CN107098318B - Fluidized bed hydrogenation reaction system and hydrogenation reaction method for producing hydrogen peroxide - Google Patents
Fluidized bed hydrogenation reaction system and hydrogenation reaction method for producing hydrogen peroxide Download PDFInfo
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- CN107098318B CN107098318B CN201710452002.8A CN201710452002A CN107098318B CN 107098318 B CN107098318 B CN 107098318B CN 201710452002 A CN201710452002 A CN 201710452002A CN 107098318 B CN107098318 B CN 107098318B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a fluidized bed hydrogenation reaction system and a hydrogenation reaction method for producing hydrogen peroxide, wherein a hydrogenated liquid outlet at the lower part of a hydrogenation reaction kettle is connected with inlets of catalyst filters through a hydrogenated liquid annular pipe; the outlet of each catalyst filter is respectively provided with a three-way valve, and the outlet of the three-way valve is respectively connected with a hydrogenated liquid outlet pipe and a hydrogenated kettle working liquid recoil pipe; a stirring shaft and stirring blades are arranged along the axis of the hydrogenation reaction kettle; the bottom of each catalyst filter is connected with a working solution supply pipe through a catalyst filter return header pipe respectively, and the working solution supply pipe is inserted into the inner cavity of the hydrogenation reaction kettle from the middle part and is bent downwards to the axis; the top of the hydrogenation reaction kettle is provided with a gas phase outlet, and a catalyst adding pipe and a hydrogen supply pipe are respectively inserted in the gas phase outlet, and the hydrogen supply pipe extends downwards to the bottom of the hydrogenation reaction kettle and turns upwards to the center of the lower part of the hydrogenation reaction kettle. The hydrogenation reaction system has low manufacturing cost and unit consumption of products and high production efficiency.
Description
Technical Field
The invention relates to a fluidized bed hydrogenation reaction system for producing hydrogen peroxide, and also relates to a hydrogenation reaction method for producing hydrogen peroxide by using a fluidized bed, belonging to the technical field of hydrogen peroxide manufacturing equipment.
Background
Hydrogen peroxide is an important inorganic chemical raw material and is widely applied to the fields of papermaking, textile, medicine, chemical industry, electronics, environmental protection and the like. The hydrogen peroxide generates water and oxygen after decomposition, has no secondary pollution to the environment, and accords with the concept of green product production.
In the prior art, hydrogen peroxide is usually prepared by an anthraquinone method, wherein 2-ethyl anthraquinone is used as a carrier, palladium is used as a catalyst, hydrogen and oxygen are directly used for synthesizing the hydrogen peroxide, and the steps of hydrogenation, oxidation, extraction, post-treatment and the like are sequentially carried out. Wherein the hydrogenation reaction is generally carried out in a fixed bed, and the anthraquinone working solution is subjected to hydrogenation reaction with hydrogen under the action of certain pressure, temperature and palladium catalyst to produce the hydroanthraquinone.
The fixed bed anthraquinone process has low production efficiency, small scale, high power consumption, heavy equipment, large occupied area and high production cost.
Disclosure of Invention
The invention aims at overcoming the problems in the prior art and providing a fluidized bed hydrogenation reaction system for producing hydrogen peroxide, which has compact equipment, can realize continuous production, and has low production consumption of unit products, high production efficiency and low manufacturing cost.
In order to solve the technical problems, the fluidized bed hydrogenation reaction system for producing hydrogen peroxide comprises a vertical hydrogenation reaction kettle, wherein the circumference of the lower part of the hydrogenation reaction kettle is uniformly provided with hydrogenation liquid outlets, each hydrogenation liquid outlet is respectively connected with a hydrogenation liquid annular pipe which surrounds the periphery of the hydrogenation reaction kettle, the hydrogenation liquid annular pipe is connected with a catalyst filter total inlet pipe, and the catalyst filter total inlet pipe is respectively connected with a filter inlet valve of each catalyst filter inlet; the outlet of each catalyst filter is respectively provided with a three-way valve, the first outlet of the three-way valve is connected with a hydrogenated liquid outlet pipe, and the second outlet of the three-way valve is connected with a hydrogenated kettle working liquid recoil pipe; a stirring shaft is arranged along the central line of the hydrogenation reaction kettle, and stirring blades are arranged on the stirring shaft; the bottom of each catalyst filter is respectively provided with a catalyst filter reflux valve, the outlet of each catalyst filter reflux valve is respectively connected with a catalyst filter reflux main pipe, the lower end of the catalyst filter reflux main pipe is connected with a working fluid supply pipe, and the working fluid supply pipe is inserted into the inner cavity of the hydrogenation reaction kettle from the middle part of the hydrogenation reaction kettle in the height direction and is bent downwards to extend to the axis of the hydrogenation reaction kettle; the top of hydrogenation cauldron is equipped with hydrogenation cauldron gaseous phase export and peg graft respectively has vertical downwardly extending catalyst to add pipe and hydrogen supply pipe, catalyst adds the upper end of pipe and adds the exit linkage of jar through the catalyst and add the valve with the catalyst, the hydrogen supply pipe extends to hydrogenation cauldron's bottom along hydrogenation cauldron's inner wall and turns round and upwards extends to hydrogenation cauldron's lower part center.
Compared with the prior art, the invention has the following beneficial effects: a catalyst adding valve is opened to put a proper amount of catalyst into the hydrogenation reaction kettle, and fresh working solution enters the center of a liquid phase space of the hydrogenation reaction kettle from a working solution supply pipe and is sprayed downwards, and the fresh working solution is diffused downwards to the periphery under the stirring of a stirring blade; fresh hydrogen is sprayed upwards from the lower port of the hydrogen supply pipe, and is dispersed into a plurality of small bubbles to be diffused upwards to the periphery under the stirring of the stirring blade, so that the fresh working solution and the hydrogen can be quickly mixed and reacted by opposite convection; anthraquinone in the working solution reacts with hydrogen to generate hydrogen anthraquinone under the action of powdery palladium catalyst, and the nitrogen and the residual unreacted hydrogen are discharged from a gas phase outlet of the hydrogenation kettle at the top of the hydrogenation reaction kettle. The circumference of the lower part of the hydrogenation reaction kettle is uniformly provided with a hydrogenated liquid outlet which is converged into a hydrogenated liquid annular pipe, so that the hydrogenated liquid can uniformly flow out on the whole circumference. Most of catalyst filters are normally in a working state, at the moment, the three-way valve is in a state that the first outlet is conducted, the second outlet is closed, and after the catalyst filter intercepts the catalyst, clean hydrogenated liquid flows out from the first outlet of the three-way valve and enters a hydrogenated liquid outlet pipe; when excessive catalyst is piled up on the filter core of the catalyst filter, on the one hand, the filtration capacity of the catalyst filter is reduced, on the other hand, the concentration of the catalyst in the hydrogenation reaction kettle is reduced, the hydrogenation reaction is affected, at the moment, the three-way valve is switched to a state that the first outlet is closed, the second outlet is conducted, the catalyst filter reflux valve is opened, the hydrogenation liquid in the working solution reflux pipe of the hydrogenation kettle enters the catalyst filter from the recoil valve, the catalyst piled up on the surface of the filter core is washed off, the catalyst enters the working solution supply pipe through the catalyst filter reflux valve and the catalyst filter reflux main pipe, the fresh working solution is returned to the hydrogenation reaction kettle, and all the catalyst is recycled. The catalyst filters are arranged, so that the back flushing of the catalyst is conveniently carried out in turn, and the fluidized bed can be ensured to be continuously and stably produced; for example, when the fluidized bed works, one catalyst filter is kept in a backflushing state, and the other catalyst filters are all in a working state, so that the production efficiency can be improved, the yield of the hydroanthraquinone can be improved, the filtering efficiency of each catalyst filter can be ensured, the concentration of the catalyst in the hydrogenation reaction kettle can be ensured, and the fluidized bed is always in a stable working state. Through the switching-over of three-way valve, the switching of normal work and recoil is very convenient and fast. The system has the advantages of rapid hydrogenation reaction, stable catalyst concentration in the hydrogenation reaction kettle, stable continuous production of high-quality hydrogenated liquid, low hydrogen unit consumption and high hydrogenation efficiency.
As an improvement of the invention, the upper part of the stirring shaft is sleeved with a central sleeve, the upper end of the central sleeve is in closed connection with the inner wall of the hydrogenation reaction kettle, and the lower end of the central sleeve is inserted into the liquid phase space of the hydrogenation reaction kettle. The central sleeve and the vent pipe form a liquid seal for the gas phase space at the top of the hydrogenation reaction kettle, the condensate channel is isolated from the gas phase space at the top of the hydrogenation reaction kettle, and condensate entering the central sleeve is sent to the central area of the liquid phase space of the reaction kettle.
As a further improvement of the invention, the gas phase outlet of the hydrogenation kettle is connected with the gas inlet of the condenser, the gas outlet of the condenser is connected with the tail gas blow-down pipe through the tail gas emission control valve, and the liquid outlet of the condenser is connected with the upper part of the central sleeve through the condensate return pipe. Non-condensable gases such as solvent vapor and the like discharged from a gas phase outlet of the hydrogenation kettle are condensed by a condenser and then become liquid again, and flow back to a central sleeve from a condensate return pipe to continue to participate in the reaction of the hydrogenation reaction kettle, so that the material loss is reduced; the tail gas emission control valve can control the emission of tail gas and adjust the pressure in the hydrogenation reaction kettle, the liquid sealing effect of the central sleeve can prevent gas at the top of the hydrogenation reaction kettle from entering the condensate return pipe, condensate directly reaches the central region of the liquid phase space of the reaction kettle after flowing out from the lower end of the central sleeve, is rapidly mixed with fresh working solution under the stirring of the stirring blade, and is jointly and downwards diffused to the periphery to be uniformly mixed with upward hydrogen for reaction.
As a further improvement of the invention, at least one vertical baffle plate is arranged along the inner wall of the liquid phase space of the hydrogenation reaction kettle, and the cross section of the vertical baffle plate extends along the diameter of the hydrogenation reaction kettle. The rotation of the stirring blade drives the working solution to rotate, a circulation is formed in the inner cavity of the hydrogenation reaction kettle, and the stable circulation makes the substances at the outer layer and the substances at the inner layer of the circulation difficult to mix; the vertical baffle is inserted into the circulation layer along the radial direction, so that the circulation layer is thoroughly destroyed, and the working solution and the hydrogen can be quickly and uniformly mixed to generate hydrogenation reaction.
As a further improvement of the invention, the lower end of the catalyst filter return manifold is connected with a return pipe elbow, the lower end of the return pipe elbow is inserted into the working fluid supply pipe, and the outlet of the return pipe elbow is positioned at the center of the working fluid supply pipe and is in the same direction as the flow direction of the working fluid. The catalyst recovered by back flushing of each catalyst filter is directly injected into the center of the working solution supply pipe from the return pipe elbow of the catalyst filter return manifold, and the back-flushing catalyst is rapidly dispersed in the fresh working solution by utilizing the jet flow action of the fresh working solution, so that the catalyst is uniformly mixed, and the catalyst is prevented from agglomerating and entering the hydrogenation reaction kettle.
As a further improvement of the invention, the lower end of the catalyst filter return manifold is connected to the circumference of the large end of the conical sleeve, the conical sleeve is sleeved on the periphery of the working solution supply pipe and is coaxial with the working solution supply pipe, the large end of the conical sleeve is closed, the small end of the conical sleeve faces the hydrogenation reaction kettle and is in butt joint with the working solution supply pipe, the part of the working solution supply pipe in the conical sleeve is provided with a throat opening with gradually reduced diameter, and the throat opening extends to the small end of the conical sleeve. Catalyst recovered by back flushing of the catalyst filter enters the conical sleeve from the back flow main pipe of the catalyst filter, fresh working solution flows forward at a high speed in the working solution supply pipe, the flow speed at the throat is increased, the pressure is reduced, the catalyst entering the conical sleeve has a suction effect, the catalyst can be rapidly and uniformly dispersed in the fresh working solution, and catalyst agglomeration is avoided from entering the hydrogenation reaction kettle.
As a further improvement of the invention, the lower part of the hydrogenation reaction kettle is provided with an annular sleeve coaxial with the hydrogenation reaction kettle, the circumference of the annular sleeve is spaced from the inner wall of the hydrogenation reaction kettle by a certain distance, and each hydrogenated liquid outlet is positioned on the circumference of the same height as the axial middle part of the hydrogenation reaction kettle and the annular sleeve; the lower part of the stirring shaft is provided with a lower stirring blade, the lower stirring blade is positioned in the annular sleeve, and the middle part of the stirring shaft is provided with an upper stirring blade; the outlet of the working fluid supply pipe is positioned above the upper stirring blade; the outlet of the hydrogen supply pipe is positioned below the center of the lower port of the annular sleeve. The annular sleeve shields the hydrogenated liquid outlets, fresh hydrogen enters the center of the annular sleeve upwards after being discharged from the port of the hydrogen supply pipe, is scattered and dispersed into a plurality of bubbles by the rotating lower stirring blades to enter the annular sleeve, and the annular sleeve prevents the hydrogen bubbles from choking out from the hydrogenated liquid outlets; fresh working solution flows out from top to bottom to the upper stirring blades, and is dispersed downwards and around under the rotation stirring of the upper stirring blades, so that the fresh working solution is favorable for being uniformly mixed with ascending hydrogen bubbles, hydrogenation reaction is rapidly carried out, and the annular sleeve can also prevent fresh working solution just entering from directly choking out from a hydrogenated solution outlet; the working solution sprayed downwards is mixed with the hydrogen bubbles below and then flows upwards, so that the freshest working solution is contacted with the area with the highest hydrogen concentration at first, and the hydrogenation efficiency is improved.
Another object of the present invention is to overcome the problems of the prior art and to provide a hydrogenation reaction method for producing hydrogen peroxide by a fluidized bed, which can realize continuous production, and has low production consumption per unit product, high production efficiency and low manufacturing cost.
In order to solve the technical problems, the hydrogenation reaction method for producing hydrogen peroxide by adopting the fluidized bed hydrogenation reaction system sequentially comprises the following steps of preparing a hydrogenation reaction solvent; secondly, adding 2-ethylanthraquinone and 2-amylanthraquinone into the solvent to form a working solution for hydrogenation reaction, wherein each liter of solvent is added with 2-ethylanthraquinone (80-110) g/L, and each liter of solvent is added with 2-amylanthraquinone (60-140) g/L; preparing a powdery palladium catalyst, wherein the particle size and volume distribution of the palladium catalyst is as follows: the volume percentage of the grain diameter is more than 120 micrometers and is not more than 4 percent; the volume percentage of the particle size is less than 80 microns and is not more than 4 percent, and the rest particle sizes are 80-120 microns; a catalyst adding valve is opened to put a proper amount of catalyst into the hydrogenation reaction kettle, and fresh working solution enters the center of a liquid phase space of the hydrogenation reaction kettle from a working solution supply pipe and is sprayed downwards, so that the fresh working solution is diffused downwards to the periphery under the stirring of a stirring blade; fresh hydrogen is sprayed upwards from the lower port of the hydrogen supply pipe, dispersed into a plurality of small bubbles to be diffused upwards to the periphery under the stirring of the stirring blade, fully mixed with fresh working solution and stirred; fifthly, reacting anthraquinone in the working solution with hydrogen to generate hydrogen anthraquinone under the action of a powdery palladium catalyst; the gas phase substances at the upper part of the hydrogenation reaction kettle are discharged from a gas phase outlet of the hydrogenation kettle and enter a condenser for condensation, the non-condensable gas including unreacted hydrogen is discharged from a tail gas blow-down pipe, and the condensate returns to the center sleeve; the hydrogenated liquid and the powdery catalyst enter a hydrogenated liquid annular pipe from each hydrogenated liquid outlet on the circumference of the lower part of the hydrogenation reaction kettle, and then enter each catalyst filter through a catalyst filter total inlet pipe for filtration; switching the three-way valve to a state that the first outlet is conducted and the second outlet is closed, and after the catalyst is intercepted by the catalyst filter, clean hydrogenated liquid flows out from the first outlet of the three-way valve and enters a hydrogenated liquid outlet pipe; and when the catalyst filters are in backflushing, the three-way valve is switched to a state that the first outlet is closed and the second outlet is communicated, the catalyst filter reflux valve is opened, hydrogenated liquid in the hydrogenated kettle working solution backflushing pipe enters the catalyst filter from the backflushing valve, catalyst accumulated on the surface of the filter element is flushed down, and the hydrogenated liquid enters the working solution supply pipe through the catalyst filter reflux valve and the catalyst filter reflux main pipe and returns to the hydrogenated reaction kettle along with fresh working solution.
Compared with the prior art, the invention has the following beneficial effects: fresh working solution is uniformly distributed on the circumference of the bottom of the hydrogenation reaction kettle and is sprayed downwards; the hydrogen is divided into a plurality of tiny hydrogen bubbles by the densely distributed hydrogen distribution holes, so that the contact area of the hydrogen and the working solution is increased, and the freshest working solution is firstly contacted with the area with the highest hydrogen concentration, thereby being beneficial to the rapid hydrogenation reaction and improving the hydrogenation efficiency. The catalyst is intercepted by the catalyst filter after flowing out along with the hydrogenation liquid, returns to the hydrogenation reaction kettle through alternate recoil, and continuously and reasonably flows through the catalyst, so that the filtering efficiency of the catalyst filter is ensured, and the catalyst concentration in the hydrogenation reaction kettle is also ensured. The catalyst and hydrogen used in the invention can be fully recycled, which is beneficial to reducing the production consumption of unit products, improving the hydrogenation efficiency and reducing the production cost.
As a preferable scheme of the invention, the hydrogenation reaction solvent in the step (A) is prepared from the following components in percentage by volume: (45-50 v%, C10 arene: (50-55 v%) and the total volume of them is 100%. C10 aromatic hydrocarbon is used for dissolving 2-ethylanthraquinone and 2-amylanthraquinone, and diisobutylcarbinol increases the solubility of 2-ethylanthraquinone and 2-amylanthraquinone.
As a preferable scheme of the invention, the hydrogenation reaction solvent in the step (A) is prepared from the following volume percent of tetrabutyl urea: (12-30 v%) trioctyl phosphate: (8-12) v%, C10 aromatic hydrocarbon: (60-76) v%, and the total volume of the three is 100%. C10 arene mainly dissolves 2-ethyl anthraquinone, 2-amyl anthraquinone and tetrahydro2-ethyl anthraquinone generated by reaction, but can not dissolve 2-ethyl hydro anthraquinone and tetrahydro2-ethyl hydro anthraquinone generated after hydrogenation; thus, trioctyl phosphate and tetrabutyl urea capable of dissolving 2-ethyl hydro anthraquinone and tetrahydro 2-ethyl anthraquinone are also needed as polar solvents. The invention has higher C10 aromatic hydrocarbon content, and can avoid the difficulty in operating the extraction tower caused by the increase of the specific gravity of the working solution; trioctyl phosphate has the advantages of high boiling point, no irritating taste and strong capability of dissolving hydroanthraquinone, but if the content is too high, the viscosity of the working solution is increased, and mass transfer is difficult; the tetrabutyl urea is transparent or slightly yellowish liquid, has slightly higher viscosity than water, has the advantages of large difference from water, large surface tension and the like, and has large solubility for 2-ethyl hydro anthraquinone and tetrahydro 2-ethyl anthraquinone relative to trioctyl phosphate and large distribution coefficient of hydrogen peroxide in two phases. The solvent component combination and proportion of the invention lead the working solution to have the advantages of small volatilization loss, safe use, favorable operation environment, reduced content of the raffinate hydrogen peroxide and improved concentration of the extraction solution, and the product quality is promoted by greatly reducing the TOC (total organic carbon) content of the hydrogen peroxide product due to the reduced spot solubility with water.
Drawings
The invention will now be described in further detail with reference to the drawings and the detailed description, which are provided for reference and illustration only and are not intended to limit the invention.
FIG. 1 is a schematic diagram of the structure of a fluidized bed hydrogenation reaction system for producing hydrogen peroxide according to the present invention.
Fig. 2 is a plan view of the hydrogenated liquid outlet and the hydrogenated liquid annular pipe in fig. 1.
FIG. 3 is a schematic illustration of a second connection scheme of the catalytic filter return manifold to the working fluid supply.
In the figure: 1. a hydrogenation reaction kettle; 1a, a gas phase outlet of a hydrogenation kettle; 1b, a hydrogenated liquid outlet; 1c, a central sleeve; 1d, a vertical baffle; 1e, an annular sleeve; 1f, a stirring shaft; 1g, stirring blades; 1h, a hydrogenated liquid annular tube; 2. a catalyst adding tank; 3. a condenser; 4. a catalyst filter; G1. a working fluid supply pipe; g1a. taper sleeve; G2. a hydrogen supply pipe; G3. a catalyst addition pipe; G4. a tail gas blow-down pipe; G5. a condensate return pipe; G6. a catalyst filter total inlet pipe; G7. a hydrogenated liquid outlet pipe; G8. a hydrogenation kettle working solution backwash tube; G9. a catalyst filter return header; v1. a catalyst addition valve; v2. a three-way valve; v3. filter inlet valve; v4. a catalytic filter return valve; v5. exhaust emission control valve.
Detailed Description
As shown in fig. 1 and 2, the fluidized bed hydrogenation reaction system for producing hydrogen peroxide of the present invention comprises a vertical hydrogenation reaction kettle 1, wherein the circumference of the lower part of the hydrogenation reaction kettle 1 is uniformly provided with hydrogenation liquid outlets 1b, each hydrogenation liquid outlet 1b is respectively connected with a hydrogenation liquid annular pipe 1h which surrounds the circumference of the hydrogenation reaction kettle, the hydrogenation liquid annular pipe 1h is connected with a catalyst filter total inlet pipe G6, and the catalyst filter total inlet pipe G6 is respectively connected with a filter inlet valve V3 of each catalyst filter 4 inlet; the outlets of the catalyst filters 4 are respectively provided with a three-way valve V2, a first outlet of the three-way valve V2 is connected with a hydrogenated liquid outlet pipe G7, and a second outlet of the three-way valve V2 is connected with a hydrogenated kettle working liquid backwash pipe G8; a stirring shaft 1f is arranged along the central line of the hydrogenation reaction kettle 1, and stirring blades 1g are arranged on the stirring shaft 1 f; the bottom of each catalyst filter 4 is respectively provided with a catalyst filter reflux valve V4, the outlet of each catalyst filter reflux valve V4 is respectively connected with a catalyst filter reflux main pipe G9, the lower end of the catalyst filter reflux main pipe G9 is connected with a working solution supply pipe G1, and the working solution supply pipe G1 is inserted into the inner cavity of the hydrogenation reactor 1 from the middle part of the hydrogenation reactor in the height direction and is downwards bent and extended to the axis of the hydrogenation reactor 1; the top of the hydrogenation reaction kettle 1 is provided with a hydrogenation kettle gas phase outlet 1a, and a catalyst adding pipe G3 and a hydrogen gas supply pipe G2 which extend downwards vertically are respectively inserted in the hydrogenation kettle gas phase outlet, the upper end of the catalyst adding pipe G3 is connected with the outlet of the catalyst adding tank 2 through a catalyst adding valve V1, and the hydrogen gas supply pipe G2 extends to the bottom of the hydrogenation reaction kettle 1 along the inner wall of the hydrogenation reaction kettle 1 and extends upwards to the center of the lower part of the hydrogenation reaction kettle 1 in a turning way.
A catalyst adding valve V1 is opened to put a proper amount of catalyst into the hydrogenation reaction kettle 1, and fresh working solution enters the center of a liquid phase space of the hydrogenation reaction kettle from a working solution supply pipe G1 and is sprayed downwards, and the fresh working solution is diffused downwards to the periphery under the stirring of a stirring blade 1G; fresh hydrogen is sprayed upwards from the lower port of the hydrogen supply pipe G2, and is dispersed into a plurality of small bubbles to be dispersed upwards to the periphery under the stirring of the stirring blade 1G, so that the fresh working solution and the hydrogen can be quickly mixed and reacted by opposite convection; anthraquinone in the working solution reacts with hydrogen to generate hydrogen anthraquinone under the action of powdery palladium catalyst, and nitrogen and residual unreacted hydrogen are discharged from a gas phase outlet 1a of the hydrogenation reactor at the top of the hydrogenation reactor. The circumference of the lower part of the hydrogenation reaction kettle 1 is uniformly provided with a hydrogenated liquid outlet 1b and is converged into a hydrogenated liquid annular pipe 1h, so that the hydrogenated liquid can uniformly flow out on the whole circumference.
Most of the catalyst filters 4 are normally in a working state, at this time, the three-way valve V2 is in a state that the first outlet is conducted, the second outlet is closed, and after the catalyst filter 4 entraps catalyst, clean hydrogenated liquid flows out from the first outlet of the three-way valve V2 and enters the hydrogenated liquid outlet pipe G7; when too much catalyst is accumulated on the filter element of the catalyst filter 4, on the one hand, the filtering capability of the catalyst filter 4 is reduced, on the other hand, the concentration of the catalyst in the hydrogenation reaction kettle 1 is reduced, the hydrogenation reaction is affected, at the moment, the three-way valve V2 is switched to a state that the first outlet is closed, the second outlet is conducted, the catalyst filter reflux valve V4 is opened, the hydrogenation liquid in the hydrogenation kettle working liquid reflux pipe G8 enters the catalyst filter from the recoil valve, the catalyst accumulated on the surface of the filter element is washed off, the catalyst enters the working liquid supply pipe G1 through the catalyst filter reflux valve V4 and the catalyst filter reflux main pipe G9, and returns to the hydrogenation reaction kettle 1 along with fresh working liquid, and all the catalyst is recycled.
The catalyst filters are arranged, so that the back flushing of the catalyst is conveniently carried out in turn, and the fluidized bed can be ensured to be continuously and stably produced; for example, when the fluidized bed works, one catalyst filter is kept in a backflushing state, and the other catalyst filters are all in a working state, so that the production efficiency can be improved, the yield of the hydroanthraquinone can be improved, the filtering efficiency of each catalyst filter can be ensured, the concentration of the catalyst in the hydrogenation reaction kettle 1 can be ensured, and the fluidized bed is always in a stable working state.
The upper part of the stirring shaft 1f is sleeved with a central sleeve 1c, the upper end of the central sleeve 1c is in closed connection with the inner wall of the hydrogenation reaction kettle 1, and the lower end of the central sleeve 1c is inserted into the liquid phase space of the hydrogenation reaction kettle 1.
The gas phase outlet 1a of the hydrogenation kettle is connected with the gas inlet of the condenser 3, the gas outlet of the condenser 3 is connected with the tail gas blow-down pipe G4 through the tail gas emission control valve V5, and the liquid outlet of the condenser 3 is connected with the upper part of the central sleeve 1c through the condensate return pipe G5. Non-condensable gases such as solvent vapor and the like discharged from a gas phase outlet 1a of the hydrogenation kettle are condensed by a condenser 3 and then become liquid again, and flow back to a central sleeve 1c from a condensate return pipe G5 to continue to participate in the reaction of the hydrogenation reaction kettle 1, so that the material loss is reduced; the tail gas emission control valve V5 can control the emission amount of tail gas and regulate the pressure in the hydrogenation reaction kettle 1; the gas phase space at the top of the hydrogenation reaction kettle is sealed by the central sleeve 1c and the gas permeability pipe, a condensate channel is isolated from the gas phase space at the top of the hydrogenation reaction kettle, gas at the top of the hydrogenation reaction kettle can be prevented from entering the condensate return pipe G5, condensate directly reaches the central area of the liquid phase space of the reaction kettle after flowing out from the lower end of the central sleeve 1c, and is rapidly mixed with fresh working solution under the stirring of the stirring blade 1G to be diffused downwards to the periphery together, so that the condensate is uniformly mixed with upward hydrogen for reaction.
At least one vertical baffle plate 1d is arranged along the inner wall of the liquid phase space of the hydrogenation reaction kettle, and the cross section of the vertical baffle plate 1d extends along the diameter of the hydrogenation reaction kettle 1. The rotation of the stirring blade 1g drives the working solution to rotate, a circulation is formed in the inner cavity of the hydrogenation reaction kettle, and the stable circulation makes the substances at the outer layer and the substances at the inner layer of the circulation difficult to mix; the vertical baffle plate 1d is inserted into the circulation layer along the radial direction, so that the circulation layer is thoroughly destroyed, and the working solution and the hydrogen can be quickly and uniformly mixed to generate hydrogenation reaction.
The lower extreme of catalyst filter return manifold G9 is connected with the return bend, and the lower extreme of return bend inserts in the working fluid supply pipe G1, and the export of return bend is located the center of working fluid supply pipe G1 and with the flow direction syntropy of working fluid. The catalyst recovered by back flushing of each catalyst filter is directly injected into the center of the working solution supply pipe G1 from the return pipe elbow of the catalyst filter return header pipe G9, and the back-flushing catalyst is rapidly dispersed in the fresh working solution by utilizing the jet flow effect of the fresh working solution, so that the catalyst is uniformly mixed, and the catalyst is prevented from agglomerating to enter the hydrogenation reaction kettle 1.
As shown in fig. 3, another scheme is: the lower extreme of catalyst filter return current house steward G9 is connected on the big end circumference of toper sleeve pipe G1a, and toper sleeve pipe G1a suit is at the periphery of working solution supply tube G1 and coaxial with working solution supply tube G1, and the big end of toper sleeve pipe G1a is sealed, and the tip of toper sleeve pipe G1a is faced hydrogenation reactor 1 and is docked with working solution supply tube G1, and the part that working solution supply tube G1 is located toper sleeve pipe G1a is equipped with the throat that the diameter reduces gradually, and the throat stretches to the tip of toper sleeve pipe G1a. Catalyst recovered by back flushing of the catalyst filter enters the conical sleeve G1a from the back flow main pipe G9 of the catalyst filter, fresh working solution flows forward at a high speed in the working solution supply pipe G1, the flow speed at the throat is increased, the pressure is reduced, the catalyst entering the conical sleeve G1a has a suction effect, the catalyst can be rapidly and uniformly dispersed in the fresh working solution, and catalyst agglomeration is avoided from entering the hydrogenation reaction kettle 1.
The lower part of the hydrogenation reaction kettle 1 is provided with an annular sleeve 1e coaxial with the hydrogenation reaction kettle, the circumference of the annular sleeve 1e is spaced from the inner wall of the hydrogenation reaction kettle 1 by a certain distance, and each hydrogenated liquid outlet 1b is positioned on the circumference of the same height as the axial middle part of the hydrogenation reaction kettle 1 and the annular sleeve; the lower part of the stirring shaft 1f is provided with a lower stirring blade, the lower stirring blade is positioned in the annular sleeve 1e, and the middle part of the stirring shaft 1f is provided with an upper stirring blade; the outlet of the working fluid supply pipe G1 is positioned above the upper stirring blade; the outlet of the hydrogen gas supply pipe G2 is located below the center of the lower port of the annular sleeve.
The annular sleeve 1e shields the hydrogenated liquid outlets 1b, fresh hydrogen enters the center of the annular sleeve 1e upwards after being discharged from the port of the hydrogen supply pipe G2, is scattered by the rotating lower stirring blades and is dispersed into a plurality of bubbles to enter the circulation in the annular sleeve 1e, and the annular sleeve 1e prevents the hydrogen bubbles from choking out from the hydrogenated liquid outlets 1 b; fresh working solution flows out from top to bottom to the upper stirring blades, and is dispersed downwards and around under the rotation stirring of the upper stirring blades, so that the fresh working solution is favorable for being uniformly mixed with ascending hydrogen bubbles, hydrogenation reaction is rapidly carried out, and the annular sleeve 1e can also prevent fresh working solution just entering from directly choking out from the hydrogenated solution outlet 1 b; the working solution sprayed downwards is mixed with the hydrogen bubbles below and then flows upwards, so that the freshest working solution is contacted with the area with the highest hydrogen concentration at first, and the hydrogenation efficiency is improved.
The invention relates to a hydrogenation reaction method for producing hydrogen peroxide by adopting a fluidized bed hydrogenation reaction system, which sequentially comprises the following steps of preparing a hydrogenation reaction solvent; secondly, adding 2-ethylanthraquinone and 2-amylanthraquinone into the solvent to form a working solution for hydrogenation reaction, wherein each liter of solvent is added with 2-ethylanthraquinone (80-110) g/L, and each liter of solvent is added with 2-amylanthraquinone (60-140) g/L; preparing a powdery palladium catalyst, wherein the particle size and volume distribution of the palladium catalyst is as follows: the volume percentage of the grain diameter is more than 120 micrometers and is not more than 4 percent; the volume percentage of the particle size is less than 80 microns and is not more than 4 percent, and the rest particle sizes are 80-120 microns; the catalyst adding valve V1 is opened to put a proper amount of catalyst into the hydrogenation reaction kettle 1, and fresh working solution enters the center of the liquid phase space of the hydrogenation reaction kettle from the working solution supply pipe G1 and is sprayed downwards, and the fresh working solution is diffused downwards to the periphery under the stirring of the stirring blade; fresh hydrogen is sprayed upwards from the lower port of the hydrogen supply pipe G2, and is dispersed into a plurality of small bubbles to be dispersed upwards to the periphery under the stirring of the stirring blade, and the small bubbles are fully mixed with fresh working solution and stirred; fifthly, reacting anthraquinone in the working solution with hydrogen to generate hydrogen anthraquinone under the action of a powdery palladium catalyst; the gas phase substances at the upper part of the hydrogenation reaction kettle 1 are discharged from a gas phase outlet 1a of the hydrogenation kettle and enter a condenser 3 for condensation, the non-condensable gas including unreacted hydrogen is discharged from a tail gas blow-down pipe G4, and the condensate returns to the center sleeve 1 c; hydrogenated liquid and powdery catalyst enter a hydrogenated liquid annular pipe 1h from each hydrogenated liquid outlet 1b on the circumference of the lower part of the hydrogenation reaction kettle, and then enter each catalyst filter through a catalyst filter total inlet pipe G6 for filtration; switching the three-way valve V2 to a state that the first outlet is conducted and the second outlet is closed, and after the catalyst is intercepted by the catalyst filter, clean hydrogenated liquid flows out of the first outlet of the three-way valve V2 and enters a hydrogenated liquid outlet pipe G7; and when the catalyst filters are back-flushed in turn, the three-way valve V2 is switched to a state that the first outlet is closed and the second outlet is conducted, the catalyst filter reflux valve V4 is opened, hydrogenated liquid in the hydrogenated kettle working liquid reflux pipe G8 enters the catalyst filters from the back-flushing valve, catalyst accumulated on the surfaces of the filter cores is flushed down, and the catalyst is fed into the working liquid supply pipe G1 through the catalyst filter reflux valve V4 and the catalyst filter reflux main pipe G9 and returns to the hydrogenation kettle 1 along with fresh working liquid.
The hydrogen supplied from the hydrogen supply pipe G2 must be continuously monitored for oxygen content and carbon monoxide content, wherein the volume percent of oxygen must be less than 1%, and above that level, the hydrogenation reactor 1 must be bypassed. The carbon monoxide content in the hydrogen supplied from the hydrogen supply pipe G2 must be less than 1.0ppm to avoid poisoning of the palladium catalyst.
The reaction temperature in the hydrogenation reaction kettle 1 is 50-65 ℃, the retention time of the working solution is 0.25-0.55 hours, the pressure in the hydrogenation reaction kettle 1 is 100-150 KPa, and the pressure of fresh hydrogen in the hydrogen supply pipe G2 is 0.25-0.35 MPa.
The hydrogenation reaction solvent in the step (a) can be prepared from the following volume percentages of diisobutyl methanol: (45-50 v%, C10 arene: (50-55 v%) and the total volume of them is 100%. C10 aromatic hydrocarbon is used for dissolving 2-ethylanthraquinone and 2-amylanthraquinone, and diisobutylcarbinol increases the solubility of 2-ethylanthraquinone and 2-amylanthraquinone.
The hydrogenation efficiencies achieved in examples one to four under this solvent formulation are shown in Table 1:
TABLE 1
The hydrogenation solvent in the step (a) can be prepared by the following volume percentage: (12-30 v%) trioctyl phosphate: (8-12) v%, C10 aromatic hydrocarbon: (60-76) v%, and the total volume of the three is 100%. C10 arene mainly dissolves 2-ethyl anthraquinone, 2-amyl anthraquinone and tetrahydro2-ethyl anthraquinone generated by reaction, but can not dissolve 2-ethyl hydro anthraquinone and tetrahydro2-ethyl hydro anthraquinone generated after hydrogenation; thus, trioctyl phosphate and tetrabutyl urea capable of dissolving 2-ethyl hydro anthraquinone and tetrahydro 2-ethyl anthraquinone are also needed as polar solvents. The invention has higher C10 aromatic hydrocarbon content, and can avoid the difficulty in operating the extraction tower caused by the increase of the specific gravity of the working solution; trioctyl phosphate has the advantages of high boiling point, no irritating taste and strong capability of dissolving hydroanthraquinone, but if the content is too high, the viscosity of the working solution is increased, and mass transfer is difficult; the tetrabutyl urea is transparent or slightly yellowish liquid, has slightly higher viscosity than water, has the advantages of large difference from water, large surface tension and the like, and has large solubility for 2-ethyl hydro anthraquinone and tetrahydro 2-ethyl anthraquinone relative to trioctyl phosphate and large distribution coefficient of hydrogen peroxide in two phases. The solvent component combination and proportion of the invention lead the working solution to have the advantages of small volatilization loss, safe use, favorable operation environment, reduced content of the raffinate hydrogen peroxide and improved concentration of the extraction solution, and the product quality is promoted by greatly reducing the TOC (total organic carbon) content of the hydrogen peroxide product due to the reduced spot solubility with water.
The hydrogenation efficiencies achieved in examples five to eight under this solvent formulation are shown in Table 2:
TABLE 2
The foregoing description is only of a preferred embodiment of the invention and is not intended to limit the scope of the invention. In addition to the above embodiments, other embodiments of the present invention are also possible, for example, the left and right directions may be interchanged, and all the technical solutions formed by using equivalent substitution or equivalent transformation fall within the scope of the present invention. The technical features of the present invention that are not described may be implemented by or using the prior art, and are not described herein.
Claims (8)
1. A fluidized bed hydrogenation reaction system for producing hydrogen peroxide comprises a vertical hydrogenation reaction kettle and is characterized in that: the circumference of the lower part of the hydrogenation reaction kettle is uniformly provided with hydrogenation liquid outlets, each hydrogenation liquid outlet is respectively connected with a hydrogenation liquid annular pipe which surrounds the periphery of the hydrogenation reaction kettle, the hydrogenation liquid annular pipe is connected with a catalyst filter total inlet pipe, and the catalyst filter total inlet pipe is respectively connected with a filter inlet valve of each catalyst filter inlet; the outlet of each catalyst filter is respectively provided with a three-way valve, the first outlet of the three-way valve is connected with a hydrogenated liquid outlet pipe, and the second outlet of the three-way valve is connected with a hydrogenated kettle working liquid recoil pipe; a stirring shaft is arranged along the central line of the hydrogenation reaction kettle, and stirring blades are arranged on the stirring shaft; the bottom of each catalyst filter is respectively provided with a catalyst filter reflux valve, the outlet of each catalyst filter reflux valve is respectively connected with a catalyst filter reflux main pipe, the lower end of the catalyst filter reflux main pipe is connected with a working fluid supply pipe, and the working fluid supply pipe is inserted into the inner cavity of the hydrogenation reaction kettle from the middle part of the hydrogenation reaction kettle in the height direction and is bent downwards to extend to the axis of the hydrogenation reaction kettle; the top of the hydrogenation reaction kettle is provided with a hydrogenation kettle gas phase outlet, and a catalyst adding pipe and a hydrogen supply pipe which extend downwards vertically are respectively inserted in the hydrogenation kettle gas phase outlet;
the upper part of the stirring shaft is sleeved with a central sleeve, the upper end of the central sleeve is in closed connection with the inner wall of the hydrogenation reaction kettle, and the lower end of the central sleeve is inserted into a liquid phase space of the hydrogenation reaction kettle;
the lower part of the hydrogenation reaction kettle is provided with an annular sleeve coaxial with the hydrogenation reaction kettle, the circumference of the annular sleeve is spaced from the inner wall of the hydrogenation reaction kettle by a certain distance, and each hydrogenated liquid outlet is positioned on the circumference of the same height as the axial middle part of the hydrogenation reaction kettle and the annular sleeve; the lower part of the stirring shaft is provided with a lower stirring blade, the lower stirring blade is positioned in the annular sleeve, and the middle part of the stirring shaft is provided with an upper stirring blade; the outlet of the working fluid supply pipe is positioned above the upper stirring blade; the outlet of the hydrogen supply pipe is positioned below the center of the lower port of the annular sleeve.
2. The fluidized bed hydrogenation reaction system for producing hydrogen peroxide according to claim 1, wherein: the gas phase outlet of the hydrogenation kettle is connected with the gas inlet of the condenser, the gas outlet of the condenser is connected with the tail gas blow-down pipe through the tail gas emission control valve, and the liquid outlet of the condenser is connected with the upper part of the central sleeve through the condensate return pipe.
3. The fluidized bed hydrogenation reaction system for producing hydrogen peroxide according to claim 1, wherein: at least one vertical baffle is arranged along the inner wall of the liquid phase space of the hydrogenation reaction kettle, and the cross section of the vertical baffle extends along the diameter of the hydrogenation reaction kettle.
4. The fluidized bed hydrogenation reaction system for producing hydrogen peroxide according to claim 1, wherein: the lower extreme of catalyst filter return manifold is connected with the back flow elbow, the lower extreme of back flow elbow inserts in the working solution supply tube, the export of back flow elbow is located the center of working solution supply tube and with the flow direction syntropy of working solution.
5. The fluidized bed hydrogenation reaction system for producing hydrogen peroxide according to claim 1, wherein: the lower extreme of catalyst filter return manifold is connected on the big end circumference of conical sleeve, and conical sleeve suit is in the periphery of working solution supply tube and coaxial with the working solution supply tube, conical sleeve's big end is sealed, conical sleeve's tip is to hydrogenation cauldron and dock with the working solution supply tube, the part that the working solution supply tube is located conical sleeve is equipped with the throat that the diameter reduces gradually, the throat stretches to conical sleeve's tip.
6. A hydrogenation reaction method for producing hydrogen peroxide by adopting the fluidized bed hydrogenation reaction system as claimed in any one of claims 3 to 5, which is characterized by comprising the following steps in sequence, namely, preparing a hydrogenation reaction solvent; secondly, adding 2-ethylanthraquinone and 2-amylanthraquinone into the solvent to form a working solution for hydrogenation reaction, wherein each liter of solvent is added with 2-ethylanthraquinone (80-110) g/L, and each liter of solvent is added with 2-amylanthraquinone (60-140) g/L; preparing a powdery palladium catalyst, wherein the particle size and volume distribution of the palladium catalyst is as follows: the volume percentage of the grain diameter is more than 120 micrometers and is not more than 4 percent; the volume percentage of the particle size is less than 80 microns and is not more than 4 percent, and the rest particle sizes are 80-120 microns; a catalyst adding valve is opened to put a proper amount of catalyst into the hydrogenation reaction kettle, and fresh working solution enters the center of a liquid phase space of the hydrogenation reaction kettle from a working solution supply pipe and is sprayed downwards, so that the fresh working solution is diffused downwards to the periphery under the stirring of a stirring blade; fresh hydrogen is sprayed upwards from the lower port of the hydrogen supply pipe, dispersed into a plurality of small bubbles to be diffused upwards to the periphery under the stirring of the stirring blade, fully mixed with fresh working solution and stirred; fifthly, reacting anthraquinone in the working solution with hydrogen to generate hydrogen anthraquinone under the action of a powdery palladium catalyst; the gas phase substances at the upper part of the hydrogenation reaction kettle are discharged from a gas phase outlet of the hydrogenation kettle and enter a condenser for condensation, the non-condensable gas including unreacted hydrogen is discharged from a tail gas blow-down pipe, and the condensate returns to the center sleeve; the hydrogenated liquid and the powdery catalyst enter a hydrogenated liquid annular pipe from each hydrogenated liquid outlet on the circumference of the lower part of the hydrogenation reaction kettle, and then enter each catalyst filter through a catalyst filter total inlet pipe for filtration; switching the three-way valve to a state that the first outlet is conducted and the second outlet is closed, and after the catalyst is intercepted by the catalyst filter, clean hydrogenated liquid flows out from the first outlet of the three-way valve and enters a hydrogenated liquid outlet pipe; and when the catalyst filters are in backflushing, the three-way valve is switched to a state that the first outlet is closed and the second outlet is communicated, the catalyst filter reflux valve is opened, hydrogenated liquid in the hydrogenated kettle working solution backflushing pipe enters the catalyst filter from the backflushing valve, catalyst accumulated on the surface of the filter element is flushed down, and the hydrogenated liquid enters the working solution supply pipe through the catalyst filter reflux valve and the catalyst filter reflux main pipe and returns to the hydrogenated reaction kettle along with fresh working solution.
7. The hydrogenation reaction method for producing hydrogen peroxide according to claim 6, wherein the hydrogenation reaction solvent in the step (c) is configured by the following volume percentage, diisobutyl methanol: (45-50 v%, C10 arene: (50-55 v%) and the total volume of them is 100%.
8. The method according to claim 6, wherein the hydrogenation solvent is prepared from tetrabutylurea by volume percent: (12-30 v%) trioctyl phosphate: (8-12) v%, C10 aromatic hydrocarbon: (60-76) v%, and the total volume of the three is 100%.
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