Maleic anhydride hydrogenation system and method

Abstract

The application discloses a maleic anhydride hydrogenation system and a maleic anhydride hydrogenation method. The maleic anhydride hydrogenation system comprises two sub-mother reactors I and II with the same structure; the sub-mother reactor comprises a mother reactor and a sleeved sub reactor, the two are coaxially arranged, an annular area is formed between the sub reactor and the mother reactor, and the sub reactor and the annular area are not communicated with each other; and the hydrogenation method is as follows: (1) the mixed material is divided into two paths and enters the sub reactor I from the bottom and the annular area I from the top, respectively, to perform hydrogenation reaction; (3) the hydrogenation material of the sub reactor I enters the annular area II, and the hydrogenation material of the annular area I enters the sub reactor II to perform hydrogenation reaction; and the reaction effluent of the hydrogenation reaction is subjected to gas-liquid separation to obtain reaction products. The application can effectively control the temperature rise of the whole maleic anhydride hydrogenation reaction process, solves the problems of concentrated heat release and easy local hot spots in the maleic anhydride hydrogenation reaction process, and improves the conversion rate and selectivity of the maleic anhydride hydrogenation process.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of succinic anhydride production, and particularly relates to a succinic anhydride system for preparing succinic anhydride by hydrogenation of maleic anhydride and a method for preparing succinic anhydride by hydrogenation of maleic anhydride. BACKGROUND

[0002] Currently, the production methods of succinic anhydride mainly include succinic acid dehydration method, biological fermentation method and maleic anhydride catalytic hydrogenation method. The maleic anhydride catalytic hydrogenation method is the method with the highest conversion rate and product, and is most suitable for large-scale industrialization. However, the production of succinic anhydride by hydrogenation of maleic anhydride is a strong exothermic reaction (△H = 128 kJ / mol), and the reaction heat cannot be removed in time by using conventional trickle bed hydrogenation and conventional liquid phase hydrogenation, so that the reaction process temperature cannot be controlled, resulting in problems such as local hot spots in the catalyst bed, serious side reactions and the like, and the safety, conversion rate and selectivity of the reaction process cannot be controlled.

[0003] CN103570650A proposes a process flow for continuously producing succinic anhydride and succinic acid by hydrogenation of maleic anhydride. The method uses two-stage hydrogenation reactors, the first-stage hydrogenation reactor is a fixed bed reactor with hydrogen and reaction liquid flowing upwards, and the second-stage hydrogenation reactor is a trickle bed reactor with hydrogen and reaction liquid flowing downwards. The method uses external circulation heat removal to remove the reaction heat, and the purpose is to control the average operating temperature of the entire reactor and make the temperature in the reactor uniform. In the method, the first-stage reactor uses the flow mode of hydrogen and reaction liquid flowing upwards, and based on the particularity of the large heat release of the hydrogenation reaction of maleic anhydride, the conventional technology cannot guarantee uniform mixing and distribution of the materials, and cannot guarantee uniform reaction and solve the problem of local hot spots. The second-stage reactor uses the flow mode of the trickle bed reactor with hydrogen and reaction liquid flowing downwards, and it is even more impossible to guarantee timely removal of the reaction heat and solve the problem of local hot spots.

[0004] CN105801536B proposes a method for preparing succinic anhydride by selective hydrogenation of maleic anhydride in liquid phase. The method uses a two-stage low-temperature and low-pressure reaction process to prepare succinic anhydride. Two reactors are used, which are a first-stage reactor and a second-stage reactor used in series. Maleic anhydride, solvent and hydrogen enter the first-stage reactor to perform partial catalytic selective hydrogenation. After the reaction, the remaining maleic anhydride, generated succinic anhydride and solvent mixture enter the second-stage reactor to perform complete catalytic selective hydrogenation. The product of the second-stage reactor is subjected to gas-liquid separation and rectification to obtain the succinic anhydride product. In the method, the two-stage reactor uses the liquid phase hydrogenation method of hydrogen and reaction liquid, and based on the particularity of the large heat release of the hydrogenation reaction of maleic anhydride, the conventional liquid phase hydrogenation mixing and reaction technology cannot guarantee uniform mixing and distribution of the materials, and cannot guarantee uniform reaction and solve the problem of local hot spots. SUMMARY

[0005] In view of the deficiencies of the prior art, the application discloses a maleic anhydride hydrogenation system and a maleic anhydride hydrogenation method.

[0006] The maleic anhydride hydrogenation system comprises a mother-son reactor I and a mother-son reactor II.

[0007] The mother-son reactor I comprises a mother reactor I (a reactor outer shell) and a son reactor I in a sleeve, and the two are coaxially arranged, and an annular zone I is formed between the son reactor I and the mother reactor I, and the son reactor I and the annular zone I are not communicated with each other; a first feeding port I is arranged at the bottom of the son reactor I, a first discharging port I is arranged at the top of the son reactor I, a first feeding port II is arranged at the top of the annular zone I, and a first discharging port II is arranged at the bottom of the annular zone I.

[0008] The mother-son reactor II comprises a mother reactor II (a reactor outer shell) and a son reactor II in a sleeve, and the two are coaxially arranged, and an annular zone II is formed between the son reactor II and the mother reactor II, and the son reactor II and the annular zone II are not communicated with each other; a second feeding port I is arranged at the bottom of the son reactor II, a second discharging port I is arranged at the top of the son reactor II, a second feeding port II is arranged at the top of the annular zone, and a second discharging port II is arranged at the bottom of the annular zone.

[0009] The son reactor I is communicated with the annular zone II, and the son reactor II is communicated with the annular zone I; specifically, the first discharging port I of the son reactor I is communicated with the second feeding port II of the annular zone II through a pipeline, and the first discharging port II of the annular zone I is communicated with the second feeding port I of the son reactor II.

[0010] The height-diameter ratio of the son reactor I is 3-20, preferably 5.0-10.0, the height-diameter ratio of the mother reactor I is 0.1-5, preferably 0.5-2.0; the height-diameter ratio of the son reactor II is 3-20, preferably 5.0-10.0, the height-diameter ratio of the mother reactor II is 0.1-5, preferably 0.5-2.0; the volume ratio of the son reactor I to the son reactor II is 1:1.1-1:10, preferably 1:1.5-1:5; the volume ratio of the mother reactor I to the mother reactor II is 1:1.1-1:10, preferably 1:1.5-1:4.

[0011] In the maleic anhydride hydrogenation system, the outer shell of the mother-son reactor (the mother-son reactor I and II) is provided with an upper head at the top and a lower head at the bottom; the top and the bottom of the son reactor are fixedly welded and sealed with the upper head and the lower head respectively, and the son reactor and the mother reactor are generally in a cylindrical shape.

[0012] The sub-mother reactor in the maleic anhydride hydrogenation system is filled with hydrogenation catalysts commonly used in the art, the catalysts filled in the sub-reactor and the annular zone can be the same or different, the catalysts filled in the sub-reactor I and II can be the same or different, and the number of catalyst beds in the sub-reactor and the annular zone is set according to the reaction requirement, and is generally 1-3.

[0013] The maleic anhydride hydrogenation system further comprises a heat-removing device for removing heat from the discharge of the sub-mother reactor I to reach the required reaction temperature of the material entering the sub-mother reactor II, such as a heat exchanger, an air cooler or a water cooler.

[0014] The maleic anhydride hydrogenation system further comprises a hydrogen supplement pipeline for providing hydrogen in the sub-mother reactor II.

[0015] The maleic anhydride hydrogenation system further comprises a hydrogen supplement pipeline for providing hydrogen in the sub-mother reactor II.

[0016] The maleic anhydride hydrogenation system further comprises a hydrogen supplement pipeline for providing hydrogen in the sub-mother reactor II.

[0017] The maleic anhydride hydrogenation system further comprises a raw material mixing device for mixing the materials of maleic anhydride, solvent and hydrogen, such as a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, a microchannel mixer and the like.

[0018] The maleic anhydride hydrogenation system further comprises a gas-liquid separation device for separating the effluent of the sub-mother reactor II, which is generally completed by a gas-liquid separation tank, gas is separated at the top of the separation tank, and liquid phase products are obtained at the bottom of the separation tank.

[0019] The method for hydrogenating maleic anhydride comprises the following steps: (1) mixing maleic anhydride, solvent and hydrogen in a certain proportion to form a mixture; (2) the mixture is divided into two parts and then enters the bottom of the sub-reactor I and the top of the annular zone I of the sub-mother reactor I respectively, and the first-stage up-flow hydrogenation reaction is carried out in the sub-reactor I and the first-stage down-flow hydrogenation reaction is carried out in the annular zone I; (3) the hydrogenation product of the sub-reactor I flows out from the top and enters the annular zone II of the sub-mother reactor II to carry out the second-stage down-flow hydrogenation reaction, and the hydrogenation product of the annular zone I flows out from the bottom and enters the sub-reactor II of the sub-mother reactor II to carry out the second-stage up-flow hydrogenation reaction; (4) the reaction effluent of the second-stage up-flow and down-flow hydrogenation reactions is subjected to gas-liquid separation to obtain the reaction product.

[0020] In the method, the mixture in step (1) is liquid-phase material with hydrogen as the dispersed phase and maleic anhydride solution as the continuous phase; the dispersed size of hydrogen is generally 100 nm-1000 μm, preferably 50 μm-600 μm; and one or more kinds of mixing devices such as static mixer, dissolved gas pump, mechanical stirring device, colloid mill, microporous plate nano / micron hydrogen dispersion assembly, micro-bubble generator, ceramic membrane nano / micron hydrogen dispersion assembly and micro-channel mixer are generally used.

[0021] In the method, the solvent in step (1) is selected from any one or more of benzene, toluene, xylene, acetone, tetrahydrofuran, γ-butyrolactone, methyl acetone, cyclohexanone, ethyl acetate, diethyl succinate and ethylene glycol monomethyl ether; and the concentration of the maleic anhydride solution is generally 0.03-0.3 g / mL, preferably 0.05-0.15 g / mL.

[0022] In the method, the hydrogen of the sub-mother reactor I is derived from the reaction raw material mixing process, the hydrogen of the sub-mother reactor II is derived from the hydrogen pipeline added between the sub-mother reactors I and II; and the hydrogen can be hydrogen with a purity of greater than 90 (v) %, preferably 99.9 % pure hydrogen.

[0023] In the method, the ratio of the volume flow rate of hydrogen (Nm 3 / h) in the sub-reactor (sub-reactor I and sub-reactor II) to the volume flow rate of fresh raw material (m 3 / h) (the sum of maleic anhydride and solvent) is 10:1-100:1, preferably 20:1-50:1.

[0024] In the method, the ratio of the volume flow rate of hydrogen (Nm 3 / h) in the annular zone (annular zone I and annular zone II) to the volume flow rate of fresh raw material (m 3 / h) (the sum of maleic anhydride and solvent) is generally 1:1-50:1, preferably 5:1-20:1.

[0025] In the method, the first up-flow hydrogenation reaction is carried out at a temperature of 40-200°C, preferably 50-90°C; a pressure of 0.5-10.0 MPa, preferably 1-5.0 MPa; and a liquid hourly space velocity (LHSV) of 0.5-20.0 h -1 , preferably 5.0-15.0 h -1 .

[0026] In the method, the first down-flow hydrogenation reaction is carried out at a temperature of 40-100°C, preferably 50-70°C; a pressure of 0.5-10.0 MPa, preferably 1-5.0 MPa; and a liquid hourly space velocity (LHSV) of 0.5-20.0 h -1 , preferably 5.0-15.0 h -1 .

[0027] In the method, the second up-flow hydrogenation reaction is carried out at a temperature of 40-200°C, preferably 50-90°C; a pressure of 0.5-10.0 MPa, preferably 1-5.0 MPa; and a liquid hourly space velocity (LHSV) of 0.1-5.0 h -1 , preferably 0.5-3.0 h -1 .

[0028] In the method, the second down-flow hydrogenation reaction is carried out at a temperature of 40-100°C, preferably 50-70°C; a pressure of 0.5-10.0 MPa, preferably 1-5.0 MPa; and a liquid hourly space velocity (LHSV) of 0.1-5.0 h -1 , preferably 0.1-3.0 h -1 .

[0029] In the method, the conversion rate of maleic anhydride in the sub-reactor I and the sub-reactor II is ≥70%, the conversion rate in the annular zone I and the annular zone II is <30%, and the conversion rate of maleic anhydride in the sub-reactor I is higher than that in the mother reactor I, and the conversion rate of maleic anhydride in the sub-reactor II is higher than that in the mother reactor II.

[0030] In the method, the space velocities of the sub-reactor I and the annular zone I in the sub-mother reactor I are the same, the hydrogenation reaction conversion rate of maleic anhydride in the annular zone I is controlled by controlling the different feed amounts into the sub-reactor I and the annular zone I, and the material flow ratio entering the sub-reactor I and the annular zone I is generally 1:2.5-1:30, preferably 1:2.5-1:10, so that the material conversion rate of the annular space is appropriately lower than that of the sub-reactor, the material of the sub-reactor is heat exchanged and temperature controlled by the high heat capacity of the material in the annular space, and the temperature of the sub-mother reactor is more balanced along the axial direction; the space velocity of the annular zone II is lower than that of the sub-reactor II in the sub-mother reactor II, and the space velocity ratio of the annular zone II to the sub-reactor II is 1:1.5-1:40, preferably 1:5-1:20. The temperature of the sub-reactor II is controlled by controlling the low space velocity and long residence time of the annular zone.

[0031] Here, in the sub-mother reactor I, the materials entering the sub-reactor I and the mother reactor I are both materials in the early stage of reaction, the reaction heat release rate is closer, the temperature interval of the sub-reactor I and the mother reactor I is narrower when the mother reactor I is used to control the temperature of the sub-reactor I, and the reaction is more likely to reach a stable heat release rate and conversion rate; similarly, the materials entering the sub-reactor II and the mother reactor II are both materials in the late stage of reaction, the reaction heat release rate is closer, the temperature interval of the sub-reactor II and the mother reactor II is narrower when the mother reactor II is used to control the temperature of the sub-reactor II, and the reaction is more likely to reach a stable heat release rate and conversion rate, which is beneficial to the balance and stability of the reaction temperature.

[0032] In the method, the sub-mother reactor is filled with maleic anhydride hydrogenation catalyst, preferably supported nickel-based catalyst, wherein the catalyst carrier can be one or more of SiO2, Al2O3, SiO2-Al2O3, TiO2, activated carbon or molecular sieve; the catalyst shape can be one of spherical, strip-shaped, trilobal, tooth spherical and the like, preferably spherical or tooth spherical catalyst.

[0033] In the method, the liquid material obtained by gas-liquid separation can be partially circulated back to the sub-mother reactor I and / or the sub-mother reactor II, and part of the material can be sent to a fractionation unit, or all of the material can be sent to the fractionation unit; if the reaction product is partially circulated, the circulating material circulating back to the sub-reactor accounts for 5-80 wt% of the fresh material entering the sub-mother reactor I, preferably 10-30 wt%; the circulating material circulating back to the inlet of the annular zone accounts for 5-50 wt% of the fresh material of the sub-mother reactor I, preferably 5-20 wt%.

[0034] In the method, the materials in the child reactor I and the parent reactor I of the child-parent reactor are all materials before hydrogenation reaction of dicyclohexanedicarboxylic anhydride, the dicyclohexanedicarboxylic anhydride has high concentration and fast reaction rate, and problems such as concentrated heat release and local hot spots are prone to occur. Under this condition, the child reactor I adopts the reaction condition of high space velocity, large height-diameter ratio and upflow type micro-expansion bed, which is beneficial to relieve local hot spots and catalyst coking. The parent reactor I is completely immersed and wrapped by the child reactor I through setting low height-diameter ratio, downflow type and high liquid holdup, and at the same time, countercurrent heat transfer is realized between the materials in the child reactor I and the parent reactor I. The heat released in the child reactor I can also be efficiently absorbed at a proper high conversion rate in the child reactor I, the temperature rise of the whole child-parent reactor is effectively controlled, and the temperature of the whole child-parent reactor is more balanced. In the child reactor II and the parent reactor II of the child-parent reactor, the child reactor II is the remaining material after reaction of the parent reactor I, the parent reactor II is the remaining material after reaction of the child reactor I, the child reactor II also countercurrently contacts with the material in the parent reactor II, the child reactor II adopts the reaction condition of high space velocity, large height-diameter ratio and upflow type micro-expansion bed, the parent reactor II also sets the reaction condition of low height-diameter ratio, downflow type and high liquid holdup, the heat released in the child reactor II is efficiently absorbed by the parent reactor II, the temperature rise of the whole child-parent reactor II is effectively controlled, and the temperature of the whole child-parent reactor is more balanced and stable. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 is a schematic diagram of a dicyclohexanedicarboxylic anhydride hydrogenation system and a dicyclohexanedicarboxylic anhydride hydrogenation method of the present application.

[0036] In the figure, 1 is a dicyclohexanedicarboxylic anhydride solution, 2 is hydrogen, 3 is a mixer, 4 is a dicyclohexanedicarboxylic anhydride hydrogenation reaction system feed, 5 is a ring zone I feed, 6 is a child reactor I feed, 7 is a child-parent reactor I, 8 is an outer shell of the child reactor I, 9 is a catalyst filled in the child reactor I, 10 is a catalyst filled in the ring zone I, 11 is an outlet of the child reactor I, 12 is an outlet of the ring zone I, 13 is a heat removal device, 14 is supplementary hydrogen, 15 is a mixer, 16 is a heat remover, 17 is supplementary hydrogen, 18 is a mixer, 19 is a child reactor II feed, 20 is a ring zone II feed, 21 is a child reactor II outlet, 22 is a ring zone II outlet, 23 is a child-parent reactor II, 24 is an outer shell of the child reactor II, 25 is a catalyst filled in the child reactor II, 26 is a catalyst filled in the ring zone II, 27 is a dicyclohexanedicarboxylic anhydride hydrogenation reaction system effluent, 28 is a gas-liquid separator, 29 is separated gas, and 30 is a separated hydrogenation product. DETAILED DESCRIPTION

[0037] The present application will be described in detail below with reference to the accompanying drawings and examples, but the present application is not limited by this.

[0038] The present application is illustrated by the accompanying drawings and examples.Figure 1 The application process of the maleic anhydride hydrogenation system and the maleic anhydride hydrogenation method of the present application is described as follows:

[0039] The maleic anhydride solution 1 and hydrogen 2 are mixed uniformly by a mixer 3 to form a reaction feed 4, which is first introduced into the maleic anhydride hydrogenation system. The reaction feed enters a mother-son reactor I, and then is divided into two paths. In one path, the reaction feed 5 enters the annular zone I of the mother-son reactor I 7 from the top, and has a downflow hydrogenation reaction with the catalyst from top to bottom. After being cooled and adjusted in temperature by a heat exchanger 16, the reaction feed 5 enters a mixer 18 together with supplemental hydrogen 17 to be mixed uniformly, and the obtained mixture 19 enters the bottom of the son reactor II of the mother-son reactor II, and has an upflow hydrogenation reaction with the catalyst from bottom to top. The reaction effluent 21 flows out of the hydrogenation system from the top of the son reactor II. In the other path, the reaction feed 6 enters the son reactor I of the mother-son reactor I 7 from the bottom, and has an upflow hydrogenation reaction with the catalyst from bottom to top. After being cooled and adjusted in temperature by a heat exchanger 13, the reaction feed 6 enters a mixer 15 together with supplemental hydrogen 14 to be mixed uniformly, and the obtained mixture 20 enters the top of the annular zone II of the mother-son reactor II, and has a downflow hydrogenation reaction with the catalyst from top to bottom. The reaction effluent 22 flows out of the hydrogenation system from the bottom of the annular zone II. The reaction effluent 27 from the hydrogenation system enters a gas-liquid separator 28, and separates into gas 29 and liquid product 30.

[0040] The method of the present application is applied to the preparation of succinic anhydride by hydrogenation of maleic anhydride. The maleic anhydride raw material and the γ-butyrolactone solvent are commercially available, and their specific properties are shown in Table 1 and Table 2, respectively. The properties of the catalyst are shown in Table 3.

[0041] Table 1 Properties of maleic anhydride raw material

[0042]

[0043] Table 2 Properties of γ-butyrolactone solvent

[0044]

[0045] Table 3 Physicochemical indexes of catalyst

[0046]

[0047] Comparative Example 1

[0048] Using the conventional fixed bed hydrogenation process, using two series of up-flow hydrogenation reactor, maleic anhydride in the first reactor and the second reactor in turn maleic anhydride hydrogenation reaction. First, the maleic anhydride raw material is dissolved in the γ-butyrolactone solvent mixed evenly, preparation of maleic anhydride solution, temperature to the reactor inlet temperature after mixing with hydrogen, from the bottom of the up-flow hydrogenation reactor, from bottom to top through the catalyst bed hydrogenation reaction, the hydrogenation product obtained by temperature after mixing with the hydrogen supplement, from the bottom of the second up-flow hydrogenation reactor, through the catalyst bed from bottom to top hydrogenation reaction, complete hydrogenation reaction after leaving the reactor, through the separator for gas-liquid separation, the separated material part of the cycle, another part into the separation unit.

[0049] The operating conditions of the first hydrogenation reactor are as follows:

[0050] The reactor inlet temperature is 50℃;

[0051] The reaction pressure is 6.0-6.5MPaG;

[0052] The reactor height-diameter ratio: 2.5

[0053] The volume space velocity: 2.0h -1

[0054] The concentration of maleic anhydride: 12g / mL

[0055] The hydrogen (Nm 3 / h) and fresh raw material (m 3 / h) (maleic anhydride dissolved in γ-butyrolactone solvent to form a solution) volume ratio of 30:1;

[0056] The mass ratio of the circulating amount of the reaction product into the first reactor to the fresh raw material: 35%;

[0057] The operating conditions of the second hydrogenation reactor are as follows:

[0058] The reactor inlet temperature is 50℃;

[0059] The reaction pressure is 6.0-6.5MPaG;

[0060] The volume space velocity: 1.0h -1 ;

[0061] The reactor height-diameter ratio: 2.5;

[0062] The hydrogen (Nm 3 / h) and fresh raw material (m 3 / h) (maleic anhydride dissolved in γ-butyrolactone solvent to form a solution) volume ratio of 20:1;

[0063] The volume ratio of the first hydrogenation reactor to the second hydrogenation reactor is 1:2.

[0064] The ratio of the amount of reaction product entering the second reactor to the mass of fresh raw material: 30%;

[0065] Under the reaction conditions, using the maleic anhydride and gamma-butyrolactone solvents in Table 1 and Table 2 as raw materials, the hydrogenation reaction was continuously carried out in the first reactor and the second reactor to obtain the hydrogenation product, the temperature rise of the first hydrogenation reactor was 45°C, and the temperature rise of the second hydrogenation reactor was 30°C. When the average total conversion rate of the maleic anhydride hydrogenation reaction was 98.0%, the average total selectivity was 95.2%-96.0%; when the average total conversion rate was ≥99.5%, the average total selectivity was 92.3%-94.7%.

[0066] Comparative Example 2

[0067] The maleic anhydride hydrogenation process was carried out in series using an upflow fixed bed and a downflow fixed bed, and the maleic anhydride hydrogenation reaction occurred in the first reactor and the second reactor in turn. First, the maleic anhydride raw material was dissolved in the gamma-butyrolactone solvent to prepare a maleic anhydride solution, which was mixed uniformly and then adjusted to the reactor inlet temperature, mixed with hydrogen, and then entered from the bottom of the upflow hydrogenation reactor, and the hydrogenation reaction occurred in the catalyst bed from bottom to top. The obtained hydrogenation product was adjusted to the temperature, mixed with additional hydrogen, and then entered from the top of the downflow hydrogenation reactor, and the hydrogenation reaction occurred in the catalyst bed from top to bottom. After the hydrogenation reaction was completed, the product left the reactor, and then the gas-liquid separation was carried out in the separator, and part of the separated material was recycled, and the other part entered the separation unit.

[0068] The operating conditions of the first hydrogenation reactor were as follows:

[0069] The reactor inlet temperature was 50°C;

[0070] The reaction pressure was 6.0-6.5 MPaG;

[0071] The reactor height-diameter ratio was 3.0

[0072] The volume space velocity was 2.5 h -1

[0073] The concentration of the maleic anhydride was 12 g / mL

[0074] The volume ratio of hydrogen (Nm 3 / h) to fresh raw material (m 3 / h) (the solution formed by dissolving maleic anhydride in gamma-butyrolactone solvent) was 45:1;

[0075] The ratio of the amount of reaction product entering the second reactor to the mass of fresh raw material: 30%;

[0076] The operating conditions of the second hydrogenation reactor were as follows:

[0077] The reactor inlet temperature was 50°C;

[0078] The reaction pressure is 6.0-6.5 MPaG;

[0079] The volume space velocity is 1.0 h -1 ;

[0080] The reactor height-diameter ratio is 3.0;

[0081] The volume ratio of hydrogen (Nm 3 / h) to fresh raw material (m 3 / h) (a solution formed by dissolving maleic anhydride in γ-butyrolactone solvent) is 30:1;

[0082] The mass ratio of the circulating amount of reaction product into the second reactor to fresh raw material is 30%;

[0083] The volume ratio of the first hydrogenation reactor to the second hydrogenation reactor is 1:2.5.

[0084] Under the reaction conditions, the maleic anhydride and γ-butyrolactone solvent in Table 1 and Table 2 are used as raw materials, and the hydrogenation reaction is continuously carried out into the first reactor and the second reactor to obtain a hydrogenation product, the temperature rise of the first hydrogenation reactor is 40℃, and the temperature rise of the second hydrogenation reactor is 22℃. When the average total conversion rate of the maleic anhydride hydrogenation reaction is 98.0%, the average total selectivity is 95.6%-96.6%; when the average total conversion rate is ≥99.5%, the average total selectivity is 93.4%-95.2%.

[0085] Example 1

[0086] The method of the present application is used, and the sub-mother reactor I and the sub-mother reactor II are set. First, the pre-prepared 12% maleic anhydride (γ-butyrolactone solvent) solution and hydrogen are uniformly mixed and then enter the maleic anhydride hydrogenation system, and then sequentially pass through the sub-mother reactor I and the sub-mother reactor II to occur hydrogenation reaction. The reaction feed is divided into two routes, one route enters the sub-reaction zone I through the bottom, and the upflow hydrogenation reaction occurs in the catalyst bed from bottom to top, the sub-reaction zone I effluent is mixed with the supplemental hydrogen after heat extraction, and then enters the annular zone II of the sub-mother reactor II, and the hydrogenation reaction occurs in the catalyst bed from top to bottom, and the annular zone II reaction product is separated after leaving the sub-mother reactor II; the other route enters the annular zone I through the top, and the downflow hydrogenation reaction occurs in the catalyst bed from top to bottom, the annular zone I effluent is mixed with the supplemental hydrogen after heat extraction, and then enters the sub-reaction zone II, and the hydrogenation reaction occurs in the catalyst bed from bottom to top, and the sub-reaction zone II reaction product is separated after leaving the sub-mother reactor II; the reaction effluent of the maleic anhydride hydrogenation system is separated after gas-liquid separation, the separated gas is led out of the reaction system, and the separated liquid part enters the subsequent separation unit, and is partially circulated back to the maleic anhydride hydrogenation system.

[0087] Reaction conditions of the sub-mother reactor I:

[0088] wherein the reaction conditions of the sub-reaction zone I are as follows:

[0089] The reaction temperature is 50°C to 80°C;

[0090] The reaction pressure is 3.0 to 4.0 MPaG;

[0091] The volume space velocity is 6.0 h -1 ;

[0092] The height-diameter ratio of the sub-reaction zone I is 6.0;

[0093] The volume ratio of hydrogen (Nm 3 / h) to fresh raw material (m 3 / h) (solution of maleic anhydride dissolved in γ-butyrolactone solvent) is 25:1;

[0094] The mass ratio of the amount of reaction product recycled into the sub-reaction zone I to fresh raw material is 10%;

[0095] wherein the reaction conditions of the annular zone I are as follows:

[0096] The reaction temperature is 50°C to 65°C;

[0097] The reaction pressure is 3.0 to 4.0 MPaG;

[0098] The volume space velocity is 6.0 h -1 ;

[0099] The height-diameter ratio of the sub-reaction zone I is 1.0;

[0100] The volume ratio of hydrogen (Nm 3 / h) to fresh raw material (m 3 / h) (solution of maleic anhydride dissolved in γ-butyrolactone solvent) is 25:1;

[0101] The mass ratio of the amount of reaction product recycled into the sub-reaction zone I to fresh raw material is 10%;

[0102] The material flow ratio of the sub-reaction zone I to the annular zone I is 1:2.

[0103] Reaction conditions of the sub-mother reactor II:

[0104] wherein the reaction conditions of the sub-reaction zone II are as follows:

[0105] The reaction temperature is 50°C to 80°C;

[0106] The reaction pressure is 3.0 to 4.0 MPaG;

[0107] The volume space velocity is 10.0 h-1 ;

[0108] The height to diameter ratio of the sub-reactor II is 6.0.

[0109] The volume ratio of hydrogen (Nm 3 / h) to fresh feedstock (m 3 / h) (a solution of maleic anhydride dissolved in γ-butyrolactone solvent) is 25:1.

[0110] The mass ratio of the circulating amount of reaction product into the sub-reactor II to fresh feedstock is 30%.

[0111] The reaction conditions in the annular zone II are as follows:

[0112] The reaction temperature is 50-65°C.

[0113] The reaction pressure is 3.0-4.0 MPaG.

[0114] The volume space velocity is 1.0 h -1 ;

[0115] The height to diameter ratio of the sub-reactor II is 1.0.

[0116] The volume ratio of hydrogen (Nm 3 / h) to fresh feedstock (m 3 / h) (a solution of maleic anhydride dissolved in γ-butyrolactone solvent) is 25:1.

[0117] The mass ratio of the circulating amount of reaction product into the sub-reactor II to fresh feedstock is 30%.

[0118] The volume ratio of the sub-reactor I to the sub-reactor II is 1:2, and the volume ratio of the mother reactor I to the mother reactor II is 1:2.5.

[0119] Under the reaction conditions, the maleic anhydride and γ-butyrolactone solvent in Table 1 and Table 2 are used as the raw materials, and the hydrogenation reaction is carried out in the maleic anhydride hydrogenation system and method of the present application, the temperature of the sub-mother reactor I is 50-68°C, and the temperature of the sub-mother reactor I is 50-57°C. When the average total conversion of the maleic anhydride hydrogenation reaction is 98.0%, the average total selectivity is 99.6%-99.69%; when the average total conversion is ≥99.5%, the average total selectivity is 98.6%-99.2%.

[0120] Example 2

[0121] The reaction system and method are the same as in Example 1. The reaction conditions are different from those in Example 1, and are as follows:

[0122] The reaction conditions of the sub-mother reactor I are as follows:

[0123] The reaction conditions in the sub-reactor I are as follows:

[0124] The reaction temperature is 50-80°C;

[0125] The reaction pressure is 3.0-4.0 MPaG;

[0126] The volume space velocity is 7.0 h -1 ;

[0127] The height-diameter ratio of the sub-reactor I is 8.0;

[0128] The volume ratio of hydrogen (Nm 3 / h) to fresh raw material (m 3 / h) (the solution of maleic anhydride dissolved in γ-butyrolactone solvent) is 25:1;

[0129] The mass ratio of the circulating amount of reaction product into the sub-reactor I to fresh raw material is 15%;

[0130] The reaction conditions in the annular zone I are as follows:

[0131] The reaction temperature is 50-65°C;

[0132] The reaction pressure is 3.0-4.0 MPaG;

[0133] The volume space velocity is 7.0 h -1 ;

[0134] The height-diameter ratio of the sub-mother reactor I is 1.5;

[0135] The volume ratio of hydrogen (Nm 3 / h) to fresh raw material (m 3 / h) (the solution of maleic anhydride dissolved in γ-butyrolactone solvent) is 25:1;

[0136] The mass ratio of the circulating amount of reaction product into the sub-reactor I to fresh raw material is 15%;

[0137] The material flow ratio of the sub-reactor I to the annular zone I is 1:3.

[0138] The reaction conditions in the sub-mother reactor II are as follows:

[0139] The reaction conditions in the sub-reactor II are as follows:

[0140] The reaction temperature is 50-75°C;

[0141] The reaction pressure is 3.0-4.0 MPaG;

[0142] The volume space velocity is 7.0 h -1 ;

[0143] Height to diameter ratio of sub-reactor II: 6.0;

[0144] Hydrogen (Nm 3 / h) to fresh feedstock (m 3 / h) (solution of maleic anhydride dissolved in γ-butyrolactone solvent) volume ratio: 25:1;

[0145] Circulation amount of reaction product into sub-reactor II to fresh feedstock mass ratio: 20%;

[0146] The reaction conditions of annular zone II are as follows:

[0147] Reaction temperature: 50-65°C;

[0148] Reaction pressure: 3.0-4.0 MPaG;

[0149] Volume space velocity: 1.5 h -1 ;

[0150] Height to diameter ratio of sub-mother reactor II: 1.0;

[0151] Hydrogen (Nm 3 / h) to fresh feedstock (m 3 / h) (solution of maleic anhydride dissolved in γ-butyrolactone solvent) volume ratio: 25:1;

[0152] Circulation amount of reaction product into sub-reactor II to fresh feedstock mass ratio: 20%;

[0153] Volume ratio of sub-reactor I to sub-reactor II: 1:3; volume ratio of mother reactor I to mother reactor II: 1:1.65.

[0154] Under the reaction conditions, using maleic anhydride and γ-butyrolactone solvent of Table 1 and Table 2 as raw materials, hydrogenation reaction was carried out in the maleic anhydride hydrogenation system and hydrogenation method of the present application, the temperature of sub-mother reactor I was 50-69°C, and the temperature of sub-mother reactor I was 50-58°C. When the average total conversion of maleic anhydride hydrogenation reaction was 98.0%, the average total selectivity was 99.5%-99.8%; when the average total conversion was ≥99.5%, the average total selectivity was 98.5%-99.0%.

[0155] Example 3

[0156] The reaction system and method were the same as in Example 1. The reaction conditions were different from Example 1, as follows:

[0157] Reaction conditions of sub-mother reactor I:

[0158] The reaction conditions of sub-reactor I are as follows:

[0159] The reaction temperature is 50-75°C.

[0160] The reaction pressure is 3.0-4.0 MPaG.

[0161] The volume space velocity is 6.0h -1 ;

[0162] The height-diameter ratio of the sub-reactor I is 8.0.

[0163] The volume ratio of hydrogen (Nm 3 / h) to fresh raw material (m 3 / h) (solution of maleic anhydride dissolved in γ-butyrolactone solvent) is 25:1.

[0164] The mass ratio of the circulating amount of reaction product into the sub-reaction zone I to fresh raw material is 10%.

[0165] The reaction conditions of the annular zone I are as follows:

[0166] The reaction temperature is 50-65°C.

[0167] The reaction pressure is 3.0-4.0 MPaG.

[0168] The volume space velocity is 6.0h -1 ;

[0169] The height-diameter ratio of the sub-mother reactor I is 1.5.

[0170] The volume ratio of hydrogen (Nm 3 / h) to fresh raw material (m 3 / h) (solution of maleic anhydride dissolved in γ-butyrolactone solvent) is 25:1.

[0171] The mass ratio of the circulating amount of reaction product into the sub-reaction zone I to fresh raw material is 8%.

[0172] The material flow ratio of the sub-reactor I to the annular zone I is 1:4.

[0173] The reaction conditions of the sub-mother reactor II are as follows:

[0174] The reaction conditions of the sub-reaction zone II are as follows:

[0175] The reaction temperature is 50-72°C.

[0176] The reaction pressure is 3.0-4.0 MPaG.

[0177] The volume space velocity is 8.0h -1 ;

[0178] The height-diameter ratio of the sub-reactor II is 8.0.

[0179] The volume ratio of hydrogen (Nm3 / h) to fresh feedstock (m 3 / h) (a solution of maleic anhydride dissolved in γ-butyrolactone solvent) at a volume ratio of 25:1;

[0180] The mass ratio of the circulating amount of the reaction product into the sub-reaction zone II to fresh feedstock is 10%;

[0181] The reaction conditions in the annular zone II are as follows:

[0182] The reaction temperature is 50-65°C;

[0183] The reaction pressure is 3.0-4.0 MPaG;

[0184] The volume space velocity is 1.0 h -1 ;

[0185] The height-diameter ratio of the sub-mother reactor II is 1.5;

[0186] The hydrogen (Nm 3 / h) to fresh feedstock (m 3 / h) (a solution of maleic anhydride dissolved in γ-butyrolactone solvent) at a volume ratio of 25:1;

[0187] The mass ratio of the circulating amount of the reaction product into the sub-reaction zone II to fresh feedstock is 10%;

[0188] The volume ratio of the sub-reaction zone I to the sub-reaction zone II is 1:2, and the volume ratio of the mother reaction zone I to the mother reaction zone II is 1:2.

[0189] Under the reaction conditions, the maleic anhydride and γ-butyrolactone solvent in Table 1 and Table 2 are used as the feedstock to carry out the hydrogenation reaction in the maleic anhydride hydrogenation system and method of the present application, the temperature of the sub-mother reactor I is 50-64°C, and the temperature of the sub-mother reactor I is 50-58°C. When the average total conversion of the maleic anhydride hydrogenation reaction is 98.0%, the average total selectivity is 99.6%-99.9%; when the average total conversion is ≥99.5%, the average total selectivity is 98.7%-99.4%.

[0190] As can be seen from the effects of the examples and the comparative examples, the maleic anhydride hydrogenation system and the maleic anhydride hydrogenation method of the present application make the reaction feed successively pass through the child-mother reactor I and the child-mother reactor II to occur hydrogenation reaction, wherein the child reaction zone I and the annular zone I of the child-mother reactor I are both early-stage materials of the reactor, the child reaction zone I is set to be under the conditions of high space velocity, large height-diameter ratio and upflow type micro-expansion bed, the annular zone I is set to be under the conditions of low height-diameter ratio, downflow type and high liquid holdup, the annular zone I completely immerses and wraps the child reaction zone I, countercurrent heat transfer is occurred between the materials in the child reaction zone I and the annular zone I, the heat released in the child reaction zone I can be efficiently absorbed, the temperature rise of the whole child-mother reactor can be effectively controlled, the temperature of the whole child-mother reactor I is more balanced, and the same is true for the child-mother reactor II. Therefore, the temperature rise of the whole maleic anhydride hydrogenation reaction process can be effectively controlled by the present application, the problems of concentrated heat release and easy generation of local hot spots in the maleic anhydride hydrogenation reaction process can be solved, and the conversion rate and the selectivity of the maleic anhydride hydrogenation process can be improved.

Claims

1. A maleic anhydride hydrogenation system characterized by: The sub-mother reactor I and the sub-mother reactor II; The sub-mother reactor I includes a mother reactor I and a nested sub reactor I, which are coaxially arranged, and an annular zone I is formed between the sub reactor I and the mother reactor I, and the sub reactor I is not communicated with the annular zone I; the sub reactor I is provided with a first feeding port I at the bottom and a first discharging port I at the top, and the annular zone I is provided with a first feeding port II at the top and a first discharging port II at the bottom; The sub-mother reactor II includes a mother reactor II and a nested sub reactor II, which are coaxially arranged, and an annular zone II is formed between the sub reactor II and the mother reactor II, and the sub reactor II is not communicated with the annular zone II; the sub reactor II is provided with a second feeding port I at the bottom and a second discharging port I at the top, and the annular zone II is provided with a second feeding port II at the top and a second discharging port II at the bottom; The sub reactor I is communicated with the annular zone II, and the sub reactor II is communicated with the annular zone I; the first discharging port I of the sub reactor I is communicated with the second feeding port II of the annular zone II through a pipeline, and the first discharging port II of the annular zone I is communicated with the second feeding port I of the sub reactor II; The height-diameter ratio of the sub reactor I is 3-20, the height-diameter ratio of the mother reactor I is 0.1-5, the height-diameter ratio of the sub reactor II is 3-20, and the height-diameter ratio of the mother reactor II is 0.1-5.

2. The maleic anhydride hydrogenation system of claim 1, wherein: The height-diameter ratio of the sub reactor I is 5.0-10.0, the height-diameter ratio of the mother reactor I is 0.5-2.0, the height-diameter ratio of the sub reactor II is 5.0-10.0, and the height-diameter ratio of the mother reactor II is 0.5-2.

0.

3. The maleic anhydride hydrogenation system of claim 1, wherein: The volume ratio of the sub reactor I to the sub reactor II is 1:1.1-1:10, and the volume ratio of the mother reactor I to the mother reactor II is 1:1.1-1:

10.

4. The maleic anhydride hydrogenation system of claim 1, wherein: The top of the shell of the sub-mother reactor is an upper head, and the bottom is a lower head; the top and the bottom of the sub reactor are fixedly welded and sealed with the upper head and the lower head respectively, and the sub reactor and the mother reactor are cylindrical.

5. The maleic anhydride hydrogenation system of claim 1, wherein: The sub-mother reactor is filled with hydrogenation catalysts, the catalysts filled in the sub reactor and the annular zone are the same or different, the catalysts filled in the sub-mother reactor I and the sub-mother reactor II are the same or different, and the number of catalyst bed layers in the sub reactor and the annular zone is set according to the reaction requirement.

6. The maleic anhydride hydrogenation system of claim 1, wherein: The sub-mother reactor includes a heat-removing device for removing heat from the discharging material of the sub-mother reactor I to reach the required reaction temperature of the material entering the sub-mother reactor II.

7. The maleic anhydride hydrogenation system of claim 1, wherein: The sub-mother reactor includes a hydrogen supplement pipeline for providing hydrogen in the sub-mother reactor II.

8. The maleic anhydride hydrogenation system of claim 1, wherein: A distribution member with a material distribution function is arranged at the material inlet position in the sub-mother reactor, which is used for uniformly distributing the material along the cross section of the reactor.

9. The maleic anhydride hydrogenation system of claim 1, wherein: The mother reactors I and II in the sub-mother reactor are provided with several groups of baffle plates, which are parallel partitions installed on the inner wall of the shell of the mother reactors I and II and perpendicular to the wall.

10. The maleic anhydride hydrogenation system of claim 1, wherein: The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer.

11. The maleic anhydride hydrogenation system of claim 1, wherein: The gas-liquid separation device is arranged in the feed inlet of the mother-son reactor II.

12. A method for hydrogenating maleic anhydride in a system according to any one of claims 1 to 11, characterized in that The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer.

13. The method of claim 12, wherein: The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer.

14. The method of claim 12, wherein: The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer.

15. The method of claim 12, wherein: The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer.

16. The method of claim 12, wherein: hydrogen gas Nm in sub-reactor I 3 / h to the volume flow rate of fresh raw material m 3 the ratio of the volume flow rates of the hydrogen gas Nm in sub-reactor I to the fresh raw material m, which is the sum of maleic anhydride and solvent, is 10:1 to 100:

1.

17. The method of claim 12, wherein: hydrogen Nm in sub-reactor II 3 / h to the volume flow of fresh raw materials m 3 the ratio of the volume flow of hydrogen Nm to the volume flow of fresh raw materials m is 10:1 to 100:1, the fresh raw materials being the sum of maleic anhydride and solvent.

18. The method of claim 12, wherein: hydrogen Nm in the annular zone I 3 / h and fresh feed m 3 the ratio of the volumetric flow rates of hydrogen Nm in the annular zone I and fresh feed m, which is the sum of maleic anhydride and solvent, is from 1 : 1 to 50:

1.

19. The method of claim 12, wherein: hydrogen Nm in the annular zone II 3 / h and fresh feed m 3 the ratio of the volumetric flow rates of hydrogen Nm in the annular zone II and fresh feed m being 1 : 1 to 50: 1, fresh feed m being the sum of maleic anhydride and solvent.

20. The method of claim 12, wherein: The first-stage up-flow hydrogenation reaction conditions are: reaction temperature 40-200°C, reaction pressure 0.5-10.0 MPa, liquid hourly space velocity 5-15.0 h -1 .

21. The method of claim 12, wherein: The first-stage downflow hydrogenation reaction conditions are: reaction temperature 40-100°C, reaction pressure 0.5-10.0 MPa, liquid hourly space velocity 5-15.0 h -1 .

22. The method of claim 12, wherein: The secondary up-flow hydrogenation reaction conditions are as follows: reaction temperature is 40-200℃, reaction pressure is 0.5-10.0 MPa, liquid hourly space velocity is 0.1-3.0 h -1 .

23. The method of claim 12, wherein: The secondary downflow hydrogenation reaction conditions are as follows: reaction temperature is 40-100℃, reaction pressure is 0.5-10.0 MPa, liquid hourly space velocity is 0.1-3.0 h -1 .

24. The method of claim 12, wherein: The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer.

25. The method of claim 12, wherein: The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer.

26. The method of claim 12, wherein: The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer, a dissolved gas pump, a mechanical stirring device, a colloid mill, a microporous plate / nano / micron hydrogen dispersion assembly, a microbubble generator, a ceramic membrane nano / micron hydrogen dispersion assembly, or a microchannel mixer. The raw material mixing device is one or more of a static mixer

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