阅读说明：本技术 一种双酚a催化加氢制备氢化双酚a的方法 (Method for preparing hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A ) 是由 司晓郡 张磊 王开林 宁小娟 李明玉 吴俊华 于 2021-09-30 设计创作，主要内容包括：本发明是一种双酚A催化加氢制备氢化双酚A的方法；双酚A溶液计量升压后与经计量的高压氢气混合后进入固定床套管式加氢反应器,在加氢催化剂床层进行加氢反应；加氢反应器采用套管热油加热的方式,分加热段和取热段两路热油循环；催化剂装填时采用惰性瓷球或载体稀释活性组分的方式避免床层局部温度过高,防止造成催化剂烧结；生成氢化双酚A溶液经气液分离后,液相脱除溶剂得到氢化双酚A产品；采用两路热油循环和活性组分稀释的方法,有效的减少加氢过程中副反应的发生,降低了产物中的副产品,同时提出催化剂床层加氢活性逐渐增加,既能使加氢平稳进行,避免集中放热,同时不会降低加氢反应效果。(The invention is a method for preparing hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A; after the bisphenol A solution is measured and pressurized, the bisphenol A solution is mixed with measured high-pressure hydrogen and then enters a fixed bed sleeve type hydrogenation reactor, and hydrogenation reaction is carried out on a hydrogenation catalyst bed layer; the hydrogenation reactor adopts a sleeve hot oil heating mode and is divided into a heating section and a heat taking section to circulate two paths of hot oil; when the catalyst is filled, the method of diluting active components by adopting inert ceramic balls or carriers is adopted to avoid overhigh local temperature of a bed layer and prevent the catalyst from sintering; carrying out gas-liquid separation on the generated hydrogenated bisphenol A solution, and then removing the solvent from the liquid phase to obtain a hydrogenated bisphenol A product; the method of two hot oil circulations and active component dilution is adopted, the occurrence of side reactions in the hydrogenation process is effectively reduced, the byproducts in the products are reduced, and the hydrogenation activity of the catalyst bed layer is gradually increased, so that the hydrogenation can be stably carried out, the concentrated heat release is avoided, and the hydrogenation reaction effect cannot be reduced.)

1. A method for preparing hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A is characterized in that a bisphenol A solution is metered and pressurized, then mixed with metered high-pressure hydrogen, and then enters a fixed bed sleeve type hydrogenation reactor, and hydrogenation reaction is carried out on a hydrogenation catalyst bed layer; the hydrogenation reactor adopts a sleeve hot oil heating mode, a jacket part is divided into a heating section and a heat taking section, two hot oil paths circulate, the hot oil heating furnace outputs two hot oil paths, and the two hot oil paths respectively control the oil outlet temperature; when the catalyst is filled, the method of diluting active components by adopting inert ceramic balls or carriers is adopted to avoid overhigh local temperature of a bed layer and prevent the catalyst from sintering; and (3) carrying out gas-liquid separation on the generated hydrogenated bisphenol A solution, and removing the solvent from the liquid phase to obtain a hydrogenated bisphenol A product.

2. The method according to claim 1, wherein the hydrogenation reactor is a single-tube type or a tubular type, and the number of the tubular type reactors is 2-10.

3. The method as claimed in claim 1, wherein the hydrogenation reactor is heated by using double-pipe hot oil, the temperature of the hot oil in the heating section is set to be the same as the hydrogenation reaction temperature, the temperature of the hot oil in the heat-taking section is set to be 2-30 ℃ lower than the temperature of the hot oil inlet in the heating section, the hot oil heating furnace outputs two hot oil paths and supplies oil to the heating section and the heat-taking section respectively, the heating furnace is a device provided with two hot oil outlets, or the two heating furnaces supply oil to the heating section and the heat-taking section respectively.

4. The method according to claim 1, wherein the hydrogenation reactor adopts a jacket hot oil heating mode, and the temperature of hot oil in the heat taking section is 5-15 ℃ lower than that of hot oil in the heating section

5. The method as claimed in claim 1, wherein the catalytic active component is diluted with inert ceramic balls, and the hydrogenation catalyst is uniformly mixed with 0.5-2 times of the volume of the inert ceramic balls and then filled into the reactor bed.

6. The method as claimed in claim 1, wherein the catalytic active component is diluted with inert ceramic balls, and the hydrogenation catalyst is uniformly mixed with 0.8-1.5 times of the volume of the inert ceramic balls and then filled into the reactor bed.

7. The method according to claim 1, wherein the catalytically active component is diluted with the carrier, and when the hydrogenation catalyst is loaded, the catalyst having a total volume of 30 to 70% is loaded from below, and then the loading amount of the catalytically active component loaded on the upper part is reduced to 50 to 90% of the loading amount of the catalyst loaded on the lower part.

8. The method according to claim 1, wherein the catalytically active component is diluted with the carrier, and when the hydrogenation catalyst is loaded, the catalyst having a total volume of 40 to 60% is loaded from the lower portion, and then the loading amount of the catalytically active component loaded on the upper portion is reduced to 60 to 80% of the loading amount of the catalyst loaded on the lower portion.

9. The method of claim 1, wherein the catalytically active component is diluted with a carrier, and when the hydrogenation catalyst is loaded, the lower catalyst volume is 20 to 60% of the total volume of the catalyst, the middle catalyst volume is 20 to 50% of the total volume of the catalyst, the middle catalyst active component loading is reduced to 60 to 80% of the lower catalyst loading, the upper catalyst volume is 20 to 50% of the total volume of the catalyst, and the upper catalyst active component loading is reduced to 50 to 70% of the lower catalyst loading.

Technical Field

The invention relates to a method for catalytic hydrogenation of bisphenol A, which comprises the following steps: after the bisphenol A solution is measured and pressurized, the bisphenol A solution is mixed with measured high-pressure hydrogen and then enters a fixed bed sleeve type hydrogenation reactor, and hydrogenation reaction is carried out on a hydrogenation catalyst bed layer; the hydrogenation reactor adopts a sleeve hot oil heating mode and is divided into a heating section and a heat taking section to circulate two paths of hot oil; when the catalyst is filled, the method of diluting active components by adopting inert ceramic balls or carriers is adopted to avoid overhigh local temperature of a bed layer and prevent the catalyst from sintering; and (3) carrying out gas-liquid separation on the generated hydrogenated bisphenol A solution, and removing the solvent from the liquid phase to obtain a hydrogenated bisphenol A product.

Background

Hydrogenated bisphenol A (BPA) is a key raw material monomer for producing hydrogenated bisphenol A type special epoxy resin, has stable molecular structure, can effectively improve the light and heat stability and weather resistance of the synthesized epoxy resin, expands the application field of epoxy resin products, and can be used in the fields of electronic packaging materials, electronic and electrical materials, sealants, automobile coatings and the like.

Hydrogenated bisphenol A is a product generated by hydrogenation reaction of bisphenol A as a raw material in a solution state under the action of a catalyst. The reaction needs to dissolve bisphenol A (BPA) raw materials in an organic solvent to form a raw material solution with a certain concentration, the raw material solution is mixed with hydrogen in a solution form and then subjected to hydrogenation reaction, and the solvent does not participate in the reaction and is beneficial to mass transfer processes such as distribution and adsorption of raw material molecules on the surface of a catalyst and desorption of reaction products from the surface of the catalyst. And (3) carrying out hydrogenation reaction on bisphenol A molecules on the surface of the catalyst at the reaction temperature of 150-170 ℃ and the pressure of 6-10 MPaG to generate hydrogenated bisphenol A.

The technological process of preparing hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A can adopt intermittent or continuous hydrogenation reaction, and the hydrogenation catalyst mainly adopts three catalysts of metal framework type catalyst, noble metal supported catalyst and alkaline earth metal catalyst. The supported catalyst has the characteristics of wide carrier diversity and active component selection range, easy preparation, easy modification and the like, the noble metal supported catalyst is most researched and reported in the preparation of hydrogenated bisphenol A, and the improvement of the performance of the hydrogenation catalyst and the prolongation of the service life of the catalyst are important directions of research.

The main reaction of bisphenol A hydrogenation is to hydrogenate and saturate two benzene rings in bisphenol A molecules. While the main reaction is carried out, hydroxyl on a small amount of hydrogenated bisphenol A molecules can react with hydrogen to remove one or two hydroxyl groups or generate chain scission reaction to generate a byproduct. The preparation of hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A is a process of benzene ring hydrogenation, the hydrogenation process is accompanied with an exothermic phenomenon, the temperature of a catalyst bed layer is increased due to reaction heat accumulation, side reactions are aggravated due to the increase of the reaction temperature, the result of the increase of byproducts is caused, and the selectivity of the catalyst is influenced. Meanwhile, the physical properties of the by-product generated in the hydrogenation process are close to those of the hydrogenated bisphenol A product, and the by-product is difficult to separate from the hydrogenated bisphenol A product in the processes of solvent removal and refining, so that the difficulty of product refining is increased due to the aggravation of side reactions. The rising of the reaction temperature can also cause the catalyst to sinter and deposit carbon, which affects the activity and the service life of the catalyst, especially when the loading of the catalyst is increased, or the concentration and the airspeed of the feeding solution are increased, the heat release phenomenon is obvious, the side reaction is aggravated, and the catalyst sintering is caused, so the reaction temperature is controlled in the bisphenol A hydrogenation process, and the problems that the heat release is concentrated and violent in the reaction process, and the performance and the service life of the catalyst are affected are avoided.

Disclosure of Invention

The invention relates to a method for preparing hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A, which comprises the following steps: the bisphenol A solution is metered and pressurized, then mixed with metered high-pressure hydrogen, and then enters a fixed bed sleeve type hydrogenation reactor, and hydrogenation reaction is carried out on a hydrogenation catalyst bed layer. The method for hydrogenating the bisphenol A catalyst is mainly a method for avoiding overhigh temperature of a catalyst bed layer and removing part of reaction heat in the process of hydrogenating the bisphenol A, avoids catalyst sintering to shorten the service life of the catalyst, and simultaneously improves the load of the hydrogenation catalyst and reduces energy consumption.

The technical scheme of the invention is as follows:

a method for preparing hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A, the bisphenol A solution measures and boosts the pressure, mixes with the high-pressure hydrogen measured, then enters a fixed bed sleeve type hydrogenation reactor, and carries out hydrogenation reaction on a hydrogenation catalyst bed; the hydrogenation reactor adopts a sleeve hot oil heating mode, a jacket part is divided into a heating section and a heat taking section, two hot oil paths circulate, the hot oil heating furnace outputs two hot oil paths, and the two hot oil paths respectively control the oil outlet temperature; when the catalyst is filled, the method of diluting active components by adopting inert ceramic balls or carriers is adopted to avoid overhigh local temperature of a bed layer and prevent the catalyst from sintering; and (3) carrying out gas-liquid separation on the generated hydrogenated bisphenol A solution, and removing the solvent from the liquid phase to obtain a hydrogenated bisphenol A product.

The hydrogenation reactor is a single-tube type or a tube type, and the number of the tube type reactors is 2-10.

The hydrogenation reactor adopts a sleeve hot oil heating mode, the set temperature of hot oil in the heating section is the same as the hydrogenation reaction temperature, and the set temperature of hot oil in the heat taking section is 2-30 ℃ lower than the inlet temperature of hot oil in the heating section.

The hot oil heating furnace outputs two paths of hot oil and supplies oil for the heating section and the heat taking section respectively, the heating furnace is a device provided with two paths of hot oil outlets, or the two heating furnaces supply oil for the heating section and the heat taking section respectively.

The hydrogenation reactor adopts a sleeve hot oil heating mode, bisphenol A hydrogenation reaction at the temperature of hot oil at the heat taking section is 5-15 ℃ lower than that of hot oil at the heating section is exothermic reaction, and in order to avoid the problems that the raw material enters a catalyst bed layer and is intensively exothermic during hydrogenation reaction, side reaction is aggravated and the service life of the catalyst is influenced, a method of diluting the catalyst by using inert ceramic balls is adopted; when the catalyst is filled, the hydrogenation catalyst is uniformly mixed with 0.5-2 times of inert ceramic balls, and then the mixture is filled into a reactor bed layer.

The method is characterized in that inert ceramic balls are used for diluting catalytic active components, preferably, a hydrogenation catalyst is uniformly mixed with 0.8-1.5 times of volume of the inert ceramic balls, and then the mixture is filled into a reactor bed layer.

In order to avoid the concentrated heat release of the hydrogenation reaction, the invention also adopts a method of diluting the catalytic active component by the carrier, the bisphenol A solution enters the catalyst bed layer from the upper end of the reactor to carry out the hydrogenation reaction, the content of the upper catalyst loaded active component is lower, the hydrogenation activity of the catalyst is lower, the content of the lower catalyst loaded active component is higher, the hydrogenation activity of the catalyst is higher, the bisphenol A raw material passes through the catalyst bed layer, and the hydrogenation activity of the catalyst bed layer is gradually increased, so that the hydrogenation can be stably carried out, the concentrated heat release is avoided, and the hydrogenation reaction effect cannot be reduced. The bisphenol A solution passes through the catalyst bed layer from top to bottom, and the active components of the catalyst passing through the catalyst bed layer gradually increase in the process. When filling the catalyst, the lower catalyst is filled first, and the upper catalyst is filled again, for easier understanding, we will take the example of filling 100 ml of catalyst to illustrate the principle that the active components of the catalyst are gradually increased: the total volume of the catalyst is 100 ml, namely the total volume of the catalyst, the lower part is filled with 30 ml of the catalyst, and the upper part is 70 ml of the catalyst, which accounts for 70% of the total volume of the catalyst. When the catalyst is filled, the catalyst with high active component content at the lower part is filled firstly, then the catalyst with low active component content is filled, if the catalyst is filled in three parts, the catalyst with highest active component content at the lower part is filled firstly, and finally the catalyst with low active component content is filled, so that the gradual decrease of the active component content of the catalyst from bottom to top is realized. For example, the catalyst having a lower loading of active component of 2% (active component loading of 2 g for 100 g of catalyst), the middle catalyst having an active component reduced to 80% of the lower loading of active component, i.e., an active component loading of 1.6%, and the upper catalyst having an active component reduced to 60% of the lower loading of active component, i.e., an active component loading of 1.2%.

The following are the preferred conditions we have studied:

the carrier is adopted to dilute the catalytic active component, and when the hydrogenation catalyst is filled, the catalyst with the total volume of 30-70% is filled from the bottom, and then the loading capacity of the catalyst active component filled at the upper part is reduced to 50-90% of that of the catalyst at the lower part.

The method adopts a carrier to dilute catalytic active components, and when a hydrogenation catalyst is filled, after the catalyst with the total volume of 40-60% is filled from the lower part, the loading capacity of the catalyst active components filled at the upper part is reduced to 60-80% of the loading capacity of the catalyst at the lower part.

The method is characterized in that a carrier is adopted to dilute catalytic active components, when a hydrogenation catalyst is filled, the volume of the lower catalyst is 20-60% of the total volume of the catalyst, the volume of the middle catalyst is 20-50% of the total volume of the catalyst, the loading of the middle catalyst active components is reduced to 60-80% of the loading of the lower catalyst, the volume of the upper catalyst is 20-50% of the total volume of the catalyst, and the loading of the upper catalyst active components is reduced to 50-70% of the loading of the lower catalyst.

The hydrogenation reactor is a sleeve type hot oil heating reactor, the sleeve is a concentric circle sleeve formed by connecting two standard pipes with different sizes, the outer surface is a shell layer medium which is heat conducting oil, the inner pipe layer is a reactor bed layer, and a catalyst and ceramic balls are filled in the inner pipe layer. The jacket is provided with an oil inlet and an oil outlet which are connected with an external heating furnace through pipelines. In the method, a partition is arranged in the middle of a shell layer of a hot oil sleeve, a jacket part is divided into two independent parts, a heating section and a heat taking section are divided into two paths of hot oil circulation, and the heating section and the heat taking section are provided with independent oil inlets and oil outlets and can be used for respectively controlling the temperature; when a common reactor is filled, inert ceramic balls are filled firstly, then a catalyst is filled, and finally the inert ceramic balls are filled.

The hydrogenation device adopted by the invention is shown in the attached figure, an inlet of a metering pump 1 is connected with a raw material solution pipeline, an outlet of the metering pump 1 is connected with an inlet of a reactor 3, a hydrogen mass flow meter 2 on a reaction hydrogen pipeline is connected with an inlet of the reactor 3, an outlet of the reactor 3 is connected with a condenser 4, an outlet of the condenser 4 is connected with a gas-liquid separator 5, a gas-phase outlet at the upper end of the gas-liquid separator 5 is connected with a back pressure valve 6 to control the pressure of the reactor, and a liquid-phase outlet pipeline at the lower end is provided with a ball valve 14 to control the liquid level. The reactor 3 is a sleeve type hot oil heating reactor, a partition is arranged in the middle of a jacket, the jacket is divided into a heating section 8 and a heat taking section 9, heat conduction oil enters the heating section 8 from the hot oil furnace 7 through a heating section hot oil inlet pipeline 10 and returns to the hot oil furnace 7 through a heating section hot oil outlet pipeline 11; hot oil enters the heat extraction section 9 through a heat extraction section inlet pipeline 12 and returns to the hot oil furnace 7 through a heat extraction section hot oil outlet pipeline 13.

The hydrogenation reactor for bisphenol A hydrogenation reaction is a fixed bed sleeve type reactor, inert ceramic balls are filled in the tube layer, then the catalyst is filled in the tube layer, and finally the inert ceramic balls are filled in the tube layer. When the catalyst is filled, the active component is diluted by adopting a method of mixing the catalyst and inert ceramic balls or changing the load of the carrier, so that the concentrated heat release of a catalyst bed layer is avoided. The medium in the jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket part is divided into two independent parts, the lower part is a heat taking section, the upper part is a heating section, and the temperature of hot oil in the heating section and the heat taking section is respectively controlled by a hot oil furnace.

Preparing a catalyst carrier, and loading an active component to obtain the hydrogenation catalyst. And filling a catalyst and a propping agent into the reactor, and reducing the catalyst in a hydrogen atmosphere.

The invention adopts two hot oil circulations and active component dilution methods, effectively reduces the occurrence of side reactions in the hydrogenation process, reduces the content of by-products in the hydrogenation crude product, reduces the difficulty of product refining, improves the product yield, simultaneously can avoid catalyst sintering, and prolongs the service life of the catalyst

Drawings

FIG. 1: a schematic diagram of a bisphenol A catalytic hydrogenation process.

Wherein:

1-metering feed pump, 2-hydrogen mass flow controller, 3-jacket reactor, 4-condenser, 5-gas-liquid separating tank, 6-back pressure valve, 7-hot oil furnace, 8-heating section, 9-heat taking section, 10-heating section inlet, 11-heating section outlet, 12-heat taking section inlet, 13-heat taking section outlet and 14-discharging ball valve

Detailed Description

The invention is described in further detail below with reference to the following figures and specific examples:

the method adopts the flow chart shown in the figure 1 to connect pipelines and equipment for carrying out experiments. 1 access connection raw materials solution pipeline of measuring pump, 1 exit linkage reactor of measuring pump 3 entry, reaction hydrogen gas pipeline goes up hydrogen mass flow 2 and reactor 3 import and links to each other, 3 exit linkage condensers 4 of reactor, 4 exit linkage vapour and liquid separator 5 of condenser, 5 upper end gas phase exit linkage back pressure valve 6 control reactor pressure of vapour and liquid separator, lower extreme liquid phase outlet pipeline installation ball valve 14 control liquid level. The reactor 3 is a sleeve type hot oil heating reactor, a partition is arranged in the middle of a jacket, and the jacket is divided into a heating section 8 and a heat taking section 9. The reactor and the hot oil furnace are connected, so that heat conduction oil enters the heating section 8 from the hot oil furnace 7 through a heating section hot oil inlet pipeline 10 and returns to the hot oil furnace 7 through a heating section hot oil outlet pipeline 11; hot oil enters the heat extraction section 9 through a heat extraction section inlet pipeline 12 and returns to the hot oil furnace 9 through a heat extraction section hot oil outlet pipeline 13.

The invention comprises a catalyst loading and distribution method, which is illustrated by taking the example of loading 200 ml of hydrogenation catalyst to carry out bisphenol A hydrogenation reaction:

preparing 200 ml of catalyst carrier, loading active components, wherein the carrier is alumina carrier, the loaded active components are noble metal of the eighth group, the mass of the active components is 1% of the mass of the catalyst, and obtaining 200 ml of hydrogenation catalyst with 1% of loading capacity. In the example of diluting the active component by the carrier, 200 ml of the catalyst carrier was prepared, and the active component was loaded in different amounts in the upper and lower portions, or the upper, middle and lower portions

After the catalyst is filled into the reactor, the inert ceramic balls are continuously filled to fill the reactor. The catalyst was reduced under a hydrogen atmosphere.

The hydrogenation reactor for bisphenol A hydrogenation reaction is a fixed bed sleeve type reactor, and a catalyst and inert ceramic balls are filled in a straight pipe. The medium in the jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket part is divided into two independent parts, the lower part is a heat taking section, the upper part is a heating section, and the temperature of hot oil in the heating section and the heat taking section is respectively controlled by a hot oil furnace.

And (3) boosting the pressure of the reactor, metering and boosting the prepared bisphenol A solution by a metering feed pump 1 after the temperature reaches a set temperature, then feeding the solution into the reactor 3, controlling the flow of the hydrogen in a pipeline or a gas cylinder by a hydrogen mass flow controller 2, feeding the hydrogen into the reactor 3, mixing the hydrogen with the bisphenol A solution, then feeding the mixture into a catalyst bed layer for hydrogenation reaction, and hydrogenating and converting the bisphenol A into the hydrogenated bisphenol A. And condensing the hydrogenated bisphenol A solution flowing out of the outlet of the hydrogenation reactor 3 through a condenser 4, then allowing the condensed hydrogenated bisphenol A solution to enter a gas-liquid separation tank 5 for gas-liquid separation, allowing the hydrogenated bisphenol A solution to flow out of the bottom of the gas-liquid separation tank 5, and measuring the composition of the hydrogenated bisphenol A solution to investigate the hydrogenation selectivity and yield of the bisphenol A. When the composition of the hydrogenated bisphenol A solution is analyzed, gas chromatography is used, and since the solvent used in the hydrogenation process does not participate in the reaction per se and the boiling point of the solvent differs greatly from that of bisphenol A and hydrogenated bisphenol A, the solvent portion is not analyzed when the product (hydrogenated bisphenol A) is subjected to chromatographic analysis, wherein the analysis results show that the by-products include unsaturated hydrogenation products and dropped hydroxyl groups and chain scission products.

Example 1

Preparing 200 ml of catalyst carrier, loading active components, wherein the carrier is alumina carrier, the loaded active components are noble metal of the eighth group, the mass of the active components is 1% of the mass of the catalyst, and obtaining 200 ml of hydrogenation catalyst with 1% of loading capacity.

After the catalyst is filled into the catalyst bed layer of the reactor, the inert ceramic balls are continuously filled to fill the reactor. The catalyst was reduced under a hydrogen atmosphere.

The hydrogenation reactor for bisphenol A hydrogenation reaction is a fixed bed sleeve type reactor, and a catalyst and inert ceramic balls are filled in a straight pipe. The medium in the jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket part is divided into two independent parts, the lower part is a heat taking section, and the upper part is a heating section. The temperature of hot oil in the heating section is set to be 160 ℃, the temperature of hot oil in the heat taking section is set to be 130 ℃, the hot oil in the heat taking section flows out from an outlet 12 and enters a jacket, and the hot oil in the heating section flows out from an outlet 10 and enters the jacket.

The equipment is boosted to 7MPa, after the temperature reaches the set temperature, bisphenol A solution with the mass concentration of 12% is prepared, the bisphenol A solution is metered by a metering pump and is boosted to enter a reactor, hydrogen enters the reactor by controlling the flow through a hydrogen mass flow controller, and the feeding airspeed of the bisphenol A solution is 4H^-1The molar hydrogen-oil ratio is 50: 1, mixing hydrogen and a bisphenol A solution, then feeding the mixture into a catalyst bed layer, carrying out hydrogenation reaction, measuring the outlet temperature of the catalyst bed layer of the reactor, and hydrogenating and converting bisphenol A into hydrogenated bisphenol A after the reaction. Condensing the hydrogenated bisphenol A solution flowing out of the outlet of the hydrogenation reactor, then feeding the condensed hydrogenated bisphenol A solution into a gas-liquid separation tank for gas-liquid separation, allowing the hydrogenated bisphenol A solution to flow out of the bottom of the gas-liquid separation tank, measuring the composition of the hydrogenated bisphenol A solution, and inspecting the hydrogenation selectivity and yield of the bisphenol A, wherein the hydrogenated bisphenol A solution is auxiliaryThe products include unsaturated hydrogenation products and hydroxyl dropping and chain scission products. The results are shown in Table 1.

Comparative example 1

Comparative example 1 the same hydrogenation process conditions and catalyst loading method as in example 1 were used, the set temperatures of the heating section and the heat removal section of the hydrogenation reactor were both 160 ℃, and the experimental results are shown in table 1.

Example 2

Preparing 200 ml of catalyst carrier, loading active components, wherein the carrier is alumina carrier, the loaded active components are noble metal of the eighth group, the mass of the active components is 1% of the mass of the catalyst, and obtaining 200 ml of hydrogenation catalyst with 1% of loading capacity.

The catalyst and 2 times volume of inert ceramic balls are uniformly mixed and filled into a reactor, and the reactor is filled with the inert ceramic balls continuously. The catalyst was reduced under a hydrogen atmosphere.

The hydrogenation reactor for bisphenol A hydrogenation reaction is a fixed bed sleeve tubular column reactor, and 3 reactor tubes with the same size are arranged in a jacket. The catalyst and inert ceramic balls are filled in the tube. The medium in the jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket part is divided into two independent parts, the lower part is a heat taking section, and the upper part is a heating section. The temperature of hot oil in the heating section is set to be 160 ℃, the temperature of hot oil in the heat taking section is set to be 158 ℃, the hot oil in the heat taking section flows out from an outlet 12 and enters a jacket, and the hot oil in the heating section flows out from an outlet 10 and enters the jacket.

The equipment is boosted to 7MPa, after the temperature reaches the set temperature, a bisphenol A solution with the mass concentration of 15% is prepared, the bisphenol A solution is metered by a metering pump and is boosted to enter a reactor, hydrogen enters the reactor by controlling the flow through a hydrogen mass flow controller, and the feeding airspeed of the bisphenol A solution is 4H^-1The molar hydrogen-oil ratio is 50: 1, mixing hydrogen and a bisphenol A solution, then feeding the mixture into a catalyst bed layer, carrying out hydrogenation reaction, measuring the outlet temperature of the catalyst bed layer of the reactor, and hydrogenating and converting bisphenol A into hydrogenated bisphenol A after the reaction. Condensing hydrogenated bisphenol A solution flowing out of the hydrogenation reactor, then feeding the condensed hydrogenated bisphenol A solution into a gas-liquid separation tank for gas-liquid separation, allowing the hydrogenated bisphenol A solution to flow out of the bottom of the gas-liquid separation tank, measuring the composition of the hydrogenated bisphenol A solution, and investigating the hydrogenation selectivity and the hydrogenation selectivity of bisphenol AThe yield and the experimental results are shown in table 1.

Example 3

Preparing 200 ml of catalyst carrier, loading active components, wherein the carrier is alumina carrier, the loaded active components are noble metal of the eighth group, the mass of the active components is 1% of the mass of the catalyst, and obtaining 200 ml of hydrogenation catalyst with 1% of loading capacity.

The catalyst and 0.5 times volume of inert ceramic balls are uniformly mixed and filled into the reactor, and the reactor is filled with the inert ceramic balls continuously. The catalyst was reduced under a hydrogen atmosphere.

The hydrogenation reactor for bisphenol A hydrogenation is a fixed bed sleeve tubular column reactor, 2 reactor tubes with the same size are arranged in a jacket, and the cross-sectional area of the two reactor tubes is equal to that of the reactor in the example 1. The catalyst and inert ceramic balls are filled in the tube. The medium in the jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket part is divided into two independent parts, the lower part is a heat taking section, and the upper part is a heating section. The temperature of hot oil in the heating section is set to be 160 ℃, the temperature of hot oil in the heat taking section is set to be 150 ℃, the hot oil in the heat taking section flows out from an outlet 12 and enters a jacket, and the hot oil in the heating section flows out from an outlet 10 and enters the jacket.

The equipment is boosted to 7MPa, after the temperature reaches the set temperature, a bisphenol A solution with the mass concentration of 15% is prepared, the bisphenol A solution is metered by a metering pump and is boosted to enter a reactor, hydrogen enters the reactor by controlling the flow through a hydrogen mass flow controller, and the feeding airspeed of the bisphenol A solution is 4H^-1The molar hydrogen-oil ratio is 50: 1, mixing hydrogen and a bisphenol A solution, then feeding the mixture into a catalyst bed layer, carrying out hydrogenation reaction, measuring the outlet temperature of the catalyst bed layer of the reactor, and hydrogenating and converting bisphenol A into hydrogenated bisphenol A after the reaction. And condensing the hydrogenated bisphenol A solution flowing out of the hydrogenation reactor, then feeding the condensed hydrogenated bisphenol A solution into a gas-liquid separation tank for gas-liquid separation, allowing the hydrogenated bisphenol A solution to flow out of the bottom of the gas-liquid separation tank, measuring the composition of the hydrogenated bisphenol A solution, and investigating the hydrogenation selectivity and yield of the bisphenol A, wherein the experimental results are shown in table 1.

Example 4

Preparing 200 ml of catalyst carrier, loading active components, wherein the carrier is alumina carrier, the loaded active components are noble metal of the eighth group, the mass of the active components is 1% of the mass of the catalyst, and obtaining 200 ml of hydrogenation catalyst with 1% of loading capacity.

The catalyst and 1 time volume of inert ceramic ball are mixed evenly and filled into the reactor, and the reactor is filled with the inert ceramic ball continuously. The catalyst was reduced under a hydrogen atmosphere.

The hydrogenation reactor for bisphenol A hydrogenation is a fixed bed sleeve tubular column reactor, 2 reactor tubes with the same size are arranged in a jacket, and the cross-sectional area of the two reactor tubes is equal to that of the reactor in the example 1. The catalyst and inert ceramic balls are filled in the tube. The medium in the jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket part is divided into two independent parts, the lower part is a heat taking section, and the upper part is a heating section. The temperature of hot oil in the heating section is set to be 160 ℃, the temperature of hot oil in the heat taking section is set to be 145 ℃, the hot oil in the heat taking section flows out from an outlet 12 and enters a jacket, and the hot oil in the heating section flows out from an outlet 10 and enters the jacket.

The equipment is boosted to 7MPa, after the temperature reaches the set temperature, bisphenol A solution with the mass concentration of 22% is prepared, the bisphenol A solution is metered by a metering pump and is boosted to enter a reactor, hydrogen enters the reactor by controlling the flow through a hydrogen mass flow controller, and the feeding airspeed of the bisphenol A solution is 4H^-1The molar hydrogen-oil ratio is 50: 1, mixing hydrogen and a bisphenol A solution, then feeding the mixture into a catalyst bed layer, carrying out hydrogenation reaction, measuring the outlet temperature of the catalyst bed layer of the reactor, and hydrogenating and converting bisphenol A into hydrogenated bisphenol A after the reaction. And condensing the hydrogenated bisphenol A solution flowing out of the hydrogenation reactor, then feeding the condensed hydrogenated bisphenol A solution into a gas-liquid separation tank for gas-liquid separation, allowing the hydrogenated bisphenol A solution to flow out of the bottom of the gas-liquid separation tank, measuring the composition of the hydrogenated bisphenol A solution, and investigating the hydrogenation selectivity and yield of the bisphenol A, wherein the experimental results are shown in table 1.

Example 5

Preparing 200 ml of catalyst carrier, loading active components, wherein the carrier is alumina carrier, the loaded active components are noble metal of the eighth group, the mass of the active components is 1% of the mass of the catalyst, and obtaining 1000 ml of hydrogenation catalyst with 1% of loading capacity.

The hydrogenation reactor for bisphenol A hydrogenation reaction is a fixed bed sleeve tubular column reactor, and 10 reactor tubes with the same size are arranged in a jacket. After the catalyst is uniformly filled into each reactor, the inert ceramic balls are continuously filled to fill the reactors. The catalyst was reduced under a hydrogen atmosphere.

The medium in the jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket part is divided into two independent parts, the lower part is a heat taking section, and the upper part is a heating section. The temperature of hot oil in the heating section is set to be 160 ℃, the temperature of hot oil in the heat taking section is set to be 155 ℃, the hot oil in the heat taking section flows out from the outlet 121 and enters the jacket, and the hot oil in the heating section flows out from the outlet 10 and enters the jacket.

The equipment is boosted to 7MPa, after the temperature reaches the set temperature, bisphenol A solution with the mass concentration of 22% is prepared, the bisphenol A solution is metered by a metering pump and is boosted to enter a reactor, hydrogen enters the reactor by controlling the flow through a hydrogen mass flow controller, and the feeding airspeed of the bisphenol A solution is 4H^-1The molar hydrogen-oil ratio is 50: 1, mixing hydrogen and a bisphenol A solution, then feeding the mixture into a catalyst bed layer, carrying out hydrogenation reaction, measuring the outlet temperature of the catalyst bed layer of the reactor, and hydrogenating and converting bisphenol A into hydrogenated bisphenol A after the reaction. And condensing the hydrogenated bisphenol A solution flowing out of the hydrogenation reactor, then feeding the condensed hydrogenated bisphenol A solution into a gas-liquid separation tank for gas-liquid separation, allowing the hydrogenated bisphenol A solution to flow out of the bottom of the gas-liquid separation tank, measuring the composition of the hydrogenated bisphenol A solution, and investigating the hydrogenation selectivity and yield of the bisphenol A, wherein the experimental results are shown in table 1.

TABLE 1 hydrogenation effect of bisphenol A

Examples 6 to 9

200 ml of catalyst carrier is prepared, active components are loaded according to the table 2, the carrier is alumina carrier, and the loaded active components are noble metals of the eighth group.

After the catalyst is filled into the catalyst bed layer of the reactor, the inert ceramic balls are continuously filled to fill the reactor. The catalyst was reduced under a hydrogen atmosphere.

The hydrogenation reactor for bisphenol A hydrogenation reaction is a fixed bed sleeve type reactor, the medium in a jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket is divided into two independent parts, the lower part is a heat taking section, and the upper part is a heating section. The temperature of hot oil in the heating section is set to be 160 ℃, the temperature of hot oil in the heat taking section is set to be 155 ℃, the hot oil in the heat taking section flows out from an outlet 12 and enters a jacket, and the hot oil in the heating section flows out from an outlet 10 and enters the jacket.

The hydrogenation process and conditions are the same as those in examples 3-5, the outlet temperature of the catalyst bed of the reactor is measured, the composition of the hydrogenated bisphenol A solution is determined, the hydrogenation selectivity and yield of bisphenol A are investigated, and the experimental results are shown in Table 3.

TABLE 2 catalyst loadings

TABLE 3 hydrogenation effect of bisphenol A

Examples 10 to 13

200 ml of catalyst carrier is prepared, and active components are loaded according to the table 4, wherein the carrier is alumina carrier, and the loaded active components are noble metals of the eighth group.

After the catalyst is filled into the catalyst bed layer of the reactor, the inert ceramic balls are continuously filled to fill the reactor. The catalyst was reduced under a hydrogen atmosphere.

The hydrogenation reactor for bisphenol A hydrogenation reaction is a fixed bed sleeve type reactor, the medium in a jacket is heat conducting oil, the middle of the jacket is provided with a partition, the jacket is divided into two independent parts, the lower part is a heat taking section, and the upper part is a heating section. The temperature of hot oil in the heating section is set to be 160 ℃, the temperature of hot oil in the heat taking section is set to be 150 ℃, the hot oil in the heat taking section flows out from an outlet 12 and enters a jacket, and the hot oil in the heating section flows out from an outlet 10 and enters the jacket.

The hydrogenation process and conditions are the same as those in examples 3-5, the outlet temperature of the catalyst bed of the reactor is measured, the composition of the hydrogenated bisphenol A solution is determined, the hydrogenation selectivity and yield of bisphenol A are investigated, and the experimental results are shown in Table 5.

TABLE 4 hydrogenation catalyst loadings

TABLE 5 hydrogenation effect of bisphenol A

In the embodiment, the reactors all adopt two sections of independent hot oil temperature-controlled sleeve type reactors, the heating section and the heat taking section in the comparative example 1 are set to have the same temperature, the effect is the same as that of the common sleeve type reactor, and the effect of removing reaction heat is not realized. Wherein, the embodiment 1 is a single-tube reactor, the embodiments 2-5 are tubular reactors, and the heating section and the heat extraction section in the embodiments are respectively set with different temperatures. In examples 2-4, the method of diluting the active component by inert ceramic balls is adopted to avoid the local temperature of the catalyst bed layer from being too high, and in examples 6-13, the method of diluting the active component by a carrier to avoid local concentrated heat release is adopted to carry out hydrogenation experiments, wherein the catalyst loaded in examples 6-9 is divided into an upper part and a lower part, and the amount of the active component loaded on the catalyst loaded in the upper part and the lower part is different and is the same as the total volume of the catalyst loaded in example 1. The catalyst loaded in the examples 10-13 is divided into an upper part, a middle part and a lower part, and the amount of the loaded active component of the catalyst in the three parts is different and is the same as the total volume of the loaded catalyst in the example 1.

While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention. The invention belongs to the known technology.