Stirring tank type reactor for heterogeneous hydrogenation reaction, application of stirring tank type reactor and heterogeneous intermittent hydrogenation method of butylbenzene block copolymer

Abstract

The invention relates to the field of stirred tank reactors for heterogeneous hydrogenation reaction, and discloses a stirred tank reactor for heterogeneous hydrogenation reaction, application of the stirred tank reactor and a heterogeneous intermittent hydrogenation method of butylbenzene block copolymer. The stirred tank reactor comprises a cylinder body and a stirring paddle arranged in the cylinder body, the ring cluster type gas distributor is positioned at the lower part of the barrel; the reaction hydrogen inlet is positioned on the upper wall of the barrel; when the stirred tank reactor is used for heterogeneous hydrogenation reaction, the mass transfer area among air-liquid-solid phases can be increased, and the hydrogenation efficiency of unsaturated polymers is improved.

Description

Technical Field

[0001] The present invention relates to a stirred tank reactor for heterogeneous hydrogenation reaction. Specifically, it relates to a stirred tank reactor for heterogeneous hydrogenation reaction, its application, and a method for heterogeneous batch hydrogenation of styrene-butadiene block copolymer. Background Art

[0002] Styrene-butadiene block copolymer is an unsaturated block copolymer obtained by batch solution polymerization of butadiene and styrene, and then a fully saturated cyclic block copolymer is prepared by carrying out a full hydrogenation reaction on this unsaturated block copolymer.

[0003] In the styrene-butadiene block copolymer obtained by the batch solution method, both the butadiene segment and the benzene ring contain unsaturated carbon-carbon double bonds. Hydrogen gas and a solid-phase hydrogenation catalyst need to be introduced into the solution, and then a full hydrogenation reaction is carried out at a certain temperature and pressure. In the prior art, a traditional stirred tank reactor is usually used to carry out the hydrogenation reaction on the unsaturated polymer solution. Among them, the main place for the hydrogenation reaction is the interface between the gas phase and the liquid phase. The gas-liquid contact area can be increased by means such as increasing the stirring speed, increasing the solution concentration, increasing the hydrogen partial pressure, and increasing the reaction temperature, so as to improve the gas-liquid mass transfer rate and further improve the efficiency of the hydrogenation reaction. These harsh reaction conditions limit the progress of the hydrogenation reaction technology of unsaturated polymer solutions and the quality of products.

[0004] In the prior art, in order to increase the gas-liquid contact area between hydrogen gas and the unsaturated polymer solution, US20020107423A discloses a hydrogenation reactor. During the reaction process, a part of the materials in the reactor are pumped out of the reactor by a pump, heat-exchanged through a heat exchanger, and then recycled into the reactor. The amount of the materials pumped out for recycling is relatively large, so a large amount of energy needs to be consumed to maintain the recycling, thereby ensuring the stable operation of the reactor.

[0005] CN101081878A discloses a rotating disk reactor. When the rotating disk rotates, the liquid flows towards the edge of the disk and forms a relatively thin liquid film under the action of centrifugal force, enabling very high mass exchange between the liquid and the rising gas. Usually, a relatively high hydrogenation degree can be achieved within a relatively short reaction time. However, the unsaturated polymer solution has a certain viscosity, and the viscosity of the system shows an obvious upward trend as the hydrogenation degree increases. Therefore, the film-forming effect of the polymer solution under the action of centrifugal force is uneven and the continuity is not good. Therefore, this reactor has not been widely used in the industrial hydrogenation of unsaturated polymers. Summary of the Invention

[0006] The object of the present invention is to overcome the problem in the prior art that the reaction hydrogen is unevenly dispersed among unsaturated polymer solutions and it is difficult to fully contact, resulting in low hydrogenation efficiency of unsaturated polymers. Provided are a stirred tank reactor for heterogeneous hydrogenation reaction, its application, and a method for heterogeneous batch hydrogenation of styrene-butadiene block copolymer. When the stirred tank reactor is used for heterogeneous hydrogenation reaction, it can increase the mass transfer area of gas-liquid-solid, and improve the hydrogenation efficiency of unsaturated polymers.

[0007] To achieve the above object, in the first aspect of the present invention, there is provided a stirred tank reactor for heterogeneous hydrogenation reaction, wherein the stirred tank reactor includes a cylinder body, a stirring paddle placed in the cylinder body, a ring cluster type gas distributor located at the lower part of the cylinder body, and a reaction hydrogen inlet located on the upper wall of the cylinder body.

[0008] In the second aspect of the present invention, there is provided an application of the above stirred tank reactor in polymer hydrogenation reaction.

[0009] In the third aspect of the present invention, there is provided a method for heterogeneous batch hydrogenation of styrene-butadiene block copolymer, wherein the method is carried out by using the above stirred tank reactor for heterogeneous hydrogenation reaction.

[0010] Through the above technical solutions, the stirred tank reactor for heterogeneous hydrogenation reaction provided by the present invention, its application, and the method for heterogeneous batch hydrogenation of styrene-butadiene block copolymer have the following beneficial effects.

[0011] The stirred tank reactor for heterogeneous hydrogenation reaction of the present invention includes a ring cluster type gas distributor, which can realize full contact, dispersion and mixing among the reaction hydrogen continuously supplemented during hydrogenation, the solid-phase hydrogenation catalyst and the styrene-butadiene block copolymer solution, thereby improving the hydrogenation efficiency of unsaturated polymers. Description of the Drawings

[0012] The drawings are used to provide further understanding of the present invention, and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention, but do not constitute a limitation to the present invention.

[0013] Figure 1 It is a schematic structural diagram of a stirred tank reactor according to an embodiment of the present invention.

[0014] Figure 2 It is a top view of a ring cluster type gas distributor according to an embodiment of the present invention.

[0015] Description of the Reference Numerals

[0016] 1 - Cylinder body; 2 - Jacket; 3 - Agitator paddle; 4 - Baffle; 5 - Ring cluster type gas distributor; 501 - Inlet pipe of the ring cluster type gas distributor; 502 - Concentric rings of the ring cluster type gas distributor; 6 - Inlet of solid phase hydrogenation catalyst; 7 - Inlet of copolymer solution; 8 - Inlet of pressurizing hydrogen; 9 - Inlet of reaction hydrogen; 10 - Outlet of copolymer solution; 11 - Drain port; 12 - Inlet of jacket medium; 13 - Outlet of jacket medium. Detailed implementation mode

[0017] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0018] In the present invention, the ceiling function refers to rounding a decimal number towards the larger integer. For example, 2.5 is rounded up to 3. The floor function refers to rounding a decimal number towards the smaller integer. For example, 2.5 is rounded down to 2.

[0019] In the present invention, the inner diameter refers to the diameter of the cylinder body; the ring diameter r refers to the diameter of the concentric rings.

[0020] In the first aspect of the present invention, a stirred tank reactor for heterogeneous hydrogenation reaction is provided, wherein the stirred tank reactor includes a cylinder body, an agitator paddle placed inside the cylinder body, a ring cluster type gas distributor located at the lower part of the cylinder body, and a reaction hydrogen inlet located on the upper wall of the cylinder body.

[0021] In the present invention, the stirred tank reactor for heterogeneous hydrogenation reaction contains a ring cluster type gas distributor, which can realize sufficient contact, dispersion and mixing among the reaction hydrogen, solid phase hydrogenation catalyst and polymer solution (such as styrene-butadiene block copolymer solution) continuously supplemented during the hydrogenation process, thereby improving the hydrogenation efficiency of unsaturated polymers.

[0022] According to the present invention, the ring cluster type gas distributor includes an inlet pipe extending downward from the reaction hydrogen inlet to the lower space of the cylinder body, and concentric rings connected by the inlet pipe.

[0023] In the present invention, the ring cluster type gas distributor refers to a gas distributor containing 2 or more annular gas distribution pipe structures, that is, the number of concentric rings of the ring cluster type gas distributor is greater than or equal to 2.

[0024] In the present invention, hydrogen is transported from the reaction hydrogen inlet to the concentric rings through the inlet pipe and enters the cylinder from the openings on the concentric rings. Through the concentric ring cluster type gas distributor, the reaction hydrogen entering the cylinder can be evenly distributed over the entire cross-section where the gas distributor is located, thereby achieving full and uniform mixing among gas, liquid, and solid, which is conducive to improving the efficiency of the hydrogenation reaction.

[0025] According to the present invention, the relationship between the number n of the concentric rings (502) and the inner diameter d of the cylinder (1) satisfies: n = dA, where A is 1 - 10 and n is an integer greater than or equal to 2.

[0026] In the present invention, A refers to the number of concentric rings per unit diameter, and the number n of the concentric rings is an integer obtained by rounding up.

[0027] In the present invention, when the relationship between the number of concentric rings and the inner diameter d of the cylinder meets the above requirements, the reaction hydrogen can be evenly distributed and the pressure of the reaction hydrogen can be maintained, thereby ensuring the hydrogen reaction concentration. Therefore, the efficiency of the hydrogenation reaction can be improved, and the energy consumption for transporting the reaction hydrogen is reduced. In the present invention, unless otherwise specified, the units of the inner diameter d, the ring diameter r, and the height of the straight cylinder section H are all meters.

[0028] In the present invention, the diameters of the ring tubes of each concentric ring of the ring cluster type gas distributor are equal, and the diameter of the inlet pipe is equal to the diameters of the ring tubes of each concentric ring. Preferably, the diameter of the inlet pipe is 1 / 50d - 1 / 20d, preferably 1 / 40d - 1 / 30d.

[0029] According to the present invention, the spacing between adjacent concentric rings in the ring cluster type gas distributor is equal.

[0030] According to the present invention, when the inner diameter of the cylinder is d, the ring diameter of the outermost concentric ring of the ring cluster type gas distributor is 1 / 2d - 9 / 10d.

[0031] In the present invention, when the ring diameter of the outermost concentric ring meets the above range, the entering reaction hydrogen can cover the liquid and solid near the inner wall of the cylinder, so that the reaction hydrogen can fully contact the liquid and solid near the inner wall of the cylinder. While improving the efficiency of the hydrogenation reaction, the effect of uniform hydrogenation of the polymer is obtained.

[0032] Furthermore, when the inner diameter of the cylinder is d, the ring diameter of the outermost concentric ring of the ring cluster type gas distributor is 3 / 5d - 4 / 5d.

[0033] According to the present invention, when the inner diameter of the cylinder is d, the ring diameter of the innermost concentric ring of the ring cluster type gas distributor is 1 / 5d - 1 / 2d.

[0034] In the present invention, when the ring diameter of the innermost concentric ring meets the above range, the incoming reaction hydrogen can cover the liquid and solid near the center of the cylinder body, so that the reaction hydrogen can fully contact the liquid and solid near the center of the cylinder body, improving the hydrogenation reaction efficiency while obtaining the effect of uniform hydrogenation of the polymer.

[0035] Further, when the inner diameter of the cylinder body is d, the ring diameter of the innermost concentric ring of the ring cluster type gas distributor is 1 / 4d - 1 / 3d.

[0036] According to the present invention, the opening distribution of the concentric rings is an equally spaced distribution.

[0037] According to the present invention, the relationship between the number of openings n of the concentric ring and the ring diameter r of the concentric ring satisfies: n = rB, where B is an integer in the range of 6 - 150 and n is an integer.

[0038] In the present invention, the number of openings n of the concentric ring is an integer rounded up.

[0039] In the present invention, in the same ring cluster type gas distributor, when the ring diameter r1 of the concentric ring > r2, the number of openings nr1 of the concentric ring > nr2, where nr1 is the number of openings on the concentric ring with a ring diameter of r1 and nr2 is the number of openings on the concentric ring with a ring diameter of r2. When the relationship between the number of openings of the concentric ring and the ring diameter r of the concentric ring meets the above relationship, the reaction hydrogen can uniformly flow into the reaction system after passing through each concentric ring, and the flow resistance of the reaction hydrogen passing through the openings of the concentric ring can be reduced, thereby ensuring the hydrogen concentration required for the hydrogenation reaction and improving the hydrogenation reaction efficiency.

[0040] Further, the relationship between the number of openings n of the concentric ring and the ring diameter r of the concentric ring satisfies: n = rB, where B is an integer in the range of 50 - 150 and n is an integer.

[0041] According to a preferred embodiment of the present invention, the opening distribution of the concentric rings is an equally spaced distribution, and the openings on adjacent concentric rings are staggered.

[0042] According to the present invention, the opening direction of the concentric ring faces the bottom of the stirred tank reactor.

[0043] According to the present invention, the opening diameter of the concentric ring is 1 - 5 mm.

[0044] Further, the opening diameter of the concentric ring is 2 - 3 mm.

[0045] According to the present invention, when the inner diameter of the cylinder body is d, the vertical distance L between the center of the ring cluster type gas distributor and the bottommost end inside the stirred tank reactor is 1 / 15d - 1 / 3d.

[0046] In the present invention, when the vertical distance L satisfies the above range, the reaction hydrogen entering the cylinder through the ring cluster gas distributor can collide violently with the liquid discharged downward by the stirring paddle during its upward movement, forming smaller bubbles, thereby increasing the contact area between the gas-liquid-solid three phases and ensuring the efficient progress of the hydrogenation reaction.

[0047] Further, when the inner diameter of the cylinder is d, the vertical distance L between the center of the ring cluster gas distributor and the bottommost end inside the stirred tank reactor is 1 / 12d - 1 / 4d.

[0048] According to the present invention, the stirring paddle is an inclined blade turbine paddle and / or an inclined blade disk turbine paddle.

[0049] In the present invention, the operation mode of the stirring paddle can be the upward lifting type or the downward pressing type; preferably the upward lifting type.

[0050] Further, the stirring paddle is an inclined blade turbine paddle.

[0051] According to a preferred embodiment of the present invention, the stirring paddle adopts an upward lifting type inclined blade turbine paddle.

[0052] In the present invention, under the synergistic action of the stirring paddle and the ring cluster gas distributor, it is more conducive to the full mixing between the gas phase, liquid phase and solid phase raw materials, increasing the mass transfer area between the gas-liquid-solid three phases, thereby improving the hydrogenation reaction efficiency.

[0053] According to the present invention, when the inner diameter of the cylinder is d, the diameter of the stirring paddle is 1 / 4d - 2 / 3d.

[0054] In the present invention, when the diameter of the stirring paddle satisfies the above range, a good axial circulation flow from bottom to top can be formed in the stirred tank, and the proportion of the loss power of the stirrer can be reduced; and due to the existence of the ring cluster gas distributor, there are concentric rings with a ring diameter larger than the diameter of the stirring paddle and concentric rings with a ring diameter smaller than the diameter of the stirring paddle, so it can reduce the formation of gas cavities behind the stirring paddle blades by hydrogen, which is beneficial to the reaction hydrogen being directly broken by the stirring paddle and being well dispersed, and the operation state is not easily changed with the change of the gas load.

[0055] Further, when the inner diameter of the cylinder is d, the diameter of the stirring paddle is 7 / 20d - 1 / 2d.

[0056] According to the present invention, the relationship between the number of the stirring paddles and the aspect ratio of the height to diameter of the cylinder satisfies: n = [(H×Y) / d] + 1, where H is the height of the straight cylinder section of the cylinder, Y is the percentage of the liquid level height in the cylinder height, and n is an integer.

[0057] In the present invention, the number n of the stirring paddles is an integer obtained by rounding down.

[0058] According to the present invention, when the number of the stirring paddles is greater than or equal to 2, the distance between adjacent stirring paddles is 1 / 6d - d.

[0059] In the present invention, when the distance between adjacent stirring paddles meets the above range, the liquid material in the cylinder can achieve an axial flow circulation from bottom to top, ensuring that the solid-phase catalyst is well suspended in the liquid material, and enabling the liquid and solid materials to collide violently with the upward-flowing reaction hydrogen coming out of the bottom ring cluster distributor, achieving good dispersion of the reaction hydrogen in the reaction materials. Through the full contact of the gas, liquid, and solid phases, the efficiency of the hydrogenation reaction and the effect of uniform hydrogenation are ensured.

[0060] Further, when the number of the stirring paddles is greater than or equal to 2, the distance between adjacent stirring paddles is 1 / 3d - 2 / 3d.

[0061] According to the present invention, the ring cluster gas distributor is located below the stirring paddle.

[0062] According to the present invention, when the inner diameter of the cylinder is d, the distance between the ring cluster gas distributor and the adjacent stirring paddle is 1 / 15d - 1 / 3d.

[0063] Further, when the inner diameter of the cylinder is d, the distance between the ring cluster gas distributor and the adjacent stirring paddle is 1 / 12d - 1 / 4d.

[0064] According to the present invention, the stirred autoclave reactor further includes a jacket, baffles, a solid-phase hydrogenation catalyst inlet, a copolymer solution inlet, a pressurizing hydrogen inlet, a copolymer solution outlet, and a drain port.

[0065] In the present invention, the jacket is provided on the outer wall side of the cylinder. The baffle is located on the inner wall side of the cylinder. The pressurizing hydrogen inlet is provided on the cylinder, preferably on the upper half of the cylinder. The drain port is provided at the lower end of the cylinder.

[0066] In the present invention, there is no special limitation on the shape of the baffle. For example, the baffle includes but is not limited to a rectangular baffle and a finger-shaped baffle; preferably, the baffle is a rectangular baffle. Preferably, the number of the baffles is 2 - 8, preferably 4 - 6.

[0067] The following combination Figure 1A stirred tank reactor for the heterogeneous hydrogenation reaction of the present invention is specifically described as follows. The stirred tank reactor includes: a cylindrical body 1, the interior of which from top to bottom includes a stirring paddle 3 and an annular cluster gas distributor 5, and the stirring paddle 3 and the annular cluster gas distributor 5 are located in the lower half of the cylindrical body; the cylindrical body 1 is provided with a solid-phase hydrogenation catalyst inlet 6, a copolymer solution inlet 7, a pressurized hydrogen inlet 8, a reaction hydrogen inlet 9 on the upper wall of the cylindrical body 1, a copolymer solution outlet 10 at the lower part of the cylindrical body 1, and a drain port 11 at the bottom end of the cylindrical body 1; a baffle 4 is arranged in the middle on the inner wall side of the cylindrical body 1, and a jacket 2 is arranged on the outer wall side of the cylindrical body 1; the annular cluster gas distributor 5 includes an inlet pipe 501 extending downward from the reaction hydrogen inlet 9 to the lower space of the cylindrical body 1, and a concentric ring 502 connected by the inlet pipe; the jacket 2 includes a jacket medium outlet 12 and a jacket medium inlet 13.

[0068] The following is described in conjunction with Figure 2 the top view of the annular cluster gas distributor. Specifically, the concentric ring 502 is connected into a whole by the inlet pipe 501; the air holes on the concentric ring 502 are evenly distributed.

[0069] The operation mode of the stirred tank reactor for the heterogeneous hydrogenation reaction of the present invention is as follows: the catalyst and the copolymer solution are respectively added from the solid-phase hydrogenation catalyst inlet and the copolymer solution inlet, and after mixing, they enter the interior of the cylindrical body; after the catalyst feeding is completed, hot oil is introduced into the jacket of the stirred tank reactor to control the temperature inside the reactor; hydrogen is introduced into the stirred tank reactor from the pressurized hydrogen inlet to start the hydrogenation reaction; when the hydrogenation reaction starts, hydrogen is added from the reaction hydrogen inlet, and the hydrogen is transported from the reaction hydrogen inlet to the concentric ring through the inlet pipe, and the hydrogen is distributed into the cylindrical body from the openings on the concentric ring. Under the action of the stirring paddle and the annular cluster gas distributor, the solid-phase catalyst can be well dispersed in the copolymer solution, and the copolymer solution forms an axial flow circulation flow from bottom to top under the stirring action, and collides violently with the upward flowing reaction hydrogen coming out of the bottom annular cluster distributor, continuously breaking the reaction hydrogen into fine bubbles, realizing the full mixing among hydrogen, copolymer solution and catalyst, thereby improving the hydrogenation reaction efficiency. The product after the hydrogenation reaction is collected at the copolymer solution outlet, and the residual catalyst is discharged from the drain port.

[0070] The second aspect of the present invention provides an application of the above-mentioned stirred tank reactor in the polymer hydrogenation reaction.

[0071] In the present invention, the stirred tank reactor for the heterogeneous hydrogenation reaction includes a ring cluster gas distributor, which can achieve sufficient contact, dispersion, and mixing among the reaction hydrogen continuously supplemented during the hydrogenation process, the solid-phase hydrogenation catalyst, and the styrene-butadiene block copolymer solution, can meet the requirements of the polymer hydrogenation reaction, and improves the hydrogenation efficiency of unsaturated polymers.

[0072] According to the present invention, the polymer is a styrene-butadiene block copolymer.

[0073] The third aspect of the present invention provides a method for heterogeneous batch hydrogenation of a styrene-butadiene block copolymer, wherein the method is carried out by using the above-mentioned stirred tank reactor for heterogeneous hydrogenation reaction.

[0074] In the present invention, the stirred tank reactor for the heterogeneous hydrogenation reaction includes a ring cluster gas distributor, which can achieve sufficient contact, dispersion, and mixing among the reaction hydrogen continuously supplemented during the hydrogenation process, the solid-phase hydrogenation catalyst, and the styrene-butadiene block copolymer solution, can meet the requirements of the polymer hydrogenation reaction, and improves the hydrogenation efficiency of unsaturated polymers.

[0075] According to the present invention, the reaction system for the heterogeneous batch hydrogenation is in a gas-liquid-solid three-phase coexistence state.

[0076] In the present invention, there is no special limitation on the mode of the hydrogenation reaction. For example, the intermittent hydrogenation reaction mode can be adopted.

[0077] In the present invention, there is no particular limitation on the method for heterogeneous batch hydrogenation of the styrene-butadiene block copolymer, and the conventional heterogeneous batch hydrogenation method in the art can be adopted. Preferably, the styrene-butadiene block copolymer solution is added to the stirred tank reactor, and a hydrogenation catalyst and hydrogen are added for hydrogenation reaction. Preferably, the mass ratio of the styrene-butadiene block copolymer to the hydrogenation catalyst is 1:0.05 - 0.2. Preferably, the concentration of the styrene-butadiene block copolymer solution is 5 - 15 wt%; preferably, the temperature of the hydrogenation reaction is 80 - 150 °C, the pressure of the hydrogenation reaction is 2 - 6 MPa, and the time of the hydrogenation reaction is 4 - 10 h.

[0078] In the present invention, unless otherwise specified, the pressure refers to the gauge pressure.

[0079] The present invention will be described in detail below through examples.

[0080] In the following examples and comparative examples, the hydrogenation degree was measured by the ultraviolet method.

[0081] In the following examples and comparative examples, the solvent in the styrene-butadiene block copolymer solution is cyclohexane; the hydrogenation catalyst is a Raney nickel-based catalyst; the volume of the stirred tank reactor is 20 L, its inner diameter is 0.25 m, and the height-to-diameter ratio of the cylinder is 1.6:1.

[0082] In the following examples and comparative examples, the normal temperature is 25 °C and the normal pressure is 100 KPa.

[0083] Other raw materials used in the examples and comparative examples are all commercially available products.

[0084] Example 1

[0085] The number of concentric rings of the ring cluster gas distributor provided in the stirred tank reactor is 3 (the relationship between the number of concentric rings n and the inner diameter d of the cylinder is n = 0.25×10 = 2.5, rounded up to 3), where the ring diameter of the outermost concentric ring is 4 / 5 of the inner diameter of the stirred tank reactor, the ring diameter of the innermost concentric ring is 1 / 3 of the inner diameter of the stirred tank reactor, and the distance between the center of the middle ring and the center of the outermost ring is equal to the distance between the center of the innermost ring. The number of openings in the outermost ring is 20, the number of openings in the innermost ring is 9, and the number of openings in the middle ring is 15. The aperture of all openings is 2 mm. The relationship between the number of openings of the concentric rings from the outermost to the innermost and the ring diameter r of the concentric rings is The distance L from the center of the ring cluster gas distributor to the bottommost part inside the cylinder of the stirred tank reactor is 1 / 6 of the inner diameter of the stirred tank reactor. There are 2 layers of four-tilted blade turbines in the stirred tank reactor (the number of stirring blades = [(HY) / d]+1 = (1.6×0.7)+1, rounded down to 2). The distance between the concentric ring and the adjacent stirring blade is 1 / 6 of the inner diameter of the stirred tank reactor; the distance between the 2 stirring blades is 1 / 3 of the inner diameter of the stirred tank reactor; the diameter of the 2 stirring blades is 2 / 5 of the inner diameter of the stirred tank reactor.

[0086] At normal temperature and pressure, an 8 wt% styrene-butadiene block copolymer solution is added to the stirred tank reactor, and a hydrogenation catalyst is added. The mass ratio of the styrene-butadiene block copolymer to the hydrogenation catalyst is 1:0.2. After the catalyst feeding is completed, hot oil is introduced into the jacket of the stirred tank reactor to raise the temperature of the reactor to 125 °C; then hydrogen is introduced into the stirred tank reactor through the hydrogen inlet for pressure building until the reactor pressure reaches 5 MPa, and then hydrogenation reaction is carried out. During the reaction, hydrogen is added through the reaction hydrogen inlet to keep the pressure inside the stirred tank reactor at 5 MPa all the time.

[0087] Starting from the beginning of the hydrogenation reaction, samples are taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer. The results are listed in Table 1 below.

[0088] Example 2

[0089] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the ring diameter of the outermost concentric ring was 7 / 10 of the inner diameter of the stirred tank reactor, the ring diameter of the innermost concentric ring was 7 / 24 of the inner diameter of the stirred tank reactor, and the distance between the center of the middle ring and the center of the outermost ring was equal to the distance between the center of the innermost ring. The number of openings in the outermost ring was 20, the number of openings in the innermost ring was 9, and the number of openings in the middle ring was 15.

[0090] Samples were taken at 4 hours, 6 hours, and 8 hours respectively since the start of the hydrogenation reaction to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0091] Example 3

[0092] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the ring diameter of the outermost concentric ring was 3 / 5 of the inner diameter of the stirred tank reactor, the ring diameter of the innermost concentric ring was 1 / 4 of the inner diameter of the stirred tank reactor, and the distance between the center of the middle ring and the center of the outermost ring was equal to the distance between the center of the innermost ring. The number of openings in the outermost ring was 20, the number of openings in the innermost ring was 9, and the number of openings in the middle ring was 15.

[0093] Samples were taken at 4 hours, 6 hours, and 8 hours respectively since the start of the hydrogenation reaction to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0094] Example 4

[0095] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the distance L between the center of the ring cluster gas distributor and the bottommost part inside the reactor body of the stirred tank reactor was 1 / 12 of the inner diameter of the stirred tank reactor.

[0096] Samples were taken at 4 hours, 6 hours, and 8 hours respectively since the start of the hydrogenation reaction to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0097] Example 5

[0098] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the distance L between the center of the ring cluster gas distributor and the bottommost part inside the reactor body of the stirred tank reactor was 1 / 4 of the inner diameter of the stirred tank reactor.

[0099] Samples were taken at 4 hours, 6 hours, and 8 hours respectively since the start of the hydrogenation reaction to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0100] Example 6

[0101] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the diameter of the two stirring paddles was 7 / 20 of the inner diameter of the stirred tank reactor.

[0102] Since the start of the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0103] Example 7

[0104] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the diameter of the two stirring paddles was 1 / 2 of the inner diameter of the stirred tank reactor.

[0105] Since the start of the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0106] Example 8

[0107] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the ring diameter of the outermost concentric ring of the ring cluster gas distributor was 9 / 10 of the inner diameter of the stirred tank reactor, and the ring diameter of the innermost concentric ring was 1 / 2 of the inner diameter of the stirred tank reactor.

[0108] Since the start of the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0109] Example 9

[0110] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the ring diameter of the outermost concentric ring of the ring cluster gas distributor was 1 / 2 of the inner diameter of the stirred tank reactor, and the ring diameter of the innermost concentric ring was 1 / 5 of the inner diameter of the stirred tank reactor.

[0111] Since the start of the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0112] Example 10

[0113] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the ring diameter of the outermost concentric ring of the ring cluster gas distributor was 23 / 25 of the inner diameter of the stirred tank reactor, and the ring diameter of the innermost concentric ring was 3 / 5 of the inner diameter of the stirred tank reactor.

[0114] Since the start of the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0115] Example 11

[0116] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the ring diameter of the outermost concentric ring of the ring cluster gas distributor was 2 / 5 of the inner diameter of the stirred tank reactor, and the ring diameter of the innermost concentric ring was 1 / 10 of the inner diameter of the stirred tank reactor.

[0117] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0118] Example 12

[0119] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the distance L from the center of the ring cluster gas distributor to the bottommost part inside the reactor body of the stirred tank reactor was 1 / 3 of the inner diameter of the stirred tank reactor.

[0120] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0121] Example 13

[0122] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the distance L from the center of the ring cluster gas distributor to the bottommost part inside the reactor body of the stirred tank reactor was 2 / 5 of the inner diameter of the stirred tank reactor.

[0123] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0124] Example 14

[0125] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the distance L from the center of the ring cluster gas distributor to the bottommost part inside the reactor body of the stirred tank reactor was 1 / 16 of the inner diameter of the stirred tank reactor.

[0126] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0127] Example 15

[0128] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the diameter of the 2 stirring paddles was 2 / 3 of the inner diameter of the stirred tank reactor.

[0129] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0130] Example 16

[0131] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the diameter of the two stirring paddles was 1 / 4 of the inner diameter of the stirred tank reactor.

[0132] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0133] Example 17

[0134] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the diameter of the two stirring paddles was 5 / 6 of the inner diameter of the stirred tank reactor.

[0135] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0136] Example 18

[0137] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the diameter of the two stirring paddles was 1 / 5 of the inner diameter of the stirred tank reactor.

[0138] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0139] Example 19

[0140] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the distance between the two stirring paddles was 1 / 6 of the inner diameter of the stirred tank reactor; the number of openings in the outermost ring was 16, the number of openings in the innermost ring was 6, and the number of openings in the middle ring was 12, and the aperture of the openings was 4 mm.

[0141] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0142] Comparative Example 1

[0143] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the ring cluster gas distributor was replaced with a single-ring gas distributor, and the number of concentric rings of the single-ring gas distributor was 1, and the ring diameter of the single ring was 4 / 5 of the inner diameter of the stirred tank reactor.

[0144] Starting from the hydrogenation reaction, samples were taken at 4 hours, 6 hours, and 8 hours respectively to detect the hydrogenation degree of the unsaturated polymer, and the results are listed in Table 1 below.

[0145] Comparative Example 2

[0146] The heterogeneous hydrogenation reaction was carried out according to the method of Example 1, except that the ring cluster gas distributor was replaced by a single-ring gas distributor. The number of concentric rings of the single-ring gas distributor was 1, and its ring diameter was 1 / 3 of the inner diameter of the stirred tank reactor.

[0147] Samples were taken at 4 hours, 6 hours, and 8 hours respectively since the start of the hydrogenation reaction, and the hydrogenation degree of the unsaturated polymer was detected. The results are listed in Table 1 below.

[0148] Table 1

[0149]

[0150] It can be seen from the data listed in Table 1 that according to the present invention, the use of the ring cluster gas distributor can enable sufficient contact and mixing among hydrogen, the catalyst, and the dissolution of the polymer, thereby improving the efficiency of the unsaturated polymer.

[0151] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A stirred tank reactor for heterogeneous hydrogenation reaction, characterized in that, The stirred tank reactor includes a cylindrical body (1), a stirring paddle (3) placed inside the cylindrical body (1), an annular cluster gas distributor (5) located at the lower part of the cylindrical body (1), and a reaction hydrogen inlet (9) located on the upper wall of the cylindrical body (1).

2. The stirred tank reactor according to claim 1, wherein, The annular cluster gas distributor (5) includes an inlet pipe (501) extending downward from the reaction hydrogen inlet (9) to the lower space of the cylindrical body (1), and concentric rings (502) connected by the inlet pipe (501); Preferably, the relationship between the number n of the concentric rings (502) and the inner diameter d of the cylindrical body (1) satisfies: n = dA, where A is 1 - 10, and n is an integer greater than or equal to 2.

3. The stirred tank reactor according to claim 1 or 2, wherein The spacing between adjacent concentric rings in the annular cluster gas distributor (5) is equal; Preferably, when the inner diameter of the cylindrical body (1) is d, the ring diameter of the outermost concentric ring (502) of the annular cluster gas distributor (5) is 1 / 2d - 9 / 10d, preferably 3 / 5d - 4 / 5d; Preferably, when the inner diameter of the cylindrical body (1) is d, the ring diameter of the innermost concentric ring (502) of the annular cluster gas distributor (5) is 1 / 5d - 1 / 2d, preferably 1 / 4d - 1 / 3d.

4. The stirred tank reactor according to claim 2 or 3, wherein, The opening distribution of the concentric rings (502) is an equally spaced distribution; Preferably, the relationship between the number n of the openings of the concentric rings (502) and the ring diameter r of the concentric rings (502) satisfies: n = rB, where B is an integer in the range of 6 - 150, and n is an integer.

5. The stirred tank reactor according to any one of claims 2-4, wherein, The opening direction of the concentric rings (502) faces the bottom of the stirred tank reactor; Preferably, the opening diameter of the concentric rings (502) is 1 - 5 mm, preferably 2 - 3 mm.

6. The stirred tank reactor according to any one of claims 1-5, wherein, When the inner diameter of the cylindrical body (1) is d, the vertical distance L between the center of the annular cluster gas distributor (5) and the bottommost end inside the stirred tank reactor is 1 / 15d - 1 / 3d, preferably 1 / 12d - 1 / 4d.

7. The stirred tank reactor according to any one of claims 1-6, wherein, The stirring paddle (3) is an inclined blade turbine paddle and / or an inclined blade disk turbine paddle; Preferably, the stirring paddle (3) is an inclined blade turbine paddle; Preferably, when the inner diameter of the cylindrical body (1) is d, the diameter of the stirring paddle (3) is 1 / 4d - 2 / 3d, preferably 7 / 20d - 1 / 2d; Preferably, the relationship between the number of the stirring paddles (3) and the height - to - diameter ratio of the cylindrical body (1) satisfies: n = [(H×Y) / d]+1, where H is the height of the straight cylinder section of the cylindrical body, Y is the percentage of the liquid level height in the height of the cylindrical body, and n is an integer; Preferably, when the number of the stirring paddles (3) is greater than or equal to 2, the spacing between adjacent stirring paddles is 1 / 6d - d, preferably 1 / 3d - 2 / 3d.

8. The stirred tank reactor according to any one of claims 1-7, wherein, The annular cluster gas distributor is located below the stirring paddle (3); Preferably, when the inner diameter of the cylindrical body (1) is d, the spacing between the annular cluster gas distributor and the adjacent stirring paddle (3) is 1 / 15d - 1 / 3d, preferably 1 / 12d - 1 / 4d.

9. The stirred tank reactor according to any one of claims 1-8, wherein, The stirred autoclave reactor further includes a jacket (2), baffles (4), a solid-phase hydrogenation catalyst inlet (6), a copolymer solution inlet (7), a pressurized hydrogen inlet (8), a copolymer solution outlet (10), and a drain port (11).

10. Use of the stirred autoclave reactor according to any one of claims 1-9 in the polymer hydrogenation reaction; Preferably, the polymer is a styrene-butadiene block copolymer.

11. A method for heterogeneous batch hydrogenation of a styrene-butadiene block copolymer, characterized in that, The method is prepared by carrying out a hydrogenation reaction using the stirred autoclave reactor for heterogeneous hydrogenation according to any one of claims 1-9; Preferably, the reaction system for the heterogeneous batch hydrogenation is a gas-liquid-solid three-phase coexisting state.

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