CN109678121A - A kind of efficient hydrogenation process and system of hydrogen dioxide solution production by anthraquinone process - Google Patents
A kind of efficient hydrogenation process and system of hydrogen dioxide solution production by anthraquinone process Download PDFInfo
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- CN109678121A CN109678121A CN201710974274.4A CN201710974274A CN109678121A CN 109678121 A CN109678121 A CN 109678121A CN 201710974274 A CN201710974274 A CN 201710974274A CN 109678121 A CN109678121 A CN 109678121A
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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
Abstract
The invention discloses the efficient hydrogenation process and system of a kind of hydrogen dioxide solution production by anthraquinone process, including following content: (1) total hydrogen of hydrogenation process being divided into two-way, respectively hydrogen I and hydrogen II；Hydrogen I and working solution enter molten hydrogen storage equipment, are dissolved in hydrogen I in working solution and obtain molten hydrogen working solution；(2) molten hydrogen working solution and hydrogen II enter the mixer containing ceramic membrane tube bank, wherein molten hydrogen working solution enters tube bank shell side, hydrogen II enters tube side side in tube bank, hydrogen II is broken up into nano/micron grade minute bubbles radial through ceramic-film tube beam tube wall, acts on obtaining microemulsion fluid with the molten hydrogen working solution of shell side；(3) microemulsion fluid enters the liquid phase hydrogenation reactor for being filled with hydrogenation catalyst, carries out hydrogenation reaction, and hydrogenation reaction product enters subsequent processing.Two kinds of different conditions in the technique by control hydrogen in working solution, carry out entire hydrogenation reaction in the liquid phase, while improving hydrogenation reaction efficiency, guarantee the uniformity of reaction, side reaction is controlled effectively, and anthraquinone consumption is greatly lowered.
Description
Technical field
The present invention relates to the effective hydrogenation process and system during a kind of hydrogen dioxide solution production by anthraquinone process.
Background technique
During hydrogen dioxide solution production by anthraquinone process, the hydrogenation process of anthraquinone hydrogenation is the core of entire hydrogen peroxide production process
Unit, hydrogenation reaction result directly affect quality level, product design and the production scale of device of working solution etc., measure hydrogenation
The main indicator of process superiority and inferiority is the technical indicators such as hydrogen effect height, how many, the single ton of catalyst production capacity of side reaction.
General anthraquinone hydrogenation reaction is that airwater mist cooling trickle bed reacts in currently available technology.Reaction temperature is general
It is 45~75 DEG C, reaction pressure is generally 0.2~0.4MPa, and gas is continuous phase, and liquid is logical with a kind of very thin form of liquid film
Cross solid catalyst, there are the following problems for the process: (1) hydrogen is first by gas phase main diffusion to phase interface, then in phase boundary
It is dissolved on face, then liquid phase main body is diffused by phase interface, hydrogenation reaction occurs in the intracorporal catalyst surface of liquid phase master, it is entire to add
Hydrogen reaction process is external diffusion control, and the diffusion mass transfer resistance of gas/liquid film is larger, and diffusion mass transfer rate is low, causes and adds hydrogen
Reaction rate is low, that is, the catalyst space velocities needed when reaching certain production capacity are small, the residence time is long；(2) hydrogen is generally from reactor
The one or many additions in top, and hydrogen be continuous phase, even if by production capacity chemistry consumption hydrogen addition will also result in initial reaction stage and
The amounts of hydrogen of mid-term is significantly superfluous, and excessive hydrogenation side reaction can occur for superfluous hydrogen, causes that practical production capacity is low, anthraquinone consumption
The problems such as height, working solution are poor, aluminium oxide consumption is big.Therefore, how to reduce diffusion mass transfer resistance, improve hydrogenation speed
Rate, inhibition or the generation for reducing excessive hydrogenation side reaction, for improving fixed bed anthraquinone hydrogenation technique and Hydrogen Peroxide Production skill
Art progress is all of great significance.
Disclose a kind of method of hydrotreating of process for prepairng hydrogen peroxide by anthraquinone in CN102009960A, this method is by hydrogen gas phase
It is distributed in the working solution containing anthraquinone derivative, obtains the gas-liquid mixture fluid containing microbubble, and then make gas-liquid mixed stream
Body is with 3-1000h-1The tubular reactor that air speed flows through filling hydrogenation catalyst completes hydrogenation process.This method only becomes hydrogen
It is dispersed in working solution for dispersed phase, but substantially still traditional gas-liquid-solid three-phase hydrogenation process, in hydrogenation process
There are still the resistance to mass tranfers of gas/liquid film, and hydrogenation reaction rate is improved without essential.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of efficient hydrogenation process of hydrogen dioxide solution production by anthraquinone process.The work
Two kinds of different conditions in skill by control hydrogen in working solution, carry out entire hydrogenation reaction in the liquid phase, improve and add
While hydrogen reaction efficiency, guarantee the uniformity of reaction, side reaction is controlled effectively, and anthraquinone consumption is greatly lowered.
The efficient hydrogenation process of hydrogen dioxide solution production by anthraquinone process of the invention, including following content:
(1) total hydrogen of hydrogenation process is divided into two-way, respectively hydrogen I and hydrogen II；Hydrogen I and working solution enter molten hydrogen and set
It is standby, it is dissolved in hydrogen I in working solution and obtains molten hydrogen working solution；
(2) molten hydrogen working solution and hydrogen II enter in the mixer containing ceramic membrane tube bank, wherein molten hydrogen working solution enters
Restrain shell side, hydrogen II enter tube bank in tube side side, hydrogen II be broken up into radial through ceramic-film tube beam tube wall receive/
Micron order minute bubbles act on obtaining microemulsion fluid with the molten hydrogen working solution of shell side；
(3) microemulsion fluid enters the liquid phase hydrogenation reactor for being filled with hydrogenation catalyst, carries out hydrogenation reaction, and hydrogenation reaction produces
Object enters subsequent processing.
In present invention process, the 0.1%~50% of the total hydrogen flowing quantity of flow Zhan of hydrogen I described in step (1), preferably 1%
~10%.
In hydrogenation process of the present invention, working solution described in step (1) is the working solution component of anthraquinone hydrogenation process routine,
Such as: solute component can be one of ethyl hydrazine, amyl anthraquinone and its isomer or a variety of, the first solvent composition
For heavy aromatics, the second solvent composition be trioctyl phosphate, tetrabutyl urea, 2- isobutyl carbinol, 2- methylcyclohexyl acetate or
One of isooctyl acetate is a variety of.
In present invention process, the flow-rate ratio of hydrogen I described in step (1) and working solution is 1:0.3~1:150, preferably
The flux unit of 1:1.5~1:15, hydrogen I are Nm3/ h, the flux unit of working solution are m3/h。
In present invention process, the operating condition of molten hydrogen storage equipment described in step (1) are as follows: 40~75 DEG C of temperature, pressure 0.1~
20.0MPa, molten hydrogen residence time are 0.5~30 minute, preferably 2~5 minutes.
In present invention process, molten hydrogen storage equipment described in step (1) is known to those skilled in the art, generally tubulose is mixed
Device shell, inside is equipped with static(al) mixing or power electric hybrid module；The static(al) electric hybrid module can be SWN type, SMX type, SMK
Any one in type, SML type, SMH type etc., or contain spiral plate, corrugated cardboard sheet, rotating vane, porous plate
Etc. the component of any strengthening fluid disturbance；The power electric hybrid module can be to contain nozzle arrangements, stirring structure, rotation knot
Structure, Venturi tube structure, air dissolved pump structure, negative pressure form any one structure in structure etc., can also be by tangential feed side
Formula realizes the component of the screw of material.
In present invention process, mixer described in step (2) is a kind of tube shell type structure containing ceramic membrane tube bank, including
Shell, ceramic membrane tube bank and inlet and outlet material pipeline etc.；The ceramic membrane tube bank is set in inner walls, and shell one end is set
The liquid phase feeding pipeline of the gas-phase feed pipeline for being connected to tube side side and connection shell side is set, the setting of the shell other end is connected to shell
The discharging pipeline on side.The pore size of the ceramic membrane tube bank is 0.1 ~ 100nm, preferably 0.5 ~ 10nm.
In the method for the present invention, the liquid-drop diameter for the microemulsion fluid that step (2) obtains is 5 ~ 100nm.
In present invention process, the operating condition of mixer described in step (2) are as follows: 40~75 DEG C of temperature, ceramic membrane tube bank
Outer housing pressure be 0.1~1.5MPa, ceramic membrane tube bank pipe in pipe external differential be 0.01~10MPa, preferably 0.5~
2.0MPa。
In present invention process, step (3) hydrogenation conditions are as follows: reaction temperature be 40~75 DEG C, reaction pressure be 0.1~
1.0MPa, volume of material air speed are 30 h-1~80h-1。
In present invention process, the liquid throughput ratio of step (3) hydrogenator charging is 1:1~1:10, preferably 1:3~
1:5, liquid phase flux unit are m3/ h, gas phase flow rate unit are Nm3/h。
In present invention process, liquid phase hydrogenation reactor described in step (3) is fixed-bed structure, and top is provided with microemulsion
Hydrogenation reaction product discharging pipeline is arranged in fluid feed pipeline and exhaust emissions pipeline, bottom；The exhaust emissions pipeline is used
Come the unreacting hydrogen and inert gas being discharged in reactor, can be operated intermittently or continuously according to hydrogenation depth.
In hydrogenation process of the present invention, hydrogenation catalyst described in step (3) is commonly to add hydrogen in anthraquinone hydrogenation
Catalyst, such as: using palladium and/or platinum as the anthraquinone hydrogenation catalyst of active component, catalyst can be for spherical, tooth is spherical, flower
Spherical or monoblock type etc..
Catalyst is completely soaked in present invention process, in hydrogenation process occurs liquid-phase hydrogenatin reaction in a liquid, and one
Aspect catalyst utilization is high；On the other hand the diffusion mass transfer resistance of gas/liquid phase is reduced, improves reaction rate, therefore this is anti-
Answer the catalyst volume air speed of process big；In addition, the microemulsion thermodynamic fluid that hydrogen can be formed with working solution is stablized, with
Reaction carries out hydrogen and is gradually consumed, i.e., gradually decreases along hydrogen content on hydrogenation reaction temperature rise direction, and hydrogen is not present
Excessive hydrogenation phenomenon caused by surplus, the side reaction made are few.
Present invention simultaneously provides a kind of liquid-phase hydrogenatin reaction system, which includes the area Rong Qing, hydrogen oil emulsion band and liquid
Phase hydroconversion reaction zone；
The area Rong Qing is used to for hydrogen I being dissolved in working solution, including several molten hydrogen storage equipments, the molten hydrogen storage equipment include
The hydrogen feed line introduced hydrogen into, the liquid phase feeding pipeline that working solution is introduced and the liquid phase for drawing molten hydrogen working solution
Discharge pipeline；
The hydrogen oil emulsion band is used to for hydrogen II being dissolved in molten hydrogen working solution, including several mixers, the mixing
Device includes the liquid phase feeding pipeline that molten hydrogen working solution is introduced to shell side, introduces hydrogen into the gas-phase feed pipeline of tube side side,
And hydrogen and molten hydrogen are formed by the discharging pipeline of microemulsion fluid extraction as liquid altogether；
The liquid-phase hydrogenatin reaction zone carries out hydrogenation reaction, including several groups liquid phase hydrogenation reactor for microemulsion fluid,
Every group of liquid phase hydrogenation reactor includes the feeding line for introducing microemulsion fluid, the discharge nozzle that hydrogenation reaction product is drawn
Line, the pipeline that unreacted hydrogen is discharged.
In above-mentioned reaction system, the molten hydrogen storage equipment is known to those skilled in the art, generally outside tubular mixer
Shell, inside is equipped with static(al) mixing or power electric hybrid module；The static(al) electric hybrid module can for SWN type, SMX type, SMK type,
Any one in SML type, SMH type etc., or contain spiral plate, corrugated cardboard sheet, rotating vane, porous plate etc. and appoint
The component that strengthening fluid of anticipating disturbs；The power electric hybrid module can for containing nozzle arrangements, stirring structure, rotational structure,
Venturi tube structure, air dissolved pump structure, negative pressure form any one structure in structure etc., can also be real by tangential feed mode
The component of the screw of existing material.
In above-mentioned reaction system, mixer is a kind of shell type structure containing ceramic membrane tube bank, including shell, ceramic-film tube
Beam and inlet and outlet material pipeline etc.；The ceramic membrane tube bank is set in inner walls, and the setting of shell one end is connected to tube side
The discharge nozzle for being connected to shell side is arranged in the gas-phase feed pipeline of side and the liquid phase feeding pipeline of connection shell side, the shell other end
Line
Existing fixed bed anthraquinone hydrogenation is gas, liquid, solid three phase trickle flow bed reaction process, and anthraquinone hydrogenation reaction is external diffusion control
System, reaction rate depends mainly on hydrogen and passes through the mass transfer rate that working solution layer resistance is spread to catalyst surface, if hydrogen is complete
It is dispersed in working solution entirely, resistance to mass tranfer can be considerably reduced, improve hydrogenation reaction rate, but since hydrogen is in bubble shape
Formula is present in working solution, contains several hydrogen molecules from microcosmic in a hydrogen gas bubbles, and hydrogen molecule is extremely easy
It is adsorbed on catalyst surface, therefore the Microscopic of hydrogenation reaction is that on catalyst surface " multiple spot " occurs for " hydrogen air mass "
Add hydrogen, that there are still reactions is uneven, local reaction rate is too high or too low, hot localised points or temperature runaway, reaction selectivity difference etc. are asked
Topic.For this purpose, the present inventor realizes two kind different conditions of the hydrogen in working solution: first by cleverly controlling
By certain molten hydrogen methods and molten hydrogen facility, it is saturated dissolved hydrogen (hydrogen I) to control in working solution, from microcosmic dissolved hydrogen
It is existed entirely in fluid molecule compared with dispersing hydrogen, and each side's uniform force in fluid molecule, therefore hydrogen I is in a liquid
Molecular arrangement it is highly uniform, secondly, the present invention by containing dissolved hydrogen working solution and dispersion hydrogen (hydrogen II), pass through control mixing
Mode makes to disperse hydrogen and saturation hydrogen liquid forms a kind of microemulsion fluid, is a kind of " oily packet gas " state by the microemulsion fluid,
Instant hydrogen working solution is used as " oily phase ", disperses hydrogen as gas phase, and continuous phase is still molten hydrogen working solution, in this, as reactor into
Material, catalyst surface covers one layer of microemulsion liquid film for being rich in dissolved hydrogen (hydrogen I) always in hydrogenation process, avoids
" multiple spot " plus hydrogen occur on catalyst surface for " hydrogen gas bubbles or air mass ", make that hydrogenation reaction occurs to be hydrogen molecule, thus
The microscopic uniformity of hydrogenation reaction is controlled, and disperses " motive force " of the hydrogen (hydrogen II) as lasting hydrogenation process, it can
Hydrogenation reaction rate is enough kept, and can guarantee the uniformity and the extent of reaction of reaction, to reach control hydrogenation reaction activity
With the purpose of selectivity.The present invention can be controlled by the exhaust emissions amount and oily mixer of liquid-phase hydrogenatin reaction zone into hydrogen amount
The depth of hydrogenation processed.Compared with the prior art, the catalyst volume air speed of hydrogenation process of the present invention can be improved to
30h-1~60 h-1, improve 30%~60%；Hydrogenation efficiency is up to 12~18g/L.Hydrogenation reaction along reactor axis to and diameter
To all more uniform, side reaction is controlled effectively, and anthraquinone consumption is made to reduce 50%~90% than the prior art.
Detailed description of the invention
Fig. 1 is present invention process method flow schematic diagram.
Fig. 2 is liquid-phase hydrogenatin reaction system schematic diagram of the invention.
Wherein, 1 is hydrogen manifold, and 2 be hydrogen II, and 3 be hydrogen I, and 4 be working solution, and 5 be molten hydrogen storage equipment, and 6 work for molten hydrogen
Liquid, 7 be heating/cooling device, and 8 be mixer, and 9 be microemulsion fluid feed, and 10 be liquid phase hydrogenation reactor, and 11 be tail gas, 12
For hydrogenation reaction product.
Specific embodiment
The present invention is described in detail with embodiment for explanation with reference to the accompanying drawing, but is not so limited the present invention.
Present invention process is realized in this way: total hydrogen 1 divides for two parts: hydrogen I 3 and hydrogen II 2；
Cause hydrogen I 3 and working solution 4 to introduce molten hydrogen storage equipment 5 first, forms a kind of molten hydrogen working solution 6 after the two mixed dissolution；It will
The liquid and hydrogen II introduce mixer 8, and molten hydrogen working solution 6 therein is heated/after cooler is adjusted to reaction required temperature
Introduce the pipe shell side of mixer 8, hydrogen II 2 introduces the tube side side of mixer 8, using the molten hydrogen working solution in shell side and receive/
Interaction between micron order minute bubbles forms a kind of microemulsion fluid as liquid phase hydrogenation reactor charging 9, into liquid phase
Hydrogenation reaction occurs for hydrogenator 10, and hydrogenation reaction product 12 enters subsequent processing, and tail gas 11 is by top discharge.
Present invention simultaneously provides a kind of liquid-phase hydrogenatin reaction system, the system include the area Rong Qing I, hydrogen oil emulsion band II and
Liquid-phase hydrogenatin reaction zone III；
The area the Rong Qing I is used to for hydrogen I being dissolved in working solution, including several molten hydrogen storage equipments, the molten hydrogen storage equipment packet
Containing the hydrogen feed line I-1 introduced hydrogen into, draw by the liquid phase feeding pipeline I-2 of working solution introducing and by molten hydrogen working solution
Liquid phase discharging pipeline I-3 out；
The hydrogen oil emulsion band II is used to for hydrogen II being dissolved in molten hydrogen working solution, including several mixers, and described is mixed
Clutch includes the liquid phase feeding pipeline II -1 that molten hydrogen working solution is introduced to shell side, introduces hydrogen into the gas-phase feed of tube side side
Pipeline II -2, and hydrogen and molten hydrogen are formed by the discharging pipeline II -3 that microemulsion fluid is drawn as liquid altogether；
The liquid-phase hydrogenatin reaction zone III carries out hydrogenation reaction, including several groups liquid-phase hydrogenatin reaction for microemulsion fluid
Device, every group of liquid phase hydrogenation reactor include the feeding line III -1 for introducing microemulsion fluid, and hydrogenation reaction product is drawn
Discharge pipeline III -2, the pipeline III -3 that unreacted hydrogen is discharged.
The embodiment of the present invention uses 2- ethyl hydrazine as working material, with heavy aromatics, trioctyl phosphate, 2- methyl cyclohexane
The mixture of base acetate forms working solution as solvent, wherein heavy aromatics, trioctyl phosphate, 2- methylcyclohexyl acetate three
The volume ratio of kind solvent is 75:10:15；Using Pd/Al2O3As hydrogenation catalyst, the property of catalyst is as follows: Ф 2
The spherical shape of~3mm, heap density are 0.5 ± 0.02g/ml；Anti-crushing power >=40N/cm；Palladium content is 0.3 ± 0.02wt%；Work
Total effective anthraquinone content is 160~200g/L in liquid.
Embodiment 1
Using hydrogenation reaction technique and liquid-phase hydrogenatin reaction system of the invention, for carrying out anthraquinone hydrogenation process.Hydrogenation
Device loads catalyst 0.072m3, first by hydrogen 13.66Nm3/ h points are II two-way of hydrogen I and hydrogen, and hydrogen I therein is
0.07Nm3/ h, using SMK type static mixer structure, residence time of material is 2.5 minutes；Hydrogen II is 13.59Nm3/ h,
Aperture is used to restrain for the shell-and-tube inoranic membrane of 5nm；First by whole working solution 4.176m3/ h and hydrogen I0.07Nm3/ h is introduced
Static mixer is dissolved under 5.0MPa pressure, forms a kind of working solution material containing saturation dissolved hydrogen；It will be containing full
With the working solution and II 13.59Nm of hydrogen of dissolved hydrogen3/ h introduces hydrogen oil mixer, and molten hydrogen working solution introduces the shell of membrane tube tube bank
Side；Hydrogen II introduces the tube side side of membrane tube tube bank, forms it into the nanoscale microbubble of 5nm~100nm；The behaviour of hydrogen oil mixer
Making pressure is 0.5MPa, forms a kind of microemulsion liquid stream with molten hydrogen working solution via the hydrogen II after hydrogen oil mixer, makees
For hydrogenator charging, liquid-phase hydrogenatin reaction occurs under the conditions of 0.2~0.4MPa, 40~75 DEG C, after completing hydrogenation reaction
Product enter subsequent processing.
After the processing of the method, hydrogenation process is relatively uniform, is 58h in catalyst space velocities-1Under the conditions of, obtained hydrogen
Effect is 12.3~12.7g/L, and anthraquinone unit consumption is 0.215kg/t (27.5% hydrogen peroxide).
Embodiment 2
Using hydrogenation reaction technique and liquid-phase hydrogenatin reaction system of the invention, for carrying out anthraquinone hydrogenation process one.Hydrogenation is anti-
Device is answered to load catalyst 0.093m3, first by hydrogen 13.66Nm3/ h points are II two-way of hydrogen I and hydrogen, and hydrogen I therein is
0.42Nm3/ h, using the static mixer structure containing spiral plate, residence time of material is 3.5 minutes；Hydrogen II is
13.24Nm3/h uses aperture to restrain for the shell-and-tube inoranic membrane of 5nm；First by whole working solution 4.176m3/ h and hydrogen I
0.42Nm3/ h introduces static mixer, is dissolved under 9.9MPa pressure, forms molten hydrogen working solution；By molten hydrogen working solution with
II 13.24Nm of hydrogen3/ h introduces hydrogen oil mixer, and molten hydrogen working solution introduces the shell side of membrane tube tube bank；Hydrogen II introduces membrane tube
The tube side side of tube bank forms it into the nanoscale microbubble of 5nm~100nm；The operating pressure of hydrogen oil hydrogen mixer is 0.4MPa,
Via after hydrogen oil mixer hydrogen II and molten hydrogen working solution form a kind of microemulsion liquid stream, as hydrogenator into
Liquid-phase hydrogenatin reaction occurs under the conditions of 0.2~0.4MPa, 40~75 DEG C for material, and the product after completing hydrogenation reaction enters next
Process.
After the processing of the method, hydrogenation process is relatively uniform, is 45h in catalyst space velocities-1Under the conditions of, obtained hydrogen
Effect is 12.9~13.5g/L, and anthraquinone unit consumption is 0.173kg/t (27.5% hydrogen peroxide).
Comparative example 1
Anthraquinone hydrogenation process is using conventional gas-liquid-solid three-phase hydrogenation reaction technique, and hydrogenator is using conventional fixed bed knot
Structure.It hydrogenates and loads catalyst 0.41m inside tower3, by whole hydrogen 13.66Nm3/ h and whole working solution 4.176m3After/h mixing
Hydrogenator is introduced, gas liquid solid three occurs under the conditions of reaction temperature is 40~75 DEG C, pressure is 0.3~0.4MP and is added
Hydrogen reaction, reaction effluent enter subsequent processing.
It after the processing of the method, is 10h in catalyst volume air speed-1, hydrogen effect is 7.25~7.46g/L, and anthraquinone unit consumption is
0.452kg/t (27.5% hydrogen peroxide).
Comparative example 2
Anthraquinone hydrogenation process uses liquid-phase hydrogenatin reaction process, and embodiment is that extensive work liquid circulation and slightly higher reaction pressure are come
Keep liquid phase reactor.It hydrogenates and loads catalyst 0.12m inside tower3, by whole hydrogen 4.5Nm3/ h and whole working solution 3.5m3/h
Hydrogenator is introduced after mixing, and liquid-phase hydrogenatin occurs under the conditions of reaction temperature is 40~75 DEG C, pressure is 1.8~2.0MP
Reaction, reaction effluent enter subsequent processing.
After the processing of the method, since working solution internal circulating load is big, the production efficiency of working unit liquid is significantly reduced, and hydrogen effect is
5.14~5.33g/L, anthraquinone unit consumption are 0.40kg/t (27.5% hydrogen peroxide).
Comparative example 3
During anthraquinone hydrogenation, disperse after hydrogen after mixing with working solution to enter reactor generation hydrogenation reaction using ceramic membrane
Technique uses aperture to restrain for the shell-and-tube inoranic membrane of 5nm.Wherein catalyst 0.15m is loaded inside hydrogenation tower3, by whole hydrogen
Gas 13.4Nm3/ h and whole working solution 2.1m3/ h occurs under the conditions of reaction temperature is 40~75 DEG C, pressure is 0.3~0.4MP
Hydrogenation reaction, reaction effluent enter subsequent processing.
After the processing of the method, catalyst volume air speed is 14h-1When, hydrogen effect is 8.77~9.10g/L, and anthraquinone unit consumption is
0.3kg/t (27.5% hydrogen peroxide).
Claims (13)
1. a kind of efficient hydrogenation process of hydrogen dioxide solution production by anthraquinone process, it is characterised in that including following content: (1) by hydrogenation process
Total hydrogen be divided into two-way, respectively hydrogen I and hydrogen II；Hydrogen I and working solution enter molten hydrogen storage equipment, and hydrogen I is made to be dissolved in work
Make to obtain molten hydrogen working solution in liquid；(2) molten hydrogen working solution and hydrogen II enter the mixer containing ceramic membrane tube bank, wherein molten
Hydrogen working solution enters tube bank shell side, and hydrogen II enters tube side side in tube bank, and hydrogen II is restrained radial through ceramic membrane
Tube wall is broken up into nano/micron grade minute bubbles, acts on obtaining microemulsion fluid with the molten hydrogen working solution of shell side；(3) microemulsion
Fluid enters the liquid phase hydrogenation reactor for being filled with hydrogenation catalyst, carries out hydrogenation reaction, and hydrogenation reaction product enters next work
Sequence.
2. technique described in accordance with the claim 1, it is characterised in that: the total hydrogen flowing quantity of flow Zhan of hydrogen I described in step (1)
0.1%~50%, preferably 1%~10%.
3. technique described in accordance with the claim 1, it is characterised in that: the flow-rate ratio of hydrogen I described in step (1) and working solution is
The flux unit of 1:0.3~1:150, hydrogen I are Nm3/ h, the flux unit of working solution are m3/h。
4. technique described in accordance with the claim 1, it is characterised in that: the operating condition of molten hydrogen storage equipment described in step (1) are as follows: temperature
40~75 DEG C, 0.1~20.0MPa of pressure of degree, molten hydrogen residence time are 0.5~30 minute.
5. technique described in accordance with the claim 1, it is characterised in that: molten hydrogen storage equipment described in step (1) is outside tubular mixer
Shell, inside is equipped with static(al) mixing or power electric hybrid module；The static(al) electric hybrid module is SWN type, SMX type, SMK type, SML type
Or it is one or more in SMH type, or disturbed for the strengthening fluid containing spiral plate, corrugated cardboard sheet, rotating vane or porous plate
Dynamic component；The power electric hybrid module is to contain nozzle arrangements, stirring structure, rotational structure, Venturi tube structure, air dissolved pump knot
Structure or negative pressure form one of structure or a variety of several, or realize by tangential feed mode the group of the screw of material
Part.
6. technique described in accordance with the claim 1, it is characterised in that: mixer described in step (2) is that one kind contains ceramic membrane
The tube shell type structure of tube bank, including the tube bank of shell, ceramic membrane and inlet and outlet material pipeline；The ceramic membrane tube bank is set to shell
On internal wall, the setting of shell one end is connected to the gas-phase feed pipeline of tube side side and the liquid phase feeding pipeline of connection shell side, shell
The discharging pipeline for being connected to shell side is arranged in the body other end；The pore size of the ceramic membrane be 0.1 ~ 100nm, preferably 0.5 ~
10nm。
7. technique described in accordance with the claim 1, it is characterised in that: the liquid-drop diameter for the microemulsion fluid that step (2) obtains is 5
~100nm。
8. technique described in accordance with the claim 1, it is characterised in that: the operating condition of mixer described in step (2) are as follows: temperature
40~75 DEG C, ceramic-film tube outer housing pressure be 0.1~1.5MPa, ceramic membrane tube bank pipe in pipe external differential be 0.01~
10MPa, preferably 0.5~2.0MPa.
9. technique described in accordance with the claim 1, it is characterised in that: step (3) hydrogenation conditions are as follows: reaction temperature be 40~
75 DEG C, reaction pressure is 0.1~1.0MPa, and volume of material air speed is 30~80h-1。
10. technique described in accordance with the claim 1, it is characterised in that: step (3) hydrogenator charging liquid throughput ratio be
For 1:1~1:10, liquid phase flux unit is m3/ h, gas phase flow rate unit are Nm3/h。
11. technique described in accordance with the claim 1, it is characterised in that: liquid phase hydrogenation reactor described in step (3) is fixed bed
Microemulsion fluid feed pipeline and exhaust emissions pipeline is arranged in structure, top, and hydrogenation reaction product discharging pipeline is arranged in bottom；Institute
The exhaust emissions pipeline stated is used to the unreacting hydrogen and inert gas that are discharged in reactor, according to hydrogenation depth interval or
Continuous operation.
12. technique described in accordance with the claim 1, it is characterised in that: hydrogenation catalyst described in step (3) be with palladium and/or
Platinum is the anthraquinone hydrogenation catalyst of active component.
13. a kind of liquid-phase hydrogenatin reaction system, it is characterised in that: the system includes that the area Rong Qing, hydrogen oil emulsion band and liquid phase add
Hydroformylation reaction zone；The area Rong Qing is used to for hydrogen I being dissolved in working solution, including several molten hydrogen storage equipments, the molten hydrogen are set
The standby hydrogen feed line comprising introducing hydrogen into is drawn by the liquid phase feeding pipeline of working solution introducing and by molten hydrogen working solution
Liquid phase discharge pipeline；The hydrogen oil emulsion band is used to for hydrogen II being dissolved in molten hydrogen working solution, including several mixers,
The mixer includes the liquid phase feeding pipeline that molten hydrogen working solution is introduced to shell side, introduces hydrogen into the gas phase of tube side side
Feeding line, and hydrogen and molten hydrogen are formed by the discharging pipeline that microemulsion fluid is drawn as liquid altogether；The liquid phase adds
Hydroformylation reaction zone carries out hydrogenation reaction, including several groups liquid phase hydrogenation reactor, every group of liquid-phase hydrogenatin reaction for microemulsion fluid
Device includes the feeding line for introducing microemulsion fluid, the discharging pipeline that hydrogenation reaction product is drawn, by unreacted hydrogen
The pipeline of discharge.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710974274.4A CN109678121B (en) | 2017-10-19 | 2017-10-19 | High-efficiency hydrogenation process and system for producing hydrogen peroxide by anthraquinone method |
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|---|---|---|---|
| CN201710974274.4A CN109678121B (en) | 2017-10-19 | 2017-10-19 | High-efficiency hydrogenation process and system for producing hydrogen peroxide by anthraquinone method |
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| CN109678121A true CN109678121A (en) | 2019-04-26 |
| CN109678121B CN109678121B (en) | 2020-06-05 |
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| CN201710974274.4A Active CN109678121B (en) | 2017-10-19 | 2017-10-19 | High-efficiency hydrogenation process and system for producing hydrogen peroxide by anthraquinone method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021047044A1 (en) * | 2019-09-14 | 2021-03-18 | 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 process |
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