CN109678121B - High-efficiency hydrogenation process and system for producing hydrogen peroxide by anthraquinone method - Google Patents
High-efficiency hydrogenation process and system for producing hydrogen peroxide by anthraquinone method Download PDFInfo
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- CN109678121B CN109678121B CN201710974274.4A CN201710974274A CN109678121B CN 109678121 B CN109678121 B CN 109678121B CN 201710974274 A CN201710974274 A CN 201710974274A CN 109678121 B CN109678121 B CN 109678121B
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- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
Abstract
The invention discloses a high-efficiency hydrogenation process and a system for producing hydrogen peroxide by an anthraquinone process, which comprise the following contents: (1) dividing the total hydrogen of the hydrogenation process into two paths, namely hydrogen I and hydrogen II; hydrogen I and working solution enter hydrogen dissolving equipment, and hydrogen I is dissolved in the working solution to obtain hydrogen dissolving working solution; (2) enabling the hydrogen-dissolved working solution and hydrogen II to enter a mixer containing a ceramic membrane tube bundle, enabling the hydrogen-dissolved working solution to enter the shell side of the tube bundle, enabling the hydrogen II to enter the inner tube side of the tube bundle, radially dispersing the hydrogen II into nano/micron-sized small bubbles through the tube wall of the ceramic membrane tube bundle, and reacting with the hydrogen-dissolved working solution on the shell side to obtain microemulsion fluid; (3) the microemulsion fluid enters a liquid phase hydrogenation reactor filled with a hydrogenation catalyst for hydrogenation reaction, and the hydrogenation reaction product enters the next working procedure. In the process, the whole hydrogenation reaction is carried out in a liquid phase by controlling two different states of hydrogen in the working solution, so that the hydrogenation reaction efficiency is improved, the reaction uniformity is ensured, the side reaction is effectively controlled, and the consumption of anthraquinone is greatly reduced.
Description
Technical Field
The invention relates to a high-efficiency hydrogenation process and a high-efficiency hydrogenation system in a hydrogen peroxide production process by an anthraquinone method.
Background
In the process of producing hydrogen peroxide by an anthraquinone method, the hydrogenation process of anthraquinone hydrogenation is a core unit of the whole hydrogen peroxide production process, the quality level of a working solution, the product concentration, the production scale of a device and the like are directly influenced by the hydrogenation reaction result, and the main indexes for measuring the quality of the hydrogenation process are technical indexes such as hydrogen efficiency, less side reactions, single-ton catalyst productivity and the like.
The common anthraquinone hydrogenation reaction in the prior art is a gas-liquid-solid three-phase trickle bed reaction. The reaction temperature is generally 45-75 ℃, the reaction pressure is generally 0.2-0.4 MPa, the gas is a continuous phase, the liquid passes through the solid catalyst in a thin liquid film mode, and the process has the following problems: (1) hydrogen is firstly diffused to a phase interface from a gas phase main body, then dissolved on the phase interface, and then diffused to a liquid phase main body from the phase interface, and a hydrogenation reaction is carried out on the surface of a catalyst in the liquid phase main body, the whole hydrogenation reaction process is controlled by external diffusion, the diffusion mass transfer resistance of a gas/liquid film is larger, the diffusion mass transfer rate is low, the hydrogenation reaction rate is low, namely, the airspeed of the catalyst required when a certain capacity is achieved is small, and the retention time is long; (2) the hydrogen is generally added from the top of the reactor once or for multiple times, and the hydrogen is a continuous phase, so that the hydrogen in the initial stage and the middle stage of the reaction is greatly excessive even if the hydrogen is added according to the chemical hydrogen consumption of the productivity, and the excessive hydrogen can generate excessive hydrogenation side reaction, thereby causing the problems of low actual productivity, high anthraquinone consumption, poor working solution quality, high alumina consumption and the like. Therefore, how to reduce the diffusion mass transfer resistance, improve the hydrogenation reaction rate and inhibit or reduce the occurrence of excessive hydrogenation side reactions has important significance for improving the fixed bed anthraquinone hydrogenation process and improving the technological progress of hydrogen peroxide production.
CN102009960A discloses a hydrogenation method for producing hydrogen peroxide by an anthraquinone method, which comprises the steps of dispersing hydrogen gas phase into working solution containing anthraquinone derivatives to obtain gas-liquid mixed fluid containing micron-sized bubbles, and enabling the gas-liquid mixed fluid to flow for 3-1000h-1The space velocity flows through the tubular reactor filled with the hydrogenation catalyst to complete the hydrogenation process. The method only changes hydrogen into a dispersed phase to be dispersed in the working solution, but is also a traditional gas-liquid-solid three-phase hydrogenation process in nature, the mass transfer resistance of a gas/liquid film still exists in the hydrogenation reaction process, and the hydrogenation reaction rate is not substantially improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an efficient hydrogenation process for producing hydrogen peroxide by an anthraquinone method. In the process, the whole hydrogenation reaction is carried out in a liquid phase by controlling two different states of hydrogen in the working solution, so that the hydrogenation reaction efficiency is improved, the reaction uniformity is ensured, the side reaction is effectively controlled, and the consumption of anthraquinone is greatly reduced.
The high-efficiency hydrogenation process for producing hydrogen peroxide by the anthraquinone process comprises the following steps:
(1) dividing the total hydrogen of the hydrogenation process into two paths, namely hydrogen I and hydrogen II; hydrogen I and working solution enter hydrogen dissolving equipment, and hydrogen I is dissolved in the working solution to obtain hydrogen dissolving working solution;
(2) the hydrogen-dissolved working solution and hydrogen II enter a mixer containing a ceramic membrane tube bundle, wherein the hydrogen-dissolved working solution enters the shell side of the tube bundle, the hydrogen II enters the inner tube side of the tube bundle, and the hydrogen II is radially dispersed into nano/micron-sized small bubbles through the tube wall of the ceramic membrane tube bundle and reacts with the hydrogen-dissolved working solution at the shell side to obtain microemulsion fluid;
(3) the microemulsion fluid enters a liquid phase hydrogenation reactor filled with a hydrogenation catalyst for hydrogenation reaction, and the hydrogenation reaction product enters the next working procedure.
In the process of the invention, the flow of the hydrogen I in the step (1) accounts for 0.1-50% of the total hydrogen flow, and preferably 1-10%.
In the hydrogenation process of the invention, the working solution in the step (1) is a conventional working solution component for the hydrogenation process by the anthraquinone method, such as: the solute component can be one or more of ethyl anthraquinone, amyl anthraquinone and isomers thereof, the first solvent component is heavy aromatic hydrocarbon, and the second solvent component is one or more of trioctyl phosphate, tetrabutyl urea, 2-isobutyl carbinol, 2-methyl cyclohexyl acetate or isooctyl acetate.
In the process, the flow ratio of the hydrogen I and the working solution in the step (1) is 1: 0.3-1: 150, preferably 1: 1.5-1: 15, and the flow unit of the hydrogen I is Nm3Flow rate of the working fluid is m3/h。
In the process, the operation conditions of the hydrogen dissolving equipment in the step (1) are as follows: the temperature is 40-75 ℃, the pressure is 0.1-20.0 MPa, and the residence time of the dissolved hydrogen is 0.5-30 minutes, preferably 2-5 minutes.
In the process of the present invention, the hydrogen dissolving device in step (1) is well known to those skilled in the art, and is generally a tubular mixer housing, in which a static mixing or dynamic mixing component is arranged; the static mixing component can be any one of SWN type, SMX type, SMK type, SML type, SMH type and the like, and can also be any component for strengthening fluid disturbance such as a spiral plate, a corrugated plate, a rotating blade, a porous plate and the like; the power mixing component can be any one of a nozzle structure, a stirring structure, a rotating structure, a Venturi structure, a dissolved air pump structure, a negative pressure forming structure and the like, and can also realize the spiral motion of materials in a tangent feeding mode.
In the process, the mixer in the step (2) is of a shell-and-tube structure containing a ceramic membrane tube bundle, and comprises a shell, the ceramic membrane tube bundle, an inlet material pipeline, an outlet material pipeline and the like; the ceramic membrane tube bundle is arranged on the inner wall of the shell, one end of the shell is provided with a gas phase feeding pipeline connected to the tube side and a liquid phase feeding pipeline connected to the shell side, and the other end of the shell is provided with a discharging pipeline connected to the shell side. The aperture size of the ceramic membrane tube bundle is 0.1-100 nm, preferably 0.5-10 nm.
In the method, the diameter of the droplet of the microemulsion fluid obtained in the step (2) is 5-100 nm.
In the process of the invention, the operation conditions of the mixer in the step (2) are as follows: the temperature is 40-75 ℃, the pressure of the outer shell of the ceramic membrane tube bundle is 0.1-1.5 MPa, and the pressure difference between the inside and the outside of the ceramic membrane tube bundle is 0.01-10 MPa, preferably 0.5-2.0 MPa.
In the process, the hydrogenation reaction conditions in the step (3) are as follows: the reaction temperature is 40-75 ℃, the reaction pressure is 0.1-1.0 MPa, and the material volume space velocity is 30h-1～80h-1。
In the process, the liquid-gas flow ratio of the feeding of the hydrogenation reactor in the step (3) is 1: 1-1: 10, preferably 1: 3-1: 5, and the unit of the liquid phase flow is m3In Nm of gas phase flow3/h。
In the process, the liquid phase hydrogenation reactor in the step (3) is in a fixed bed structure, a microemulsion fluid feeding pipeline and a tail gas discharge pipeline are arranged at the top, and a hydrogenation reaction product discharging pipeline is arranged at the bottom; the tail gas discharge pipeline is used for discharging unreacted hydrogen and inert gas in the reactor, and can be operated intermittently or continuously according to the hydrogenation reaction depth.
In the hydrogenation process of the present invention, the hydrogenation catalyst in step (3) is a hydrogenation catalyst commonly used in hydrogenation reaction of anthraquinone process, for example: the catalyst for hydrogenation of anthraquinone with palladium and/or platinum as active component may be in the form of sphere, tooth sphere, flower sphere, integral, etc.
In the process, the catalyst is completely soaked in the liquid to generate liquid-phase hydrogenation reaction in the hydrogenation reaction process, so that the catalyst has high utilization rate on one hand; on the other hand, the diffusion mass transfer resistance of a gas/liquid phase is reduced, and the reaction rate is improved, so that the volume airspeed of the catalyst in the reaction process is large; in addition, the microemulsion fluid formed by the hydrogen and the working solution is thermodynamically stable, the hydrogen is gradually consumed along with the reaction, namely, the hydrogen content is gradually reduced along the temperature rise direction of the hydrogenation reaction, and the excessive hydrogenation phenomenon caused by the excessive hydrogen is avoided, so that the side reaction is less.
The invention also provides a liquid phase hydrogenation reaction system, which comprises a hydrogen dissolving area, a hydrogen-oil emulsifying area and a liquid phase hydrogenation reaction area;
the hydrogen dissolving area is used for dissolving hydrogen I into working solution and comprises a plurality of hydrogen dissolving devices, and each hydrogen dissolving device comprises a hydrogen feeding pipeline for introducing hydrogen, a liquid phase feeding pipeline for introducing the working solution and a liquid phase discharging pipeline for leading out the hydrogen dissolving working solution;
the hydrogen-oil emulsification zone is used for dissolving hydrogen II in hydrogen-dissolved working solution and comprises a plurality of mixers, wherein each mixer comprises a liquid-phase feeding pipeline for introducing the hydrogen-dissolved working solution to the shell side, a gas-phase feeding pipeline for introducing hydrogen to the tube side, and a discharge pipeline for leading out microemulsion fluid formed by the hydrogen and the hydrogen-dissolved working solution;
the liquid-phase hydrogenation reaction zone is used for carrying out hydrogenation reaction on the microemulsion fluid and comprises a plurality of groups of liquid-phase hydrogenation reactors, wherein each group of liquid-phase hydrogenation reactor comprises a feeding pipeline for introducing the microemulsion fluid, a discharging pipeline for leading out a hydrogenation reaction product and a pipeline for discharging unreacted hydrogen.
In the above reaction system, the hydrogen dissolving device is well known to those skilled in the art, and is generally a tubular mixer housing, in which a static mixing or dynamic mixing component is arranged; the static mixing component can be any one of SWN type, SMX type, SMK type, SML type, SMH type and the like, and can also be any component for strengthening fluid disturbance such as a spiral plate, a corrugated plate, a rotating blade, a porous plate and the like; the power mixing component can be any one of a nozzle structure, a stirring structure, a rotating structure, a Venturi structure, a dissolved air pump structure, a negative pressure forming structure and the like, and can also realize the spiral motion of materials in a tangent feeding mode.
In the reaction system, the mixer is of a shell type structure containing a ceramic membrane tube bundle, and comprises a shell, the ceramic membrane tube bundle, an inlet material pipeline, an outlet material pipeline and the like; the ceramic membrane tube bundle is arranged on the inner wall of the shell, one end of the shell is provided with a gas phase feeding pipeline connected to the tube side and a liquid phase feeding pipeline connected to the shell side, and the other end of the shell is provided with a discharging pipeline connected to the shell side
The existing fixed bed anthraquinone hydrogenation is a gas, liquid and solid three-phase trickle bed reaction process, the anthraquinone hydrogenation reaction is controlled by external diffusion, the reaction rate is mainly determined by the mass transfer rate of hydrogen which passes through the resistance of a working liquid layer and diffuses to the surface of a catalyst, if the hydrogen is completely dispersed in the working liquid, the mass transfer resistance can be greatly reduced, and the hydrogenation reaction rate is improved. Therefore, the inventor of the invention realizes two different states of hydrogen in the working solution through smart control: firstly, controlling saturated dissolved hydrogen (hydrogen gas I) in working solution by means of a certain hydrogen dissolving method and hydrogen dissolving facility, microscopically completely making the dissolved hydrogen be present in liquid molecule compared with dispersed hydrogen, and uniformly applying force to every part in the liquid molecule so as to make molecular arrangement of hydrogen gas I in the liquid be very uniform, and secondly, controlling mixing mode to make the dispersed hydrogen and saturated dissolved hydrogen (hydrogen gas II) be in the invented working solution containing dissolved hydrogen and dispersed hydrogenThe microemulsion fluid and hydrogen liquid form a microemulsion fluid, the microemulsion fluid is in a ' gas-in-oil ' state, namely, the hydrogen-dissolved working solution is used as an ' oil phase ', the dispersed hydrogen is used as a gas phase, the continuous phase is still the hydrogen-dissolved working solution, the microemulsion fluid is used as the feed of a reactor, a layer of microemulsion liquid film rich in the dissolved hydrogen (hydrogen I) is always covered on the surface of the catalyst in the hydrogenation reaction process, the ' multipoint ' hydrogenation of ' hydrogen bubbles or gas clusters on the surface of the catalyst is avoided, the hydrogen molecules are generated in the hydrogenation reaction, the microscopic uniformity of the hydrogenation reaction is controlled, the dispersed hydrogen (hydrogen II) is used as the ' driving force ' in the continuous hydrogenation reaction process, the hydrogenation reaction rate can be kept, the uniformity and the reaction degree of the reaction can be ensured, and the aim of controlling the activity and the selectivity of the hydrogenation reaction is. The invention can control the depth of hydrogenation reaction by the tail gas discharge amount of the liquid phase hydrogenation reaction zone and the hydrogen inlet amount of the oil mixer. Compared with the prior art, the catalyst volume space velocity in the hydrogenation reaction process can be increased to 30h-1～60 h-1The improvement is 30 to 60 percent; the hydrogenation efficiency can reach 12-18 g/L. The hydrogenation reaction is more uniform along the axial direction and the radial direction of the reactor, the side reaction is effectively controlled, and the consumption of the anthraquinone is reduced by 50 to 90 percent compared with the prior art.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
FIG. 2 is a schematic diagram of a liquid phase hydrogenation reaction system of the present invention.
Wherein, 1 is a hydrogen header pipe, 2 is hydrogen II, 3 is hydrogen I, 4 is working liquid, 5 is hydrogen dissolving equipment, 6 is hydrogen dissolving working liquid, 7 is a heater/cooler, 8 is a mixer, 9 is microemulsion fluid feeding, 10 is a liquid phase hydrogenation reactor, 11 is tail gas, and 12 is hydrogenation reaction products.
Detailed Description
The invention is described in detail below with reference to the figures and examples, but the invention is not limited thereby.
The process of the invention is realized by the following modes: the total hydrogen 1 is divided into two parts: hydrogen I3 and hydrogen II 2; firstly, introducing hydrogen I3 and working solution 4 into hydrogen dissolving equipment 5, and mixing and dissolving the hydrogen I3 and the working solution to form hydrogen dissolving working solution 6; introducing the liquid and hydrogen II into a mixer 8, adjusting the dissolved hydrogen working solution 6 to the temperature required by the reaction through a heater/cooler, introducing the dissolved hydrogen working solution into the side of a tube shell of the mixer 8, introducing hydrogen II 2 into the side of a tube pass of the mixer 8, forming a microemulsion fluid as a feed 9 of a liquid phase hydrogenation reactor by utilizing the interaction between the dissolved hydrogen working solution at the shell side and nano/micron-sized small bubbles, entering the liquid phase hydrogenation reactor 10 for hydrogenation reaction, introducing a hydrogenation reaction product 12 into the next working procedure, and discharging a tail gas 11 from the top.
The invention also provides a liquid phase hydrogenation reaction system, which comprises a hydrogen dissolving zone I, a hydrogen-oil emulsifying zone II and a liquid phase hydrogenation reaction zone III;
the hydrogen dissolving area I is used for dissolving hydrogen I into working solution and comprises a plurality of hydrogen dissolving devices, and each hydrogen dissolving device comprises a hydrogen feeding pipeline I-1 for introducing hydrogen, a liquid phase feeding pipeline I-2 for introducing the working solution and a liquid phase discharging pipeline I-3 for leading out the hydrogen dissolving working solution;
the hydrogen-oil emulsification zone II is used for dissolving hydrogen II in hydrogen-dissolved working solution and comprises a plurality of mixers, wherein each mixer comprises a liquid-phase feeding pipeline II-1 for introducing the hydrogen-dissolved working solution to the shell side, a gas-phase feeding pipeline II-2 for introducing hydrogen to the tube side and a discharge pipeline II-3 for leading out microemulsion fluid formed by the hydrogen and the hydrogen-dissolved working solution;
the liquid phase hydrogenation reaction zone III is used for carrying out hydrogenation reaction on the microemulsion fluid and comprises a plurality of groups of liquid phase hydrogenation reactors, wherein each group of liquid phase hydrogenation reactor comprises a feeding pipeline III-1 for introducing the microemulsion fluid, a discharging pipeline III-2 for leading out a hydrogenation reaction product and a pipeline III-3 for discharging unreacted hydrogen.
In the embodiment of the invention, 2-ethyl anthraquinone is used as a working carrier, a mixture of heavy aromatic hydrocarbon, trioctyl phosphate and 2-methyl cyclohexyl acetate is used as a solvent to form a working solution, wherein the volume ratio of the heavy aromatic hydrocarbon, the trioctyl phosphate and the 2-methyl cyclohexyl acetate is 75:10: 15; by using Pd/Al2O3As hydrogenation catalysts, properties of the catalystsThe quality is as follows: 2-3 mm of spherical shape, and the bulk density is 0.5 +/-0.02 g/ml; the crushing resistance is more than or equal to 40N/cm; the palladium content is 0.3 +/-0.02 wt%; the total effective anthraquinone content in the working solution is 160-200 g/L.
Example 1
The hydrogenation reaction process and the liquid phase hydrogenation reaction system are adopted for carrying out the anthraquinone hydrogenation process. The hydrogenation reactor is filled with 0.072m catalyst3First, hydrogen gas was supplied at 13.66Nm3H is divided into two paths of hydrogen I and hydrogen II, wherein the hydrogen I is 0.07Nm3Adopting an SMK type static mixer structure, wherein the material retention time is 2.5 minutes; hydrogen II is 13.59Nm3H, adopting a shell-and-tube inorganic membrane tube bundle with the aperture of 5 nm; firstly, 4.176m of all the working solution3H and hydrogen I0.07Nm3H, introducing the mixture into a static mixer, and dissolving the mixture under the pressure of 5.0MPa to form a working solution material containing saturated dissolved hydrogen; working solution containing saturated dissolved hydrogen and hydrogen II are mixed to form 13.59Nm3Introducing hydrogen-oil mixer, and introducing the hydrogen-dissolved working solution to the shell side of the membrane tube bundle; introducing hydrogen II into the tube side of the membrane tube bundle to form 5-100 nm nanometer micro bubbles; the operating pressure of the hydrogen-oil mixer is 0.5MPa, the hydrogen II passing through the hydrogen-oil mixer and the hydrogen-dissolved working solution form a microemulsion liquid material flow which is used as the feeding material of the hydrogenation reactor, the liquid-phase hydrogenation reaction is carried out under the conditions of 0.2-0.4 MPa and 40-75 ℃, and the product after the hydrogenation reaction enters the next procedure.
After the treatment by the method, the hydrogenation reaction process is relatively uniform, and the space velocity of the catalyst is 58h-1Under the condition, the obtained hydrogen efficiency is 12.3-12.7 g/L, and the unit consumption of anthraquinone is 0.215kg/t (27.5% hydrogen peroxide).
Example 2
The hydrogenation reaction process and the liquid phase hydrogenation reaction system are adopted for carrying out the first anthraquinone hydrogenation process. The hydrogenation reactor is filled with 0.093m of catalyst3First, hydrogen gas was supplied at 13.66Nm3H is divided into two paths of hydrogen I and hydrogen II, wherein the hydrogen I is 0.42Nm3Adopting a static mixer structure containing spiral plates, wherein the material retention time is 3.5 minutes; the hydrogen II is 13.24Nm3/h and the pore diameter is5nm of shell-and-tube inorganic membrane tube bundle; firstly, 4.176m of all the working solution3H and hydrogen I0.42Nm3Introducing the solution into a static mixer for dissolving under the pressure of 9.9MPa to form hydrogen-dissolved working solution; mixing the hydrogen-dissolved working solution with hydrogen II to obtain 13.24Nm3Introducing hydrogen-oil mixer, and introducing the hydrogen-dissolved working solution to the shell side of the membrane tube bundle; introducing hydrogen II into the tube side of the membrane tube bundle to form 5-100 nm nanometer micro bubbles; the operating pressure of the hydrogen-oil-hydrogen mixer is 0.4MPa, the hydrogen II passing through the hydrogen-oil mixer and the hydrogen-dissolved working solution form a microemulsion liquid material flow which is used as the feeding material of the hydrogenation reactor, the liquid-phase hydrogenation reaction is carried out under the conditions of 0.2-0.4 MPa and 40-75 ℃, and the product after the hydrogenation reaction enters the next procedure.
After the treatment by the method, the hydrogenation reaction process is relatively uniform, and the space velocity of the catalyst is 45h-1Under the condition, the obtained hydrogen efficiency is 12.9-13.5 g/L, and the unit consumption of anthraquinone is 0.173kg/t (27.5% hydrogen peroxide).
Comparative example 1
The anthraquinone hydrogenation process adopts a conventional gas-liquid-solid three-phase hydrogenation reaction process, and the hydrogenation reactor adopts a conventional fixed bed structure. The hydrogenation tower is internally filled with a catalyst of 0.41m3All hydrogen 13.66Nm3H and total working solution 4.176m3After mixing, introducing the mixture into a hydrogenation reactor, carrying out gas/liquid/solid three-phase hydrogenation reaction at the reaction temperature of 40-75 ℃ and the pressure of 0.3-0.4 MP, and enabling the reaction effluent to enter the next working procedure.
After the treatment by the method, the space velocity of the catalyst volume is 10h-1The hydrogen efficiency is 7.25-7.46 g/L, and the unit consumption of anthraquinone is 0.452kg/t (27.5% hydrogen peroxide).
Comparative example 2
The anthraquinone hydrogenation process adopts a liquid phase hydrogenation reaction process, and the implementation mode is that a large amount of working solution circulates and the liquid phase reaction is maintained by slightly high reaction pressure. The hydrogenation tower is filled with 0.12m of catalyst3All hydrogen is 4.5Nm3H and 3.5m of total working solution3The mixture is introduced into a hydrogenation reactor after being mixed, liquid phase hydrogenation reaction is carried out under the conditions that the reaction temperature is 40-75 ℃ and the pressure is 1.8-2.0 MP, and the reaction effluent enters the next working procedure。
After the treatment by the method, the working solution circulation volume is large, the production efficiency of unit working solution is obviously reduced, the hydrogen efficiency is 5.14-5.33 g/L, and the unit consumption of anthraquinone is 0.40kg/t (27.5% hydrogen peroxide).
Comparative example 3
In the hydrogenation process of anthraquinone, a ceramic membrane is adopted to disperse hydrogen, then the hydrogen is mixed with working solution and enters a reactor to carry out hydrogenation reaction, and a shell-and-tube inorganic membrane tube bundle with the aperture of 5nm is adopted. Wherein the hydrogenation tower is filled with 0.15m catalyst3All hydrogen 13.4Nm3H and 2.1m of total working solution3And h, carrying out hydrogenation reaction at the reaction temperature of 40-75 ℃ and the pressure of 0.3-0.4 MP, and enabling the reaction effluent to enter the next working procedure.
After the treatment by the method, the volume space velocity of the catalyst is 14h-1When the hydrogen efficiency is 8.77-9.10 g/L, the unit consumption of anthraquinone is 0.3kg/t (27.5% hydrogen peroxide).
Claims (13)
1. The high-efficiency hydrogenation process for producing hydrogen peroxide by the anthraquinone method is characterized by comprising the following steps of: (1) dividing the total hydrogen of the hydrogenation process into two paths, namely hydrogen I and hydrogen II; hydrogen I and working solution enter hydrogen dissolving equipment, and hydrogen I is dissolved in the working solution to obtain hydrogen dissolving working solution; (2) enabling the hydrogen-dissolved working solution and hydrogen II to enter a mixer containing a ceramic membrane tube bundle, enabling the hydrogen-dissolved working solution to enter the shell side of the tube bundle, enabling the hydrogen II to enter the inner tube side of the tube bundle, radially dispersing the hydrogen II into nano/micron-sized small bubbles through the tube wall of the ceramic membrane tube bundle, and reacting with the hydrogen-dissolved working solution on the shell side to obtain microemulsion fluid; (3) the microemulsion fluid enters a liquid phase hydrogenation reactor filled with a hydrogenation catalyst for hydrogenation reaction, and the hydrogenation reaction product enters the next working procedure.
2. The process of claim 1, wherein: the flow of the hydrogen I in the step (1) accounts for 0.1-50% of the total hydrogen flow.
3. The process of claim 1, wherein: step (a)1) The flow ratio of the hydrogen I to the working solution is 1: 0.3-1: 150, and the flow unit of the hydrogen I is Nm3Flow rate of the working fluid is m3/h。
4. The process of claim 1, wherein: the operation conditions of the hydrogen dissolving equipment in the step (1) are as follows: the temperature is 40-75 ℃, the pressure is 0.1-20.0 MPa, and the residence time of the dissolved hydrogen is 0.5-30 minutes.
5. The process of claim 1, wherein: the hydrogen dissolving equipment in the step (1) is a tubular mixer shell, and a static mixing component or a dynamic mixing component is arranged in the tubular mixer shell; the static mixing component is one or more of SWN type, SMX type, SMK type, SML type or SMH type, or is a reinforced fluid disturbance component containing a spiral plate, a corrugated plate, a rotating blade or a porous plate; the power mixing component is a component which contains one or more of a nozzle structure, a stirring structure, a rotating structure, a Venturi structure, a dissolved air pump structure or a negative pressure forming structure, or realizes the spiral motion of materials in a tangent feeding mode.
6. The process of claim 1, wherein: the mixer in the step (2) is of a shell-and-tube structure containing a ceramic membrane tube bundle, and comprises a shell, the ceramic membrane tube bundle and an inlet and outlet material pipeline; the ceramic membrane tube bundle is arranged on the inner wall of the shell, one end of the shell is provided with a gas phase feeding pipeline connected to the tube side and a liquid phase feeding pipeline connected to the shell side, and the other end of the shell is provided with a discharging pipeline connected to the shell side; the aperture size of the ceramic membrane is 0.1-100 nm.
7. The process of claim 1, wherein: the diameter of the droplet of the microemulsion fluid obtained in the step (2) is 5-100 nm.
8. The process of claim 1, wherein: the operation conditions of the mixer in the step (2) are as follows: the temperature is 40-75 ℃, the pressure of the outer shell of the ceramic membrane tube is 0.1-1.5 MPa, and the pressure difference between the inside and the outside of the ceramic membrane tube bundle is 0.01-10 MPa.
9. The process of claim 1, wherein: the hydrogenation reaction conditions in the step (3) are as follows: the reaction temperature is 40-75 ℃, the reaction pressure is 0.1-1.0 MPa, and the material volume space velocity is 30-80 h-1。
10. The process of claim 1, wherein: the liquid-gas flow ratio of the feeding of the hydrogenation reactor in the step (3) is 1: 1-1: 10, and the unit of the liquid flow is m3In Nm of gas phase flow3/h。
11. The process of claim 1, wherein: the liquid phase hydrogenation reactor in the step (3) is of a fixed bed structure, a microemulsion fluid feeding pipeline and a tail gas discharge pipeline are arranged at the top, and a hydrogenation reaction product discharging pipeline is arranged at the bottom; the tail gas discharge line is used for discharging unreacted hydrogen and inert gas in the reactor, and is operated intermittently or continuously according to the hydrogenation reaction depth.
12. The process of claim 1, wherein: the hydrogenation catalyst in the step (3) is an anthraquinone hydrogenation catalyst taking palladium and/or platinum as an active component.
13. A liquid phase hydrogenation reaction system, characterized by: the system comprises a hydrogen dissolving area, a hydrogen-oil emulsifying area and a liquid-phase hydrogenation reaction area; the hydrogen dissolving area is used for dissolving hydrogen I into working solution and comprises a plurality of hydrogen dissolving devices, and each hydrogen dissolving device comprises a hydrogen feeding pipeline for introducing hydrogen, a liquid phase feeding pipeline for introducing the working solution and a liquid phase discharging pipeline for leading out the hydrogen dissolving working solution; the hydrogen-oil emulsification zone is used for dissolving hydrogen II in hydrogen-dissolved working solution and comprises a plurality of mixers, wherein each mixer comprises a liquid-phase feeding pipeline for introducing the hydrogen-dissolved working solution to the shell side, a gas-phase feeding pipeline for introducing hydrogen to the tube side, and a discharge pipeline for leading out microemulsion fluid formed by the hydrogen and the hydrogen-dissolved working solution; the liquid-phase hydrogenation reaction zone is used for carrying out hydrogenation reaction on the microemulsion fluid and comprises a plurality of groups of liquid-phase hydrogenation reactors, wherein each group of liquid-phase hydrogenation reactor comprises a feeding pipeline for introducing the microemulsion fluid, a discharging pipeline for leading out a hydrogenation reaction product and a pipeline for discharging unreacted hydrogen.
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| CN112499592A (en) * | 2019-09-14 | 2021-03-16 | 南京延长反应技术研究院有限公司 | System and process for preparing hydrogen peroxide based on anthraquinone method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB867679A (en) * | 1958-10-06 | 1961-05-10 | Allied Chem | Improved process for the preparation of hydrogen peroxide |
| JPS6011208A (en) * | 1983-06-25 | 1985-01-21 | ゴスダルストベニイ・ナウチノ−イススレドバテルスキイ・インステイテユト・ヒミイ・イ・テクノロジイ・エレメントオルガニチエスキフ・ソエデイネニイ | Manufacture of hydrogen peroxide |
| CN1069469A (en) * | 1991-08-09 | 1993-03-03 | 巴陵石油化工公司洞庭氮肥厂 | Alkalizing-dehydrating technology for hydrogen peroxide solution |
| DE19808385A1 (en) * | 1998-02-27 | 1999-09-02 | Basf Ag | Process for the suspension hydrogenation of an anthraquinone compound in a special reactor for the production of hydrogen peroxide |
| EP1209122A1 (en) * | 2000-11-24 | 2002-05-29 | Degussa AG | Process for continuous oxidation |
| CN102051207A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for enhancing mass transfer through suspension bed hydrogenation technology |
| CN105540551B (en) * | 2014-11-03 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of efficient hydrogenation process in Hydrogen Peroxide Production |
| CN105621365B (en) * | 2014-11-03 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of hydrogenation process in Hydrogen Peroxide Production |
| CN105800565A (en) * | 2014-12-31 | 2016-07-27 | 湖南长岭石化科技开发有限公司 | Hydrogenation method for hydrogen peroxide preparation through anthraquinone process and method for producing hydrogen peroxide |
| CN106892408B (en) * | 2015-12-18 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of method for oxidation of hydrogen peroxide production process |
| CN107098317B (en) * | 2017-06-15 | 2023-06-27 | 扬州惠通科技股份有限公司 | System and method for producing hydrogen peroxide by anthraquinone process |
| CN107098318B (en) * | 2017-06-15 | 2023-07-14 | 扬州惠通科技股份有限公司 | Fluidized bed hydrogenation reaction system and hydrogenation reaction method for producing hydrogen peroxide |
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