the pore volume is 0.30ml/g, and the average pore diameter is 5.4 nm.
Example 6
Adding 500ml of water and 100g of strip-shaped alumina carrier into a 1L high-pressure reaction kettle in sequence, sealing, heating to 140 ℃, keeping for 4 hours, and filtering and drying the material when the temperature is reduced to below 50 ℃ to obtain the required carrier. The catalyst preparation is carried out in a closed reaction kettle according to the following steps. Preparing nickel ammonia solution: and slowly dripping the ammonia water solution into 500ml of 2M nickel nitrate solution to ensure that the pH value is 9.2, and preparing a clear nickel-ammonia complex solution with the nickel content of 12.7 percent. Dipping: 80g of the carrier is added into the solution of the nickel-ammonia complex of the formula I, the temperature is controlled to 65 ℃, the solution is kept for 4 hours under the stirring pressure of-0.05 MPa, and the impregnation is finished. ③ separating, drying and roasting for 4 hours at 480 ℃. And fourthly, uniformly spraying 0.05M of 100mL of manganese nitrate solution on the semi-finished product of the catalyst, drying and roasting for 3.5 hours at 480 ℃. Keeping the temperature at 450 ℃ for 3 hours in a 10 vol% hydrogen/nitrogen atmosphere to obtain a catalyst finished product F. The nickel content of the catalyst F is 18.9 percent, the content of the auxiliary agent Mn is 0.31 percent, the specific surface area of the catalyst is 123.6m2/g, the pore volume is 0.34ml/g, and the average pore diameter is 5.3 nm.
Example 7
Adding 500ml of water and 100g of microsphere silicon dioxide carrier into a 1L high-pressure reaction kettle in sequence, sealing, heating to 180 ℃, keeping for 2 hours, and filtering and drying the material when the temperature is reduced to below 50 ℃ to obtain the required carrier. The catalyst preparation is carried out in a closed reaction kettle according to the following steps. Preparing nickel ammonia solution: the ammonia solution was slowly added dropwise to 500ml of 3M nickel nitrate solution to a pH of 10.0 to prepare a clear nickel ammonia complex solution with a nickel content of 19.8%. Dipping: 80g of the carrier is added into the solution of the nickel-ammonia complex of the formula I, the temperature is controlled at 60 ℃, the solution is kept for 3 hours under the stirring pressure of-0.05 MPa, and the impregnation is finished. ③ separating, drying and roasting for 3 hours at 500 ℃. Fourthly, keeping the mixture for 2 hours at 500 ℃ in a hydrogen/nitrogen atmosphere with the concentration of 10 vol% to obtain a finished product G of the catalyst. The nickel content of catalyst G was 30.5%, the specific surface was 265.3m2/G, the pore volume was 0.68ml/G, and the average pore diameter was 5.2 nm.
Comparative examples
Adding 500ml of water and 100g of strip-shaped alumina carrier into a 1L high-pressure reaction kettle in sequence, sealing, heating to 140 ℃, keeping for 4 hours, and filtering and drying the material when the temperature is reduced to below 50 ℃ to obtain the required carrier. The catalyst preparation is carried out in a closed reaction kettle according to the following steps. Preparing nickel ammonia solution: and slowly dripping the ammonia water solution into 500ml of 2M nickel nitrate solution to ensure that the pH value is 9.2, and preparing a clear nickel-ammonia complex solution with the nickel content of 12.7 percent. Dipping: 80g of the carrier is added into the solution of the nickel-ammonia complex of the formula I, the temperature is controlled to 65 ℃, and the solution is kept for 4 hours under the condition of stirring and normal pressure, so that the impregnation is finished. Thirdly, separating, drying and roasting for 4 hours at 480 ℃ to obtain a semi-finished catalyst. And fourthly, uniformly spraying 0.05M of 100mL of manganese nitrate solution on the semi-finished product of the catalyst, drying and roasting for 3.5 hours at 480 ℃. Keeping the reaction product at 450 ℃ for 3 hours in a 10 vol% hydrogen/nitrogen atmosphere to obtain a catalyst finished product H. The nickel content of the catalyst H is 8.2 percent, the specific surface area is 203.4m2/g, the pore volume is 0.28ml/g, the average pore diameter is 3.5nm, and the content of the auxiliary agent Mn is 0.36 percent.
And (3) carrying out catalytic hydrogenation reaction on the catalyst products obtained in the embodiments 1-7 and the comparative example in a fixed bed reactor with the specification of phi 28 multiplied by 3mm, wherein the loading of the catalyst is 20ml, hydrogen passes through a mass flow meter, bisphenol A is preheated by mixing with the hydrogen through a metering pump, and then enters a hydrogenation reactor from the bottom of the reactor for catalytic hydrogenation, after condensation and separation of the products, hydrogen is discharged, liquid products are collected for analysis, and the products before and after hydrogenation are analyzed by adopting gas chromatography, so that the conversion rate of the bisphenol A and the selectivity of the hydrogenated bisphenol A are calculated. The specific catalyst and process conditions and test results are as follows:
Figure BDA0001831114540000071
Figure BDA0001831114540000081
the data in the table show that the prepared series of catalysts have higher bisphenol A conversion rate under proper process conditions, and simultaneously have higher selectivity of hydrogenated bisphenol A, and have good industrial application prospect.

Claims (3)

1. A process for producing hydrogenated bisphenol A, characterized by comprising: hydrogenating bisphenol A in a fixed bed reactor in the presence of a nickel catalyst and a solvent to generate hydrogenated bisphenol A; the technological conditions of the bisphenol A hydrogenation reaction are as follows: the reaction temperature is 120-200 ℃, the pressure is 3-5 MPa, the feeding concentration is 10-50%, and the liquid airspeed is 1-2 h-1And hydrogen gas BPA (mol) = 3-10, and the nickel catalyst comprises the following components: the mass content of nickel is 15-45%, the mass content of an auxiliary agent is 0.2-2%, and the balance is a catalyst carrier;
the auxiliary agent is one of Mn, Co and Mg
The carrier is alumina or silicon dioxide, wherein the specific surface area of the alumina carrier is 70-140 m2The pore volume is 0.15-0.45 mL/g; the specific surface area of the silicon dioxide carrier is 100-300 m2(iv)/g, pore volume of 0.45-1.0 mL/g.
2. The method for producing hydrogenated bisphenol A according to claim 1, wherein said reaction temperature is 140 to 180 ℃; the mass concentration of bisphenol A in the mixed liquid of bisphenol A and the solvent is 20-50%; the solvent is one of ethanol, isopropanol, n-propanol and butanol.
3. The process for producing hydrogenated bisphenol A according to any of claims 1 to 2, wherein said nickel catalyst is produced by the following steps:
(1) pretreatment of a carrier: carrying out hydro-thermal treatment on the carrier in a closed reaction kettle at the temperature of 120-180 ℃, and drying to obtain a carrier A;
(2) preparing an immersion liquid: preparing a nickel-ammonia solution B by using nickel nitrate and ammonia water, wherein the nickel content in the solution B is 10-20 g/L, and the pH value of the solution B is 8.5-10;
(3) dipping: adding the carrier A into the solution B, dipping for 3-6 hours at the temperature of 60-80 ℃ and under the pressure of-0.08 to-0.04 MPa, filtering out solids, drying, and roasting for 3-5 hours at the temperature of 350-500 ℃ to obtain a semi-finished catalyst C;
(4) auxiliary agent impregnation and reduction: and (3) dipping the auxiliary agent solution onto the semi-finished catalyst C by adopting an equivalent dipping method, roasting for 3-5 hours at the temperature of 350-500 ℃, and reducing for 2-4 hours at the temperature of 400-500 ℃ by using hydrogen after roasting to obtain the nickel catalyst.
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CN114643060B (en) * 2020-12-18 2023-08-01 湖南长炼新材料科技股份公司 Hydrogenation catalyst, preparation method and application thereof, and hydrogenation reaction method
CN113292396A (en) * 2021-06-02 2021-08-24 中国科学院大连化学物理研究所 Preparation of load type catalyst and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone in fixed bed
CN115739116A (en) * 2022-11-29 2023-03-07 本源精化环保科技有限公司 Catalyst, preparation method and regeneration method thereof, and hydrogenated bisphenol A production method

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