A device, method and application for refining hydrogenated bisphenol a

Abstract

This invention proposes an apparatus, method, and application for refining hydrogenated bisphenol A. The apparatus for refining hydrogenated bisphenol A includes a supply end for the hydrogenated bisphenol A to be refined, a supply end for solvent b, a distillation column, a cooling assembly, a solid-liquid separator, and piping. The distillation column is placed vertically and includes an inlet a, an inlet b, an outlet c, and an outlet d. The height of inlet a is higher than that of inlet b and outlet d. The supply end for the hydrogenated bisphenol A to be refined is connected to inlet b, and the supply end for solvent b is connected to inlet a. The distillation column, cooling assembly, and solid-liquid separator are sequentially connected via piping, and the cooling assembly is connected to outlet c of the distillation column. Using the apparatus and method of this invention to refine hydrogenated bisphenol A, the obtained refined bisphenol A has high purity and can be applied in fields such as 3D printing materials and electronic packaging materials.

Description

Technical Field

[0001] This invention relates to the field of hydrogenated bisphenol A preparation, and specifically to an apparatus, method, and application for refining hydrogenated bisphenol A. Background Technology

[0002] Bisphenol A type epoxy resin is a linear polymer formed by the condensation polymerization of bisphenol A and epichlorohydrin in the presence of a catalyst. Bisphenol A type epoxy resin is widely used in plastic encapsulation materials due to its excellent mechanical and electrical insulation properties, chemical resistance, and stability. However, ordinary bisphenol A type epoxy resin contains an unsaturated benzene ring structure in its molecular chain, making it prone to aging and discoloration under long-term ultraviolet light exposure, leading to a significant decrease in its transparency, insulation, and strength. Replacing the benzene ring in the molecular chain with a saturated cyclic hydrocarbon structure, the resulting hydrogenated bisphenol A type epoxy resin can effectively overcome these shortcomings without reducing its mechanical and heat resistance properties. Hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane) is an important monomer for manufacturing hydrogenated bisphenol A type specialty epoxy resins. Hydrogenated bisphenol A has a stable molecular structure and can be used not only to manufacture special epoxy resins, but also to manufacture unsaturated polyester resins, polycarbonates, polyacrylic acid resins and other polymer synthetic materials. It can effectively improve the weather resistance and light and heat stability of synthetic resins, expand the application fields of resin products, and can be used in aerospace materials, electronic packaging materials, electronic and electrical materials, sealants, automotive coatings and other fields.

[0003] Hydrogenated bisphenol A is an alicyclic diol obtained by catalytic hydrogenation, which involves hydrogenating and saturating the two benzene rings in the bisphenol A (BPA) molecule. The preparation of hydrogenated bisphenol A from bisphenol A uses bisphenol A (BPA) as a raw material, and the hydrogenation reaction is carried out in solution under the action of a catalyst. The process can be batch or continuous. Regardless of whether the hydrogenation reaction is batch or continuous, a solvent is used. The reaction requires dissolving the bisphenol A (BPA) raw material in an organic solvent to form a raw material solution of a certain concentration. The hydrogenation reaction takes place in solution form. The solvent itself does not participate in the reaction; its role is to facilitate the distribution and adsorption of raw material molecules on the catalyst surface, as well as the desorption of reaction products from the catalyst surface, and other mass transfer processes. Simultaneously, the solvent also has good solubility for bisphenol A at room temperature, which facilitates fluid transport.

[0004] In existing technologies, literature and patents concerning hydrogenated bisphenol A focus on hydrogenation processes, hydrogenation catalysts, and applications in the preparation of synthetic materials such as epoxy resins and polycarbonates. There are relatively few reports on the desolventizing and refining processes of hydrogenated bisphenol A. A concentration of 96% or higher in commercially available hydrogenated bisphenol A is sufficient for the production of general hydrogenated bisphenol A-type epoxy resins. However, for high-end applications such as 3D printing materials and electronic packaging materials, higher purity of hydrogenated bisphenol A and lower content of byproducts are required.

[0005] Bisphenol A and hydrogenated bisphenol A have good solubility in solution. The boiling points of the selected solvents and hydrogenated bisphenol A differ significantly under normal pressure and vacuum conditions. Therefore, the main purification method for hydrogenated bisphenol A is to remove solvents and by-products using equipment such as distillation columns and evaporators. However, since the by-products generated by the side reaction during hydrogenation are similar to those of hydrogenated bisphenol A in terms of boiling point, polarity, and other physical properties, if it is necessary to remove by-products during the purification process to obtain a product with high purity of hydrogenated bisphenol A, the distillation column and evaporator must have a high separation efficiency, resulting in large equipment investment and energy consumption. Summary of the Invention

[0006] To address the aforementioned problems in the prior art, this invention proposes an apparatus, method, and application for refining hydrogenated bisphenol A.

[0007] In a first aspect, the present invention provides an apparatus for refining hydrogenated bisphenol A.

[0008] This includes the supply end for the hydrogenated bisphenol A to be purified, the supply end for solvent b, the distillation column, the cooling components, the solid-liquid separator, and the piping.

[0009] The distillation column is placed vertically and includes inlet a, inlet b, outlet c and outlet d. The height of inlet a is higher than that of inlet b and outlet d. The hydrogenated bisphenol A to be purified is supplied to inlet b and the solvent b is supplied to inlet a.

[0010] The distillation column, cooling unit, and solid-liquid separator are connected sequentially via pipelines, and the cooling unit is connected to the outlet c of the distillation column;

[0011] The hydrogenated bisphenol A to be purified includes hydrogenated bisphenol A and solvent a;

[0012] The distillation column is used to replace solvent a in the hydrogenated bisphenol A to be purified with solvent b;

[0013] The cooling component is used to precipitate hydrogenated bisphenol A from solvent b;

[0014] The solid-liquid separator is used to separate hydrogenated bisphenol A precipitated in the cooling unit from solvent b.

[0015] In a specific embodiment of the present invention, the solid-liquid separator is a centrifuge.

[0016] Preferably, the boiling point of solvent b is higher than that of solvent a, and the difference between the boiling points of solvent a and solvent b is less than or equal to 30°C. When the difference between the boiling points of solvent a and solvent b is greater than 30°C, a reaction vessel with an external heating jacket or an internal heating coil can be used to replace the distillation column.

[0017] As a specific embodiment of the present invention, the apparatus for refining hydrogenated bisphenol A further includes a solvent recovery tank, which is connected to the outlet d of the distillation column and is used to recover the solvent, specifically to recover solvent a.

[0018] In a specific embodiment of the present invention, a condenser is also provided in the solvent recovery tank and the discharge port d. The condenser is used to condense the gaseous solvent a discharged from the distillation column.

[0019] As a specific embodiment of the present invention, the apparatus for refining hydrogenated bisphenol A further includes a vacuum pump, which is connected to a solvent recovery tank to establish vacuum conditions within the apparatus for refining hydrogenated bisphenol A.

[0020] In a specific embodiment of the present invention, the hydrogenated bisphenol A supply end includes a hydrogenated bisphenol A storage tank and a hydrogenated bisphenol A feed pump; the hydrogenated bisphenol A feed pump is used to control the feed rate of the hydrogenated bisphenol A to be refined.

[0021] As a specific embodiment of the present invention, the solvent b supply end also includes a solvent b storage tank and a solvent b feed pump; the solvent b feed pump is used to control the feeding speed of solvent b.

[0022] As a specific embodiment of the present invention, the apparatus for refining hydrogenated bisphenol A further includes a flow valve installed in the feed pipeline of the distillation column. The flow valve is used to control the flow rate of the feed to the distillation column. Under high vacuum conditions, it is not necessary to install a feed pump for the hydrogenated bisphenol A to be refined and a feed pump for solvent b. Instead, a flow control valve needs to be installed in the feed pipeline of the distillation column to ensure a smooth entry of the hydrogenated bisphenol A to be refined and solvent b into the distillation column, and to achieve flow control.

[0023] As a specific embodiment of the present invention, the apparatus for refining hydrogenated bisphenol A includes a discharge pump connected to a discharge port b, which is used to control the discharge from the discharge port d of the distillation column.

[0024] In a specific embodiment of the present invention, the cooling assembly includes a reaction vessel, a cooler, and a temperature controller. The cooler is used to reduce the temperature inside the reaction vessel, and the temperature controller is used to control the cooling rate of the cooler. Specifically, the cooler in the present invention is a heating jacket disposed outside the reaction vessel or a heating coil disposed inside the reaction vessel. Specifically, the temperature controller is a temperature-controlled circulator.

[0025] In a specific embodiment of the present invention, the reactor includes an inlet e and an outlet f. The reactor is placed vertically, with the inlet e located at the top and the outlet f located at the bottom. The inlet e is connected to the outlet c of the distillation column, and the outlet f is connected to the solid-liquid separator.

[0026] As a specific embodiment of the present invention, the reaction vessel is equipped with a stirring device.

[0027] As a specific embodiment of the present invention, the apparatus further includes a drying chamber, which is used to dry the hydrogenated bisphenol A obtained after separation by a solid-liquid separator.

[0028] In a second aspect, the present invention provides a method for purifying hydrogenated bisphenol A using the apparatus provided in the first aspect of the present invention, comprising the following steps:

[0029] Step S1: The hydrogenated bisphenol A to be purified is introduced into the distillation column. The hydrogenated bisphenol A to be purified is separated into bisphenol A and solvent a in the distillation column. Solvent a is discharged from the distillation column.

[0030] Step S2: Introduce solvent b into the distillation column, and mix solvent b with hydrogenated bisphenol A;

[0031] Step S3: Precipitate hydrogenated bisphenol A from solution b;

[0032] Step S4: Separate the hydrogenated bisphenol A precipitated in step S3 from solvent b to obtain hydrogenated bisphenol A.

[0033] As a specific embodiment of the present invention, step S4 is followed by step S5, in which the hydrogenated bisphenol A obtained after solid-liquid separation in step S4 is dried.

[0034] As a specific embodiment of the present invention, solvent a includes at least one of ethanol, isopropanol, isobutanol, and cyclohexanol.

[0035] As a specific embodiment of the present invention, solution b includes one or more of toluene, p-xylene, o-xylene, m-xylene, mixed xylene, mesitylene, and mesitylene.

[0036] As a specific embodiment of the present invention, the amount of solvent b added to the distillation column is 20% to 300% of the mass of the hydrogenated bisphenol A to be purified.

[0037] Preferably, the amount of solvent b added to the distillation column is 40% to 100% of the mass of the hydrogenated bisphenol A to be purified.

[0038] In a specific embodiment of the present invention, the amount of solvent b added to the distillation column is 2 to 10 times the mass of hydrogenated bisphenol A in the hydrogenated bisphenol A to be purified.

[0039] Preferably, the amount of solvent b added to the distillation column is 3 to 6 times the mass of hydrogenated bisphenol A in the hydrogenated bisphenol A to be purified.

[0040] And / or, as a specific embodiment of the present invention, solution b is introduced into the distillation column when the mass of the remaining solvent a in the distillation column is 50% of the total mass of the solution in the distillation column or when the mass of the remaining solvent a in the distillation column is less than 50% of the total mass of the solution in the distillation column.

[0041] In a specific embodiment of the present invention, the pressure in the distillation column is atmospheric pressure or a controlled pressure of 0 to -0.09 MPaG. During the solvent replacement process, when the boiling point of solvent a is less than 85°C, solvent replacement is performed under atmospheric pressure, and the removal of solvent a and the replenishment of solvent b can be carried out simultaneously. When the boiling point of solvent a is greater than 85°C, solvent replacement is performed under reduced pressure; the higher the boiling point, the higher the required vacuum level. When the boiling point of solvent b is higher than that of solvent a, and the difference between the two is greater than 20°C, the removal of solvent a and the replenishment of solvent b can be carried out simultaneously. When the difference between the two is less than or equal to 20°C, or even when the boiling point of solvent b is lower than that of solvent a, solvent a is removed first, and after achieving the required solvent removal rate, solvent b is slowly replenished under controlled temperature.

[0042] And / or, as an embodiment of the present invention, step 3 involves placing a mixture of hydrogenated bisphenol A and solution b in a reaction vessel, and precipitating hydrogenated bisphenol A from solution b by lowering the temperature of the reaction vessel.

[0043] Preferably, when the temperature of the mixture is above 60°C, the cooling rate of the reactor is 5–15°C / H1.

[0044] Thirdly, the present invention provides an application of the apparatus provided in the first aspect of the present invention or the method provided in the second aspect of the present invention in the purification of hydrogenated bisphenol A.

[0045] Fourthly, the present invention provides a purified hydrogenated bisphenol A prepared using the apparatus provided in the first aspect of the present invention or the method provided in the second aspect of the present invention, wherein the purified hydrogenated bisphenol A has a mass content of more than 98%.

[0046] Compared with the prior art, the present invention has the following beneficial effects.

[0047] The apparatus and method of this invention refine hydrogenated bisphenol A products, resulting in high-purity refined bisphenol A suitable for applications in 3D printing materials, electronic packaging materials, and other fields. The refined hydrogenated bisphenol A obtained by this invention achieves a bisphenol A mass content of up to 98%, and a single-pass yield of 93%. Attached Figure Description

[0048] Figure 1 This is a schematic diagram of the hydrogenated bisphenol A refining process of the present invention;

[0049] 1- Hydrogenated bisphenol A supply end to be refined, 11- Hydrogenated bisphenol A storage tank to be refined, 12- Hydrogenated bisphenol A feed pump to be refined.

[0050] 2- Solvent b supply end, 21- Solvent b storage, 22- Solvent b feed pump,

[0051] 3-Distillation column, 31-Inlet a, 32-Inlet b, 33-Outlet c, 34-Outlet d,

[0052] 4-Cooling component, 41-Reaction vessel, 42-Cooler, 43-Temperature controller and circulator, 411-Inlet e, 412-Outlet f,

[0053] 5-Solid-liquid separator, 6-Solvent recovery tank, 7-Condenser,

[0054] 8-Vacuum pump, 9-Discharge pump, 10-Drying oven. Detailed Implementation

[0055] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0056] Example 1

[0057] An apparatus for refining hydrogenated bisphenol A includes a hydrogenated bisphenol A supply end 1, a solvent b supply end 2, a distillation column 3, a cooling assembly 4, a solid-liquid separator 5, and pipelines.

[0058] The distillation column 3 is placed vertically. The distillation column 3 includes a feed inlet a31, a feed inlet b32, a discharge outlet c33 and a discharge outlet d34. The height of the feed inlet a is higher than that of the feed inlet b. The supply end of the hydrogenated bisphenol A to be purified is connected to the feed inlet b32, and the supply end of the solvent b is connected to the feed inlet 31.

[0059] Distillation column 3, cooling assembly 4, and solid-liquid separator 5 are connected sequentially through pipelines, and cooling assembly 4 is connected to the bottom of distillation column 3.

[0060] Specifically, the hydrogenated bisphenol A to be purified includes hydrogenated bisphenol A and solvent a;

[0061] Specifically, distillation column 3 is used to replace solvent a in the hydrogenated bisphenol A to be purified with solvent b;

[0062] Specifically, the cooling component is used to precipitate hydrogenated bisphenol A from solvent b;

[0063] Specifically, the solid-liquid separator 5 is used to separate the hydrogenated bisphenol A precipitated in the cooling component 4 from the solvent b.

[0064] Furthermore, the apparatus for refining bisphenol A also includes a solvent recovery tank 6, which is connected to the top of the distillation column 3 at outlet d34. A condenser 7 is also installed directly between the solvent recovery tank 6 and outlet d34. The condenser 7 is used to condense the gaseous solvent a discharged from the distillation column 3.

[0065] Specifically, the apparatus for refining hydrogenated bisphenol A also includes a vacuum pump 8, which is connected to a solvent recovery tank 6 to establish vacuum conditions within the apparatus for refining hydrogenated bisphenol A.

[0066] Furthermore, the hydrogenated bisphenol A supply end 1 to be refined includes a hydrogenated bisphenol A storage tank 11 and a hydrogenated bisphenol A feed pump 12; the hydrogenated bisphenol A feed pump 12 is used to control the feed rate of the hydrogenated bisphenol A to be refined.

[0067] Specifically, the solvent b supply end 2 also includes a solvent b storage tank 21 and a solvent b feed pump 22; the solvent b feed pump 22 is used to control the feed rate of solvent b.

[0068] Specifically, the apparatus for refining hydrogenated bisphenol A also includes a flow valve installed in the feed pipeline of the distillation column. The flow valve is used to control the flow rate of the feed to the distillation column. Under high vacuum conditions, it is not necessary to install a feed pump for the hydrogenated bisphenol A to be refined and a feed pump for solvent b. Instead, a flow control valve needs to be installed in the feed pipeline of the distillation column to ensure that the hydrogenated bisphenol A to be refined and solvent b enter the distillation column smoothly and to achieve flow control.

[0069] The apparatus for refining hydrogenated bisphenol A includes a discharge pump 9, which is connected to a discharge port b34. The discharge pump 9 is used to control the discharge from the discharge port d34 of the distillation column.

[0070] Furthermore, the cooling assembly 4 includes a reaction vessel 41, a cooler 42, and a temperature controller 43.

[0071] The reactor 41 includes a feed inlet e411 and a discharge outlet f412. The reactor 41 is placed vertically, with the feed inlet e411 located at the top of the reactor 41 and the discharge outlet f412 located at the bottom of the reactor. The feed inlet e411 is connected to the discharge outlet c33 of the distillation column 3, and the discharge outlet f412 is connected to the solid-liquid separator.

[0072] Furthermore, the cooling device 42 is a heating jacket installed in the reactor 41, and the temperature controller 43 is a temperature control circulator connected to the heating jacket to control the temperature of the heating jacket, thereby controlling the temperature of the reactor 41.

[0073] Specifically, a stirring device with controllable rotation speed is installed inside the reactor.

[0074] Specifically, the solid-liquid separator 5 is a centrifuge, which is used to separate the hydrogenated bisphenol A precipitated in the reaction vessel 41 from the solvent b.

[0075] Furthermore, the apparatus for refining hydrogenated bisphenol A also includes a drying oven 10, which is used to dry the hydrogenated bisphenol A obtained after centrifugation, and the hydrogenated bisphenol A is purified after drying.

[0076] Example 2

[0077] The hydrogenated bisphenol A to be purified includes isopropanol (solvent a) and crude hydrogenated bisphenol A with a mass purity of 96.12%, with a mass concentration of 10% in the hydrogenated bisphenol A to be purified. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters the distillation column. After the column reaches 2 / 3 of its capacity in the bottom, the distillation column is heated until the vapor temperature at the top of the column reaches 82–84°C. Solvent a vaporizes and is discharged from the top of the distillation column. The vaporized solvent a is condensed and refluxed in a condenser and then collected in a solvent recovery tank. The medium temperature in the condenser is 15–20°C. When the remaining proportion of solvent a reaches 60% (the mass of undistilled solvent a is 60% of the total mass of the solution in the distillation column), the solvent b feed pump is started. Solvent b is p-xylene. The temperature is gradually adjusted... The flow rate of hydrogenated bisphenol A to be purified was set to 10 kg / h, and the flow rate of p-xylene was set to 10 kg / h. The operating conditions of the distillation column were adjusted so that 8 kg / h of solvent a was collected, the remaining proportion of solvent a reached 50% (the mass of undistilled solvent a is 50% of the total mass of the solution in the distillation column), and the liquid level in the distillation column was stable. The discharge pump was turned on, and the discharge flow rate of hydrogenated bisphenol A and solvent b was set to 12 kg / h. After the solvent was replaced, the newly formed hydrogenated bisphenol A and solvent b were pumped out from the bottom of the distillation column by the discharge pump and entered the reactor equipped with a controllable speed stirring device. The reactor was operated intermittently, with the stirring speed maintained at a constant 30-50 rpm. The reactor was jacketed, with a heat-conducting medium inside. Temperature-controlled circulators were connected to the inlet and outlet pipes of the medium. During the pumping of hydrogenated bisphenol A and solvent b, the pipes were insulated and heated to maintain a constant temperature within the reactor. Feeding was stopped when the liquid level reached 50-70% of the flow rate. The temperature was then lowered to 60°C at a rate of 5°C per hour, and then further lowered to 30°C at a rate of 15°C per hour. The mixture was stirred at 30°C for 2 hours to obtain a solid-liquid mixture. This mixture was then discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven, where nitrogen gas was introduced at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0078] Example 3

[0079] The hydrogenated bisphenol A to be purified includes ethanol (solvent a) and crude hydrogenated bisphenol A with a purity of 96.12%, which has a mass concentration of 30% in the hydrogenated bisphenol A to be purified. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters the distillation column. After the column reaches 2 / 3 of its capacity in the bottom, the distillation column is heated until the vapor temperature at the top of the column reaches 78–80°C. Solvent a vaporizes and is discharged from the top of the distillation column. The vaporized solvent a is condensed and refluxed in a condenser and then collected in a solvent recovery tank. The medium temperature in the condenser is 15–20°C. When the remaining proportion of solvent a reaches 60% (the mass of undistilled solvent a is 60% of the total mass of the solution in the distillation column), the solvent b feed pump is started. Solvent b consists of o-xylene and toluene. A 1:1 mixture of solutions was prepared. The flow rates were gradually adjusted, and the feed flow rate of the hydrogenated bisphenol A to be purified was set to 10 kg / h, while the feed flow rate of the mixed solution was set to 30 kg / h. The operating conditions of the distillation column were adjusted until the remaining proportion of solvent a reached 50% (the mass of undistilled solvent a is 50% of the total mass of the solution in the distillation column) and the liquid level in the distillation column was stable. The discharge pump was turned on, and the discharge flow rate of hydrogenated bisphenol A and solvent b was set to 36 kg / h. After the solvent was replaced, the newly formed hydrogenated bisphenol A and solvent b were pumped out from the bottom of the distillation column by the discharge pump and entered the reactor equipped with a controllable speed stirrer. The reactor was operated intermittently, with the stirring speed maintained at a constant rate. The reactor was jacketed, with a heat-conducting medium inside. Temperature-controlled circulators were connected to the inlet and outlet pipes of the medium. During the pumping of hydrogenated bisphenol A and solvent b, the pipes were insulated and heated to maintain a constant temperature within the reactor. Feeding was stopped when the liquid level reached 70% of the capacity, and the temperature was lowered to 30°C at a rate of 5°C per hour. The mixture was then stirred at 30°C for 2 hours. The solid-liquid mixture was discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven, where nitrogen gas was introduced at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0080] Example 4

[0081] The hydrogenated bisphenol A to be purified consists of isopropanol (solvent a) and crude hydrogenated bisphenol A with a mass purity of 96.12%, where the crude hydrogenated bisphenol A has a mass concentration of 20% in the hydrogenated bisphenol A to be purified. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters the distillation column. After the column bottom reaches 2 / 3 of the liquid level, the vacuum pump is started. The vacuum pump is connected to the solvent recovery tank to provide the vacuum conditions for this process, and the vacuum degree is controlled at -0.02 MPa. After the vacuum is established, the distillation column is heated until the vapor temperature at the top of the column reaches 72-74°C. Solvent a vaporizes and is discharged from the top of the distillation column. The vaporized solvent a is condensed and refluxed in the condenser and then collected in the solvent recovery tank. The medium temperature in the condenser is 15-20°C. When the remaining proportion of solvent a reaches 60% (the mass of undistilled solvent a is 60% of the total mass of the solution in the distillation column), the solvent b feed pump is started. Solvent b is m-xylene. The flow rate is gradually adjusted, and the hydrogenation temperature to be purified is set. The bisphenol A feed flow rate is set to 10 kg / h, and the m-xylene feed flow rate is set to 6 kg / h. The operating conditions of the distillation column are adjusted so that the remaining proportion of solvent a reaches 40% (the mass of undistilled solvent a is 40% of the total mass of the solution in the distillation column) and the liquid level in the distillation column is stable. The discharge pump is turned on, and the discharge flow rate of hydrogenated bisphenol A and solvent b is set to 9.4 kg / h. After the solvent is replaced, the newly formed hydrogenated bisphenol A and solvent b are pumped out from the bottom of the distillation column by the discharge pump and enter the reaction vessel equipped with a controllable speed stirrer. The reactor was operated intermittently, with the stirring speed maintained at a constant speed. The reactor was jacketed, with a heat-conducting medium inside. Temperature-controlled circulators were connected to the inlet and outlet pipes of the medium. During the pumping of hydrogenated bisphenol A and solvent b, the pipes were insulated and heated to maintain a constant temperature inside the reactor. Feeding was stopped when the liquid level reached 70% of the capacity. The temperature was then reduced to 60°C at a rate of 10°C per hour, and then further reduced to 30°C at a rate of 15°C per hour. The mixture was stirred at 30°C for 2 hours. The solid-liquid mixture was then discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven. Nitrogen gas was introduced into the drying oven at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0082] Example 5

[0083] The hydrogenated bisphenol A to be purified includes isobutanol (solvent a) and crude hydrogenated bisphenol A with a mass purity of 96.12%, and the mass concentration of crude hydrogenated bisphenol A in the hydrogenated bisphenol A to be purified is 15%. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters the distillation column. After the column bottom reaches 2 / 3 liquid level, the vacuum pump is started to establish vacuum conditions. The vacuum pump is connected to the solvent recovery tank to provide vacuum conditions for this process, and the vacuum degree is controlled at -0.03 MPa. After the vacuum is established, the distillation column is heated until the vapor temperature at the top of the column reaches 73-75°C. Solvent a vaporizes and is discharged from the top of distillation column 3. The vaporized solvent a is condensed and refluxed in the condenser and then collected in the solvent recovery tank. The medium temperature in the condenser is 15-20°C. When the remaining proportion of solvent a reaches 60% (the mass of undistilled solvent a is 60% of the total mass of the solution in the distillation column), the solvent b feed pump is started. Solvent b is a mixture of xylenes containing p-xylene, m-xylene, and o-xylene. The flow rate is gradually adjusted. The feed flow rate of the hydrogenated bisphenol A to be purified was set to 10 kg / h, and the feed flow rate of the mixed xylene was set to 3 kg / h. The operating conditions of the distillation column were adjusted so that the remaining proportion of solvent a reached 35% (the mass of the undistilled solvent a is 35% of the total mass of the solution in the distillation column) and the liquid level in the distillation column was stable. The discharge pump was then turned on, and the discharge flow rate of hydrogenated bisphenol A and solvent b was set to 5.3 kg / h. After the solvent was replaced, the newly formed hydrogenated bisphenol A and solvent b were pumped out from the bottom of the distillation column by the discharge pump and entered the reactor equipped with a controllable speed stirrer. The reactor was operated intermittently, with the stirring speed maintained at a constant speed. The reactor was jacketed, with a heat-conducting medium inside. Temperature-controlled circulators were connected to the inlet and outlet pipes of the medium. During the pumping of hydrogenated bisphenol A and solvent b, the pipes were insulated and heated to maintain a constant temperature inside the reactor. Feeding was stopped when the liquid level reached 70% of the capacity. The temperature was then reduced to 60°C at a rate of 10°C per hour, and then further reduced to 30°C at a rate of 15°C per hour. The mixture was stirred at 30°C for 2 hours. The solid-liquid mixture was then discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven. Nitrogen gas was introduced into the drying oven at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0084] Example 6

[0085] The hydrogenated bisphenol A to be purified includes isopropanol (solvent a) and crude hydrogenated bisphenol A with a purity of 95.76%, where the crude hydrogenated bisphenol A has a mass concentration of 10% in the hydrogenated bisphenol A to be purified. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters distillation column 3. After the bottom reaches 2 / 3 of the liquid level, the distillation column is heated until the vapor temperature at the top of the column reaches 82-84°C. Solvent a vaporizes and is discharged from the top of the distillation column. The vaporized solvent a is condensed and refluxed in a condenser and then collected in a solvent recovery tank. The medium temperature in the condenser is 15-20°C. When the remaining proportion of solvent a reaches 60% (the mass of undistilled solvent a is 60% of the total mass of the solution in the distillation column), the solvent b feed pump is started. Solvent b is... Toluene was gradually introduced, and the feed flow rate of the hydrogenated bisphenol A to be purified was set to 10 kg / h, and the feed flow rate of toluene was set to 2 kg / h. The operating conditions of distillation column 3 were adjusted until the residual proportion of solvent a reached 25% (the mass of undistilled solvent a is 25% of the total mass of the solution in the distillation column) and the liquid level in distillation column 3 was stable. The discharge pump was turned on, and the discharge flow rate of hydrogenated bisphenol A and solvent b was set to 3.3 kg / h. After the solvent was replaced, the newly formed hydrogenated bisphenol A and solvent b were pumped out from the bottom of the distillation column by the discharge pump and entered the reactor equipped with a controllable speed stirrer. The reactor was operated intermittently, with the stirring speed maintained at a constant speed. The reactor featured a coil design containing a heat-conducting medium. Temperature-controlled circulators were connected to the inlet and outlet of the coil. During the pumping of hydrogenated bisphenol A and solvent b, the pipeline was insulated and heated to maintain a constant temperature within the reactor. Feeding was stopped when the liquid level reached 70% of the capacity. The temperature was then lowered to 30°C at a rate of 5°C per hour and maintained at 30°C with stirring for 2 hours. The solid-liquid mixture was then discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven. Nitrogen gas was introduced into the drying oven at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0086] Example 7

[0087] The hydrogenated bisphenol A to be purified includes cyclohexanol (solvent a) and crude hydrogenated bisphenol A with a mass purity of 95.76%, and the mass concentration of crude hydrogenated bisphenol A in the hydrogenated bisphenol A to be purified is 15%. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters the distillation column 3. After the column bottom reaches 2 / 3 liquid level, the vacuum pump is started to establish vacuum conditions. The vacuum pump is connected to the solvent recovery tank to provide vacuum conditions for this process, and the vacuum degree is controlled at -0.09 MPa. After the vacuum is established, the distillation column is heated until the vapor temperature at the top of the column reaches 65-68°C. Solvent a vaporizes and is discharged from the top of the distillation column. The vaporized solvent a is condensed and refluxed in the condenser and then collected in the solvent recovery tank. The medium temperature in the condenser is 15-20°C. When the remaining proportion of solvent a reaches 60% (the mass of undistilled solvent a is 60% of the total mass of the solution in the distillation column), the solvent b feed pump is started. Solvent b is mesitylene. The flow rate is gradually adjusted, and the hydrogenated bisphenol to be purified is set. The feed flow rate of A is 10 kg / h, and the feed flow rate of mesitylene is set to 10 kg / h. The operating conditions of the distillation column are adjusted so that the remaining proportion of solvent a reaches 30% (the mass of undistilled solvent a is 30% of the total mass of the solution in the distillation column) and the liquid level in the distillation column is stable. The discharge pump is turned on, and the discharge flow rate of hydrogenated bisphenol A and solvent b is set to 12.1 kg / h. After the solvent is replaced, the newly formed hydrogenated bisphenol A and solvent b are pumped out from the bottom of the distillation column by the discharge pump and enter the reaction vessel equipped with a controllable speed stirrer. The reactor was operated intermittently, with the stirring speed maintained at a constant rate. The reactor was jacketed, with a heat-conducting medium inside. Temperature-controlled circulators were connected to the inlet and outlet pipes of the medium. During the pumping of hydrogenated bisphenol A and solvent b, the pipes were insulated and heated to maintain a constant temperature within the reactor. Feeding was stopped when the liquid level reached 70% of the capacity, and the temperature was lowered to 30°C at a rate of 15°C per hour. The mixture was then stirred at 30°C for 2 hours. The solid-liquid mixture was discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven, where nitrogen gas was introduced at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0088] Example 8

[0089] The hydrogenated bisphenol A to be purified includes isopropanol (solvent a) and crude hydrogenated bisphenol A with a mass purity of 95.76%. The mass concentration of crude hydrogenated bisphenol A in the hydrogenated bisphenol A to be purified is 15%. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters the distillation column. After the bottom of the column reaches 2 / 3 of the liquid level, the distillation column is heated until the vapor temperature at the top of the distillation column reaches 82-84°C. Solvent a vaporizes and is discharged from the top of the distillation column. The vaporized solvent a is condensed and refluxed in a condenser and then collected as solvent a in a solvent recovery tank. The medium temperature in the condenser is 15-20°C. When the remaining proportion of solvent a reaches 60% (the undistilled solvent...), The mass of solvent a is 60% of the total mass of the solution in the distillation column. The feed pump for solvent b, which is toluene, is turned on. The flow rate is gradually adjusted, and the feed flow rate of the hydrogenated bisphenol A to be purified is set to 10 kg / h, and the feed flow rate of toluene is set to 6 kg / h. The operating conditions of the distillation column are adjusted until the remaining proportion of solvent a reaches 35% (the mass of the undistilled solvent a is 35% of the total mass of the solution in the distillation column) and the liquid level in the distillation column is stable. The discharge pump is turned on, and the discharge flow rate of hydrogenated bisphenol A and solvent b is set to 7.5 kg / h. After the solvent is replaced, the newly formed hydrogenated bisphenol A and solvent b are pumped out from the bottom of the distillation column by the discharge pump and enter the reaction vessel equipped with a controllable speed stirrer. The reactor was operated intermittently, with the stirring speed maintained at a constant rate. The reactor was jacketed, with a heat-conducting medium inside. Temperature-controlled circulators were connected to the inlet and outlet pipes of the medium. During the pumping of hydrogenated bisphenol A and solvent b, the pipes were insulated and heated to maintain a constant temperature within the reactor. Feeding was stopped when the liquid level reached 70% of the capacity, and the temperature was lowered to 30°C at a rate of 5°C per hour. The mixture was then stirred at 30°C for 2 hours. The solid-liquid mixture was discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven, where nitrogen gas was introduced at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0090] Example 9

[0091] The hydrogenated bisphenol A to be purified consists of isopropanol (solvent a) and crude hydrogenated bisphenol A with a purity of 95.76%, where the crude hydrogenated bisphenol A has a mass concentration of 15% in the hydrogenated bisphenol A to be purified. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters the distillation column. After the column bottom reaches 2 / 3 of its capacity, the vacuum pump is started to establish vacuum conditions. The vacuum pump is connected to a solvent recovery tank to provide the vacuum conditions for this process, and the vacuum level is controlled at -0.07 MPa. After vacuum is established, the distillation column is heated until the vapor temperature at the top of the column reaches 60–62°C. Solvent a vaporizes and is discharged from the top of the distillation column. The vaporized solvent a is condensed and refluxed in a condenser and then collected in a solvent recovery tank. The medium temperature in the condenser is 15–20°C. When the remaining proportion of solvent a reaches 60% (the mass of undistilled solvent a is 60% of the total mass of the solution in the distillation column), the solvent b feed pump is started. Solvent b is mesitylene. The flow rate is gradually adjusted, and the hydrogenated dimethyl ether to be purified is set. The phenol A feed flow rate is set to 10 kg / h, and the mesitylene feed flow rate is set to 20 kg / h. The operating conditions of the distillation column are adjusted so that the remaining proportion of solvent a reaches 45% (the mass of undistilled solvent a is 45% of the total mass of the solution in the distillation column) and the liquid level in the distillation column is stable. The discharge pump is turned on, and the discharge flow rate of hydrogenated bisphenol A and solvent b is set to 12 kg / h. After the solvent is replaced, the newly formed hydrogenated bisphenol A and solvent b are pumped out from the bottom of the distillation column by the discharge pump and enter the reaction vessel equipped with a controllable speed stirrer. The reactor was operated intermittently, with the stirring speed maintained at a constant speed. The reactor featured an internal coil design containing a heat-conducting medium. Temperature-controlled circulators were connected to the coil's inlet and outlet. During the pumping of hydrogenated bisphenol A and solvent b, the pipeline was insulated and heated to maintain a constant reactor temperature. Feeding was stopped when the reactor level reached 70% of its capacity, and the temperature was lowered to 30°C at a rate of 15°C per hour. The mixture was then stirred at 30°C for 2 hours. The solid-liquid mixture was discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven, where nitrogen gas was introduced at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0092] Example 10

[0093] The hydrogenated bisphenol A to be purified includes ethanol (solvent a) and crude hydrogenated bisphenol A with a mass purity of 95.76%, and the mass concentration of crude hydrogenated bisphenol A in the hydrogenated bisphenol A to be purified is 20%. This embodiment does not require a distillation column. The hydrogenated bisphenol A to be purified is pumped into a controlled-speed stirred reactor by a feed pump. The reactor has a coil design with a heat transfer medium inside. Temperature-controlled circulators are connected to the inlet and outlet of the coil. When the liquid level in the reactor reaches 70% of its capacity, the reactor temperature is increased. After reaching 78°C, the ethanol vaporization rate increases. The vaporized ethanol is collected after condensation. The solvent b feed pump is then turned on to pump p-xylene into the reactor, slowly increasing the reactor temperature and controlling the p-xylene temperature. The benzene feed rate was maintained at 70% of the reactor's capacity. When the cooling ethanol flow rate decreased to the point where no ethanol distilled off, the solvent b feed pump was stopped. The reactor temperature was controlled and lowered to 30°C at a rate of 10°C per hour. The mixture was then stirred at 30°C for 2 hours. The solid-liquid mixture was discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to drying oven 10. Nitrogen gas was introduced into drying oven 10, and the solvent was removed at 100°C to obtain purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0094] Example 11

[0095] The hydrogenated bisphenol A to be purified includes isobutanol (solvent a) and crude hydrogenated bisphenol A with a mass purity of 95.76%, and the mass concentration of crude hydrogenated bisphenol A in the hydrogenated bisphenol A to be purified is 20%. In this embodiment, isobutanol and toluene have similar boiling points. Isobutanol is separated by distillation before toluene is added. The hydrogenated bisphenol A to be purified is pumped out by the hydrogenated bisphenol A feed pump and enters the distillation column. After the column bottom reaches 3 / 4 liquid level, the vacuum pump is started to establish vacuum conditions. The vacuum pump is connected to the solvent recovery tank to provide vacuum conditions for this process. The vacuum degree is controlled at -0.08 MPa. After the vacuum is established, the distillation column is heated until the vapor temperature at the top of the column reaches 64-65°C. Then, the feed pump for the hydrogenated bisphenol A to be purified is stopped. Solvent a vaporizes and is discharged from the top of the distillation column. The vaporized solvent a is condensed and refluxed in the condenser and collected into the solvent recovery tank. The medium temperature in the condenser is 15-20°C. Isobutanol solvent is collected until the top temperature reaches above 75°C. The feed pump for solvent b (toluene) is then started. The flow rate of solvent b is adjusted until the bottom liquid level returns to 3 / 4, at which point the feed pump is stopped. The solvent b feed pump is then stopped, and the temperature inside the distillation column is maintained at 75-80°C. After one hour of continuous heating to equilibrium, solvent replacement is completed. The newly formed hydrogenated bisphenol A and solvent b are pumped out from the bottom of the distillation column by the discharge pump and enter a reactor equipped with a controllable speed stirrer. The reactor was operated intermittently, with the stirring speed maintained at a constant speed. The reactor featured an internal coil design containing a heat-conducting medium. Temperature-controlled circulators were connected to the coil's inlet and outlet. During the pumping of hydrogenated bisphenol A and solvent b, the pipeline was insulated and heated to maintain a constant reactor temperature. Feeding was stopped when the reactor level reached 70% of its capacity, and the temperature was lowered to 30°C at a rate of 10°C per hour. The mixture was then stirred at 30°C for 2 hours. The solid-liquid mixture was discharged into a centrifuge for solid-liquid separation. The solid containing a certain amount of solvent was transferred to a drying oven, where nitrogen gas was introduced at 100°C to remove the solvent, yielding purified hydrogenated bisphenol A. The composition of hydrogenated bisphenol A was analyzed, and its yield and purity were investigated. The experimental results are shown in Table 1.

[0096] Table 1. Refining Effect of Hydrogenated Bisphenol A

[0097]

[0098] Note: (1) Crude hydrogenated bisphenol A is a self-made product.

[0099] (2) Gas chromatography was used to analyze the components of the mother liquor and purified hydrogenated bisphenol A. The mother liquor was analyzed directly, while the purified bisphenol A was dissolved in methanol before analysis. The solvent was not integrated during component analysis, and the results were obtained by gas chromatography. The mother liquor was the liquid separated in a centrifuge.

[0100] (3) Single-pass yield of refined bisphenol A = (quality of refined hydrogenated bisphenol A product ÷ quality of crude hydrogenated bisphenol A input) × 100%.

[0101] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for purifying hydrogenated bisphenol A, characterized in that, The apparatus for refining hydrogenated bisphenol A includes: a supply end for hydrogenated bisphenol A to be refined, a supply end for solvent b, a distillation column, a cooling assembly, a solid-liquid separator, and pipelines. The distillation column is placed vertically and includes inlet a, inlet b, outlet c and outlet d. The height of inlet a is higher than that of inlet b. The supply end of the hydrogenated bisphenol A to be purified is connected to inlet b, and the supply end of solvent b is connected to inlet a. The distillation column, the cooling component, and the solid-liquid separator are connected sequentially via pipelines, and the cooling component is connected to the outlet c of the distillation column. The hydrogenated bisphenol A to be purified includes hydrogenated bisphenol A and solvent a; The distillation column is used to replace solvent a in the hydrogenated bisphenol A to be purified with solvent b; The refining method includes the following steps: Step S1: The hydrogenated bisphenol A to be purified is introduced into a distillation column, where it is separated into bisphenol A and solvent a. Solvent a is discharged from the distillation column. Step S2: Solvent b is introduced into the distillation column, and solvent b is mixed with hydrogenated bisphenol A and then discharged from the distillation column; Step S3: Precipitate hydrogenated bisphenol A from solution b; Step S4: Separate the hydrogenated bisphenol A precipitated in step S3 from solvent b to obtain purified hydrogenated bisphenol A; The boiling point of solvent b is higher than that of solvent a, and the difference between the boiling point of solvent b and the boiling point of solvent a is less than or equal to 30°C. Solvent a includes at least one of ethanol, isopropanol, isobutanol, and cyclohexanol; solvent b includes one or more of toluene, p-xylene, o-xylene, m-xylene, mixed xylene, mesitylene, and mesitylene.

2. The method according to claim 1, characterized in that, The cooling component is used to precipitate hydrogenated bisphenol A from the solvent b; The solid-liquid separator is used to separate the hydrogenated bisphenol A precipitated in the cooling component from the solvent b. And / or, the apparatus for refining hydrogenated bisphenol A further includes a solvent recovery tank, which is connected to the outlet d of the distillation column; And / or, a condenser is also provided between the solvent recovery tank and the discharge port d; And / or, the apparatus for refining hydrogenated bisphenol A further includes a vacuum pump connected to a solvent recovery tank for establishing vacuum conditions within the apparatus for refining hydrogenated bisphenol A.

3. The method according to claim 1 or 2, characterized in that, The hydrogenated bisphenol A supply end to be refined includes a hydrogenated bisphenol A storage tank and a hydrogenated bisphenol A feed pump; and / or, the solvent b supply end includes a solvent b storage tank and a solvent b feed pump.

4. The method according to claim 1 or 2, characterized in that, The cooling assembly includes a reaction vessel, a cooler, and a temperature controller. The cooler is used to reduce the temperature inside the reaction vessel, and the temperature controller is used to control the cooling rate of the cooler.

5. The method according to claim 1 or 2, characterized in that, The step S4 is followed by a step S5, in which the hydrogenated bisphenol A obtained after solid-liquid separation in step S4 is dried.

6. The method according to claim 1 or 2, characterized in that, The amount of solvent b added to the distillation column is 20% to 300% of the mass of the hydrogenated bisphenol A solution to be purified; And / or, the amount of solvent b added to the distillation column is 2 to 10 times the mass of hydrogenated bisphenol A in the hydrogenated bisphenol A solution to be purified; And / or, when the mass of the remaining solvent a in the distillation column is 50% of the total mass of the solution in the distillation column, or when the mass of the remaining solvent a in the distillation column is less than 50% of the total mass of the solution in the distillation column, solvent b and hydrogenated bisphenol A shall be discharged. And / or, the pressure in the distillation column is atmospheric pressure or the control pressure is 0 to -0.09 MPaG; And / or, step 3 involves placing a mixture of hydrogenated bisphenol A and solution b in a reaction vessel, and precipitating hydrogenated bisphenol A from solution b by lowering the temperature of the reaction vessel.

7. The method according to claim 6, characterized in that, The amount of solvent b added to the distillation column is 40% to 100% of the mass of the hydrogenated bisphenol A solution to be purified; And / or, the amount of solvent b added to the distillation column is 3-6 times the mass of hydrogenated bisphenol A in the hydrogenated bisphenol A solution to be purified.

8. The method according to claim 6, characterized in that, When the temperature of the mixture is above 60℃, the cooling rate of the reactor is 5-15℃ / Hr.

9. The application of the method according to any one of claims 1-8 in the purification of hydrogenated bisphenol A.

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