CN206616014U - A kind of hydrogenation apparatus of hydrogeneous anthraquinone working solution - Google Patents
A kind of hydrogenation apparatus of hydrogeneous anthraquinone working solution Download PDFInfo
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- CN206616014U CN206616014U CN201720194905.6U CN201720194905U CN206616014U CN 206616014 U CN206616014 U CN 206616014U CN 201720194905 U CN201720194905 U CN 201720194905U CN 206616014 U CN206616014 U CN 206616014U
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Abstract
The utility model discloses a kind of hydrogenation apparatus of hydrogeneous anthraquinone working solution, including hydrogenation liquid preparing system and nitrogen hydrogen mixed tail gas processing system：Hydrogenation liquid preparing system includes fluid bed, hydride head tank, hydride grade one filter, hydride cooler, hydride groove, hydride circulating pump, hydride secondary filter and the security filter being sequentially connected；Nitrogen hydrogen mixed tail gas processing system includes recycle hydrogen condenser, circulating hydrogen liquid/gas separator, circulating hydrogen filter and the circulating hydrogen press being sequentially connected；Recycle hydrogen condenser air inlet is connected with the outlet of fluidized bed circulation gas, and circulating hydrogen press exhaust outlet is connected with fluidized bed circulation gas import, and tail gas is back in fluid bed recycles after treatment.The present apparatus provides good Equipment Foundations for the hydrogenation fluidized-bed process of anthraquinone legal system hydrogen peroxide, and the shell and tube film blender of bottom can greatly accelerate pipe heat exchanger on reaction rate, return duct being capable of effective controlling reaction temperature.
Description
Technical field
The utility model is related to a kind of hydrogenation apparatus of hydrogeneous anthraquinone working solution.
Background technology
In the prior art, the preparation of hydrogen peroxide is typically realized by anthraquinone.It is anthraquinone using 2- EAQs as
Carrier, palladium (or nickel) is catalyst, by H2And O2Directly it is combined to H2O2.It is divided into hydrogenation, oxidation, extraction, four works of post processing
Sequence.
Hydrogenation process therein typically use fixed-bed process, using alkyl-anthraquinone as carrier, using heavy aromatics, tetrabutyl urea as
Solvent constitutes working solution.Working solution carries out hydrogenation in the presence of certain pressure, temperature and palladium catalyst with hydrogen,
Solution (abbreviation hydride) of the generation containing corresponding alkyl hydrogen anthraquinone.Its reaction equation is as follows：
The anthraquinone production technology of fixed bed, although be the main flow of domestic production hydrogen peroxide unit, but also show life
Produce low efficiency, poor product quality, high unit product production consumption, production equipment heaviness, big, the production operation security difference of investment etc.
More shortcoming.
The content of the invention
Technical problem to be solved in the utility model is to be directed to the deficiencies in the prior art, and provides a kind of hydrogeneous
The hydrogenation apparatus of anthraquinone working solution, using anthracene of the gas-liquid-solid three-phase self-loopa fluidized-bed reactor in anthraquinone legal system hydrogen peroxide
The technique that quinone is hydrogenated.
To achieve these goals, the utility model is adopted the following technical scheme that：
A kind of hydrogenation apparatus of hydrogeneous anthraquinone working solution, including hydrogenation liquid preparing system and nitrogen hydrogen mixed tail gas processing system
System：Described hydrogenation liquid preparing system includes fluid bed, hydride head tank, hydride grade one filter, the hydrogen being sequentially connected
Change liquid cooler, hydride groove, hydride circulating pump, hydride secondary filter and security filter, raw material is in fluid bed
Interior progress, which is reacted after obtained working solution eventually passes through the filtering of security filter, to be flowed into deoxidation tower；Described nitrogen hydrogen mixing tail
Gas processing system includes recycle hydrogen condenser, circulating hydrogen liquid/gas separator, circulating hydrogen filter and the recycle hydrogen being sequentially connected
Aerostatic press, the air inlet of recycle hydrogen condenser is connected with the circulating air outlet of fluid bed, the exhaust outlet of circulating hydrogen press with
The circulating air import of fluid bed is connected, and the tail gas formed after being reacted in fluid bed, which enters in recycle hydrogen condenser, sequentially passes through place
It is back in fluid bed and is recycled by circulating hydrogen press after reason.
In above-mentioned technical proposal, described fluid bed is gas-liquid-solid three-phase self-circulation type reactor, including reactor shell
And internals, wherein：
The bottom of described reactor shell is provided with working solution import, newly reaction hydrogen inlet, circulation fluid import B, bottom
Endless tube, circulating air import, circulation fluid import A are distributed with one heart provided with cyclic nitrogen hydrogen, and top is exported provided with circulation fluid, and top is provided with
Circulating air is exported；
Working solution import in reactor shell bottom is connected with the tube side of the shell and tube film blender positioned at housing bottom,
New reaction hydrogen inlet is connected with the shell side of shell and tube film blender；The membrane tube tube side of described shell and tube film blender and reaction
Connected inside device, the outlet of membrane tube tube side is provided with anti-settling poly- device；
The frid of annular is fixed with along inwall in reactor internal upper part, frid bottom is provided with 8~20 outages, frid
Between design gas passage, be provided with above umbellate form baffle plate, umbellate form baffle plate above the passage and be provided with demister, set above demister
There is the flushing liquor distribution apparatus of anti-anthraquinone condensation；
Described circulation fluid outlet is positioned at the lower section of frid, and circulation fluid import B is located at the lower section of shell and tube film blender, followed
Ring liquid import A is located at shell and tube film blender, cyclic nitrogen hydrogen and is distributed with one heart between endless tube；
Endless tube is distributed with one heart provided with described cyclic nitrogen hydrogen above described shell and tube film blender；
It is conversion zone that described cyclic nitrogen hydrogen is distributed between endless tube, frid with one heart, and conversion zone is built with catalyst；
The outside of described fluid bed is also equipped with catalyst feeder, passes through the reaction inside feeding tube and fluid bed
Duan Liantong.
In above-mentioned technical proposal, described working solution import is connected with providing the device of working solution, and new reaction hydrogen enters
Mouthful with provide hydrogen device be connected, circulating air import is connected with the exhaust outlet of circulating hydrogen press, circulating air export and
The air inlet of recycle hydrogen condenser is connected；Working solution is connected between the device of described offer working solution, working solution import
Preheater.
In above-mentioned technical proposal, described hydride head tank, middle part is provided with import A, and bottom is provided with broken spigot and is provided with
Export A；Import A is connected by pipeline with the circulation fluid outlet of fluid bed；It is two-way to export A points：All the way with hydride one-level
The import B of filter is connected, and is connected all the way with the circulation fluid import B of fluid bed, valve or road are fitted with two-way
Valve.
In above-mentioned technical proposal, described hydride grade one filter, middle part goes out provided with import B, top provided with reaction solution
Mouth, bottom are provided with outlet B；Import B is connected with the outlet A of hydride head tank, and outlet B passes through circulation fluid cooler and fluidisation
The circulation fluid import A of bed is connected；Reaction solution outlet is divided into two-way, and the import with hydride cooler all the way is connected, all the way
Anti- purge pump and blind controller system are connected with, the entrance of anti-purge pump is connected with hydride groove.Hydride one-level filter
After longtime running, catalyst filter cake is blocked up, it is necessary to blowback on its filtering membrane tube；Program automatic back blow system is provided with by the present invention
System, is made up of anti-purge pump and blind controller system.
In above-mentioned technical proposal, described hydride head tank, the composition outer circulation of hydride grade one filter and discharging is set
It is standby, 6-12 described outer circulations of shell Ligation in vitro of fluid bed and discharging equipment.
The utility model also provides a kind of method for hydrogenation of hydrogeneous anthraquinone working solution, comprises the following steps：Hydrogen-containing gas and
Anthraquinone working solution carries out hydrogenation reaction under the catalytic action of catalyst and generates hydrogeneous anthraquinone working solution；Produced in hydrogenation process
Raw tail gas is utilized by condensation, separation, filtering, pressurization Posterior circle；The hydrogeneous anthraquinone working solution of generation, a portion is passed through
Remove catalyst after filter, then carry out after cooling, filtering, security filtering follow-up oxidation reaction, most of hydrogeneous anthraquinone work
Liquid re-starts hydrogenation.
In above-mentioned technical proposal, described method for hydrogenation specifically includes following steps：
(1) hydrogeneous anthraquinone working solution is prepared：Anthraquinone working solution is entered after the preheating of working solution preheater by working solution import
Enter into the tube side of the shell and tube film blender of fluidized-bed bottom, hydrogen-containing gas enters shell and tube film by newly reacting hydrogen inlet
In the shell side of blender, hydrogen-containing gas, anthraquinone working solution carry out solution-air in shell and tube film blender and are pre-mixed to form mixing
Thing；Gas-pressurized in circulating hydrogen compressor enters fluid bed bottom and concentric by cyclic nitrogen hydrogen by circulating air import
Endless tube is distributed to disperse；Cocurrent together with behind mixture and gas-pressurized interflow and up to conversion zone of the fluid bed built with catalyst
In, enter under the catalytic action of the solid particle of the catalyst in fluid bed, under conditions of 0.10~0.8MPa, 30~80 DEG C
The hydrogeneous anthraquinone working solution of row continuously hydrogen adding reaction generation；During hydrogenation reaction, make in the air lift of circulating air compressor
Under, the gas-liquid-solid three in fluid bed keeps bubbling or turbulence state in fluid bed, and solid two of liquid is then under gas stripping
In hydride head tank being imported into from the circulation fluid outlet on fluid bed top；
Temperature, pressure, the control of hydrogen dividing potential drop and catalyst activity come determine will according to the requirement of hydrogenation efficiency by it is low gradually
Improve and dose.
(2) vent gas treatment：After hydrogenation in step (1) terminates, the hydrogen-containing gas of reaction is not participated in by fluid bed
Circulating air outlet is expelled in recycle hydrogen condenser, sequentially passes through the condensation of recycle hydrogen condenser, circulating hydrogen liquid/gas separator
It is back in circulating hydrogen compressor and recycles after separation, the filtering of circulating hydrogen filter；
The addition of nitrogen is flexibly controlled with displacement according to the activity of catalyst, hydrogenation efficiency and hydrogenation temperature in hydrogen-containing gas
System, partial tail gas is separated after contained solvent by circulating hydrogen liquid/gas separator (3), is vented through spark arrester, circulating hydrogen liquid/gas separator
Condensate liquid containing organic solvent and a small amount of anthraquinone is reclaimed.
(3) hydrogeneous anthraquinone working solution post processing：After hydrogenation in step (1) terminates, the hydrogen anthraquinone working solution of generation
By the pressure in fluid bed in hydride head tank after gas-liquid separation, the hydrogen anthraquinone working solution of liquid phase flows into hydride
In grade one filter, a part removes contained catalyst (entrained powder catalyst and other miscellaneous in hydrogen anthraquinone working solution by filtering
Otherwise matter take the decomposition that oxidation operation causes hydrogen peroxide to, it is necessary to remove) after, then after the cooling of hydrogenated liquid cooler flow into hydrogen
Change in liquid groove；The hydrogen anthraquinone working solution flowed into hydride groove, is pumped out, successively hydrogenated liquid two by hydride circulation
Entered after level filter, the filtering of security filter security and follow-up oxidation operation is carried out in oxidizing tower；Another part (big portion
Point) cooled down through circulation fluid cooler after be back to by circulation fluid import A in fluid bed and carry out further hydrogenation；
In circulation hydride provided with bypass：Hydride head tank is connected by pipeline with circulation fluid import B, is set on pipeline
There is road valve；In system shutdown or filter checking maintenance (system shutdown does not stop circulating air, to avoid catalyst from being deposited in tower),
The road valve by circulation pipe is opened, valve of the hydride head tank to hydride grade one filter route, recycle hydrogen is simultaneously closed off
Change liquid is no longer pass through hydride grade one filter, circulation fluid cooler, circulation fluid import A and is back in fluid bed, but passes through
Circulation fluid bypass is directly back in fluid bed via circulation fluid import B.
In above-mentioned technical proposal, in step (1), during hydrogenation reaction, the tower top of fluid bed and the differential pressure of bottom of towe
For 80~150kPa, total superficial gas velocity of the hydrogen-containing gas in fluid bed is that 5~100cm/s, apparent slurry speed are 2~30cm/s,
The settled bed concentration of fluidized-bed reactor is not less than 2g/L；
In above-mentioned technical proposal, in step (1), described hydrogen-containing gas includes hydrogen and nitrogen, wherein：The volume of hydrogen
Account for volume of gas 30~99%, remaining be nitrogen.
In above-mentioned technical proposal, in step (1), in described anthraquinone working solution, solute is that anthraquinone, the concentration of anthraquinone are
140~240g/L；Described anthraquinone is in 2- EAQs, tetrahydrochysene 2- EAQs, 2- amyl anthraquinones, tetrahydrochysene 2- amyl anthraquinone
Any one, the mixture that is mixed with arbitrary proportion of two kinds and the above；Solvent is polyalkylbenzene, the pungent fat of tricresyl phosphate, two
In isobutyl carbinol, tetrabutyl urea, acetic acid methyl cyclohexane fat any one, two kinds and the above mix with arbitrary proportion
Mixture, the concentration of solvent is 760~860g/L.
In above-mentioned technical proposal, in step (1), the solid particle of the catalyst loaded in described fluidized-bed reactor,
Including active ingredient and carrier, the percentage by weight of active ingredient be 1%~3%, carrier percentage by weight be 97%~
99%, the two is combined together by traditional infusion process, deposition-precipitation method, ion-exchange even load technology；
Described active ingredient be preferably in palladium, platinum, cobalt, nickel, iron any one, two kinds and the above it is mixed with arbitrary proportion
The mixture closed；
Described carrier is preferably sodium silicoaluminate, silica, alundum (Al2O3), silica-alumina, activity
In charcoal, silica-titania any one, the mixture that is mixed with arbitrary proportion of two kinds and the above；Described carrier,
Particle mean size is 70~300 microns, average pore size(angstrom), specific surface area are 80~200 meters squared per grams, pore-body
0.6~0.8mL/g of product；
The solid particle of described catalyst, density is less than 1g/cm3, particle diameter is 40~400 microns, more preferably
80-250 microns.
In above-mentioned technical proposal, in step (1), the temperature of hydrogenation reaction is preferably 35~70 DEG C.
In above-mentioned technical proposal, in step (1), described anthraquinone working solution is heated to after 35~60 DEG C being passed through fluidisation again
In bed reactor.
In above-mentioned technical proposal, in step (3), the described hydrogen anthraquinone working solution flowed into hydride grade one filter,
It is most of cooled down through circulation fluid cooler after be back to by circulation fluid import A in fluid bed recycle, small part is filtered through filtering
After catalyst, flowed into after hydrogenated liquid cooler cooling in hydride groove, the volume ratio of the two is 1：3~40.
The utility model is main to be produced with solving existing hydrogen peroxide process low production efficiency, poor product quality, unit product
The technical problems such as consumption is high, production equipment is heavy, big, the production operation security difference of investment.For anthraquinone legal system hydrogen peroxide
Hydrogenate fluidized-bed process and good Processes and apparatus basis is provided, the shell and tube film blender of reactor bottom can greatly add
Pipe heat exchanger on fast response speed, return duct being capable of effective controlling reaction temperature., can be existing after this process industryization
There is raising production efficiency more than 40% on domestic fixed bed hydrogenation Process ba- sis, and in production principle and the substantially solution of technique
Certainly produce in hazards, can make product design by 30% improve more than 40%, and product quality leading indicator if any
Machine carbon content, non-volatile content etc. is better than the product that fixed-bed process is produced.Development for China's hydrogen peroxide has
Epoch-making promotion meaning.
Brief description of the drawings
Fig. 1：The structural representation of the utility model hydrogenation apparatus；
Fig. 2：The structural representation of the gas-liquid-solid three-phase self-circulation type reactor of the utility model hydrogenation apparatus；
Wherein：1 circulating hydrogen press, 2 circulating hydrogen filters, 3 circulating hydrogen liquid/gas separators, the condensation of 4 recycle hydrogens
Device, 5 catalyst feeders, 6 fluid beds, 7 working solution preheaters, 8 hydride head tanks, 9 hydride grade one filters,
10 circulation fluid coolers, 11 anti-purge pumps, 12 hydride coolers, 13 hydride grooves, 14 hydride circulating pumps, 15
Hydride secondary filter, 16 security filters, 61 reactor shells, 62 working solution imports, 63 new reaction hydrogen inlets,
64 circulating air imports, 65 circulation fluid import A, 66 circulation fluid import B, the outlet of 67 circulation fluids, the outlet of 68 circulating air, 69 row
Tubular membrane blender, 610 cyclic nitrogen hydrogen are distributed endless tube, 611 frids, 612 umbellate form baffle plates, 613 demistings, 614 punchings with one heart
Wash liquid distribution device, the outlet of 615 reaction solutions.
Embodiment
The embodiments of technical solutions of the utility model is described in detail below, but the utility model be not limited to
Lower description content：
The utility model develops anthraquinone hydroperoxy- according to hydrogen peroxide process, raw material, reaction and production control feature
Change the hydrogenation process that hydrogen production prepares hydrogeneous anthraquinone working solution.Done furtherly for the utility model with reference to embodiments
Bright, embodiment is only used for explaining rather than limits protection domain of the present utility model.
The raw material of the present embodiment is broadly divided into three parts：1. hydrogen gas, 2. Anthraquinones working solutions, 3. contain catalysis
The solid particle of agent, wherein：
1. hydrogen gas.The hydrogen needed for hydrogen anthraquinone is generated, is entered simultaneously in fluidized-bed reactor bottom and working solution
High performance membrane blender, the gas-liquid mixed for fill part is latter with the conversion zone for containing catalyst into reactor, and from hydrogen
The circulating air and nitrogen of recycle compressor mix secondary mixing and reacted, and mixed hydrogen accounts for the 40 of hydrogen gas volume
~98%.Feed hydrogen into reactor should make the partial pressure (PH2) in reacted circulating air reach about 150~400KPa.
The partial pressure is a dynamic indicator, according to catalytic amount in hydrogenation system and activity come dynamic control, i.e., according to analysis hydrogen
Change the data of efficiency to control hydrogen dividing potential drop.In order to ensure the pressure at the top of hydrogenation fluidized-bed reactor maintains 150~800KPa
With guarantee hydrogenation efficiency, that is, improve the hydrogen dividing potential drop in reaction system, it is necessary to displace the nitrogen in a part of recyclegas, replace
Pneumatic transmission to full factory's gas distribution system, gas network finally removes torch.
2. Anthraquinones working solution.2- EAQs, tetrahydrochysene 2- EAQs, 2- amyl groups are mainly contained in Anthraquinones working solution
Anthraquinone, tetrahydrochysene 2- amyl anthraquinones, tertiary butyl anthraquinone or itself or mixture as solute, also containing polyalkylbenzene, the pungent fat of tricresyl phosphate,
The mixture of diisobutyl carbinol (DIBC) and tetrabutyl urea is used as solvent.Working solution is stored in working solution storage tank, by work liquid pump
Through work liquid filter, working solution preheater, adjust the temperature to 30~60 DEG C, with pressure-swing absorption apparatus come through decompression, filtering
Hydrogen afterwards is mixed in high performance membrane blender, while into fluidized-bed reactor.
3. the solid particle containing catalyst, catalyst is palladium, platinum, cobalt, nickel or the iron for having carrier.Carrier is selected from aluminosilicate
Sodium, silica, alundum (Al2O3), silica/alundum (Al2O3), activated carbon, silicon/titanium and its mixture, most
Large aperture is 80~180, and particle mean size is 40~300 microns, average pore size(angstrom), specific surface area is 80~200
Meters squared per gram, 0.6~0.8mL/g of pore volume.For containing gas-liquid-solid ternary of the particle diameter for 40-300 microns of solid particle
For reacting fluid bed, particle has a wider particle diameter distribution, more preferably at least 40 microns, and most preferably at least 70~200 is micro-
Rice.Compatibly the size of solid particle contained by fluid bed meets following separate one or more standards：(1) at least 90%
Particle particle diameter be in 80-200 micrometer ranges in；(2) particle diameter of the particle less than 10% is less than 70 microns；And (3) are less than
The particle diameter of 5% particle is more than 300 microns.
The reactor used in the present embodiment can be gas-liquid-solid three-phase self-circulation type bubbling reactor, bubbling reactor
4~12 gas-liquid separators are also distributed with top, and the reaction utensil has air speed big, and pressure drop is small, and uniformity of temperature profile is controllable, mass transfer
With conduct heat, high length service cycle of catalyst utilization, the advantages of safe operating environment is high.
Hydrogen gas and Anthraquinones working solution are passed through in the fluid bed of the solid particle containing catalyst and are hydrogenated with
Reaction, generates the working solution containing hydrogen anthraquinone, the pressure of hydrogenation is 0.10~0.8MPa, and temperature is 30~80 DEG C, is being hydrogenated
Gas-liquid two-phase is sufficiently mixed in fluid bed using film mixing in journey, makes gas-liquid-solid three using circulating air compressor gas stripping
Keep bubbling or turbulent flow in bed, solid two of liquid then in the presence of air lift from tower top through many outer circulating tubes again by bottom of towe
Return and reacted again in tower, total superficial gas velocity that tower includes hydrogen gas is 10~100cm/s, apparent slurry speed is 2~30cm/s,
Wherein hydrogen accounts for the 30~98% of the volume of gas, and remaining is nitrogen, and the settled bed concentration of fluid bed is not less than 2g/L, fluidisation
Density of solid particles in bed is less than 1g/cm3, and particle size distribution range is that the anthraquinone in 40~300 microns, Anthraquinones working solution is dense
Spend for 140~240g/L, hydrogenation reactor tower top is 0.08~0.15MPa with bottom of towe pressure difference, by tower top come out it is unreacted
Hydrogen gas is increased again after purification by recycle compressor to be reacted in laggard fluidized bed, the hydrogen after hydrogenation
The working solution of anthraquinone by gas-liquid separation, filter out contained catalyst after enter hydride degassing tank after cooling, be prepared to enter into
Oxidation reactor is reacted, and the heat exchanger heat exchange Posterior circle that most of liquid phase is passed through under filter, which is returned in fluid bed, to be carried out again
Reaction, circulation gas phase is collected after cooling obtains the solvent containing a small amount of anthraquinone.Due to there is gas delay in reactor,
Therefore the density in reactor is smaller by 30~60% or so than the density in liquid circulating pipe, here it is the air lift of recyclegas is made
With.Under substantial amounts of recurrent state, liquid phase circulation amount is usually the biography in a few to tens of times for adding material, fluidized-bed reactor
Matter effect (feature) can be ideal.
Hydride therein flow to hydride groove after being separated with catalyst, a part of liquid is still recycled to reaction system,
With hydrogen together so that catalyst keeps suspended state.Form the liquid phase circulation of anthraquinone hydrogenation system in working solution.Working solution
Hydrogenation system gas circulation can be realized by recycle compressor.
After over hydrogenation, the hydride containing hydrofenating anthraquinone continues through separation, filtering, cooling into hydrogenation liquid bath,
Prepare the redox reaction of next process, wherein unreacted hydrogen and nitrogen mixture in reactor head through separation, cold
Coagulate, separate again, filter again by hydrogen recycle compressor pressurize again with and the fresh hydrogen that mixes by film blender of working solution
Gas converges in reactor bottom to carry out fluidizing stirring and reacts to the working solution in reactor and catalyst mixed liquid.Wherein come from
The working solution containing anthraquinone of working solution circulating slot is passed into after film blender with fresh after filtering, heat exchange from reactor bottom
Hydrogen together enters fluidized-bed reactor.Multiple tubular heat exchangers under the outer grade one filter of reactor are to reactor reaction temperature
Degree control effectively.
The utility model provides a kind of method for hydrogenation of hydrogeneous anthraquinone working solution, comprises the following steps：Hydrogen-containing gas and anthracene
Quinone working solution carries out hydrogenation reaction under the catalytic action of catalyst and generates hydrogeneous anthraquinone working solution；Produced in hydrogenation process
Tail gas by condensation, separation, filtering, pressurization Posterior circle utilize；Generate hydrogeneous anthraquinone working solution, a part is directly and hydrogen
Body re-starts reaction, and a part removes catalyst after filtering, and follow-up oxidation is carried out after cooling, filtering, security filtering
Reaction.
The utility model provides also a kind of hydrogenation apparatus of hydrogeneous anthraquinone working solution, including hydrogenation liquid preparing system and nitrogen hydrogen
Mixed tail gas processing system, it is characterised in that：Described hydrogenation liquid preparing system includes fluid bed 6, the hydride being sequentially connected
Head tank 8, hydride grade one filter 9, hydride cooler 12, hydride groove 13, hydride circulating pump 14, hydride two
Level filter 15 and security filter 16, raw material carries out reacting obtained working solution in fluid bed eventually passes through security filter
Flowed into after filtering in deoxidation tower；Described nitrogen hydrogen mixed tail gas processing system include be sequentially connected recycle hydrogen condenser 4, follow
Ring hydrogen liquid/gas separator 3, circulating hydrogen filter 2 and circulating hydrogen press 1, the air inlet of recycle hydrogen condenser and fluid bed
Circulating air outlet is connected, and the exhaust outlet of circulating hydrogen press is connected with the circulating air import of fluid bed, is reacted in fluid bed
The tail gas formed afterwards, which enters to sequentially pass through to be back in fluid bed by circulating hydrogen press after processing in recycle hydrogen condenser, to be circulated
Utilize.
Wherein fluid bed 6 is gas-liquid-solid three-phase self-circulation type reactor, as shown in Fig. 2 including reactor shell 61 and interior
Portion's component：
The bottom of described reactor shell 61 is provided with working solution import 62, new reaction hydrogen inlet 63, circulation fluid import B
66, bottom is distributed endless tube 610, circulating air import 64, circulation fluid import A65 with one heart provided with cyclic nitrogen hydrogen, and top is provided with circulation
Liquid outlet 67, top is provided with circulating air outlet 68；
Working solution import and the tube side of the shell and tube film blender 69 positioned at housing bottom in reactor shell bottom connect
Connect, new reaction hydrogen inlet is connected with the shell side of shell and tube film blender；The membrane tube tube side of described shell and tube film blender with
Inside reactor is connected, and the outlet of membrane tube tube side is provided with anti-settling poly- device；
The frid 611 of annular is fixed with along inwall in reactor internal upper part, frid bottom is provided with 8~20 outages, groove
It is provided with above plate medium design gas passage, the passage above umbellate form baffle plate 612, umbellate form baffle plate and is provided with demister 613, is removed
The flushing liquor distribution apparatus 614 of anti-anthraquinone condensation is provided with above day with fog；
Described circulation fluid outlet is positioned at the lower section of frid, and circulation fluid import B is located at the lower section of shell and tube film blender, followed
Ring liquid import A is located at shell and tube film blender, cyclic nitrogen hydrogen and is distributed with one heart between endless tube；
Endless tube is distributed with one heart provided with described cyclic nitrogen hydrogen above described shell and tube film blender；
It is conversion zone that described cyclic nitrogen hydrogen is distributed between endless tube, frid with one heart, and conversion zone is built with catalyst；
The outside of described fluid bed is also equipped with catalyst feeder 5, by feeding tube with it is anti-inside fluid bed
Section is answered to connect；
Described working solution import is connected with providing the device of working solution, dress of the new reaction hydrogen inlet with providing hydrogen
Put and be connected, circulating air import is connected with the exhaust outlet of circulating hydrogen press, circulating air outlet is entered with recycle hydrogen condenser
Gas port is connected；Working solution preheater 7 is connected between the device of described offer working solution, working solution import；
Described hydride head tank, middle part is provided with import A, and bottom is provided with broken spigot and provided with outlet A；Import A passes through
Pipeline is connected with the circulation fluid outlet of fluid bed；It is two-way to export A points：All the way with the import B phases of hydride grade one filter
Connection, is connected with the circulation fluid import B of fluid bed, valve or road valve is fitted with two-way all the way；
Described hydride grade one filter (9), middle part is set provided with import B, top provided with reaction solution outlet 615, bottom
There is outlet B；Import B is connected with the outlet A of hydride head tank, and outlet B is followed by circulation fluid cooler 10 and fluid bed
Ring liquid import A is connected；Reaction solution outlet is divided into two-way, and the import with hydride cooler all the way is connected, and is connected with all the way
Anti- purge pump 11 and blind controller system, the entrance of anti-purge pump are connected with hydride groove 13；
Described hydride head tank, the composition outer circulation of hydride grade one filter and discharging equipment, the housing of fluid bed
Outer connection 6-12 described outer circulations and discharging equipment.
The utility model is specifically illustrated with reference to specific embodiment：
Embodiment 1：
A kind of method for hydrogenation of hydrogeneous anthraquinone working solution, it is characterised in that comprise the following steps：
(1) hydrogeneous anthraquinone working solution is prepared：Hydrogen-containing gas and anthraquinone working solution are each led into fluid bed 6, it is hydrogeneous
Gas gas and anthraquinone working solution are sufficiently mixed in the shell and tube film blender 69 of fluidized-bed bottom, and then gas-liquid mixture enters
Enter to fluid bed built with catalyst solid particle reaction section；Hydrogen-containing gas and anthraquinone working solution are in catalyst solid particle
Hydrogenation reaction generation hydrogen anthraquinone working solution is carried out under effect, under conditions of 0.30~0.5MPa, 45~60 DEG C；
During hydrogenation reaction, make gas-liquid-solid three in fluid bed using the gas stripping of circulating air compressor 1
Interior holding bubbling or turbulence state, and solid two of liquid is then back under gas stripping from fluid bed top through many outer circulating tubes
In shell and tube film blender and it is back in conversion zone and reacts again；Total superficial gas velocity of hydrogen-containing gas in fluidized-bed reactor
It is 5~10cm/s for 15~30cm/s, apparent slurry speed, the settled bed concentration of fluidized-bed reactor is not less than 2g/L, and fluid bed is anti-
It is 0.08~0.10MPa with bottom of towe pressure difference to answer device tower top；
Described hydrogen-containing gas includes hydrogen and nitrogen, wherein：The volume of hydrogen account for volume of gas 70%, remaining be
Nitrogen；
In described anthraquinone working solution, the concentration of anthraquinone is 200g/L, and described anthraquinone is 2- EAQs, tetrahydrochysene 2- second
Base anthraquinone, 2- amyl anthraquinones, tetrahydrochysene 2- amyl anthraquinones are with 2：2：0.5：The mixture that 0.5 ratio is mixed.
The catalyst solid particle loaded in fluidized-bed reactor, the density of catalyst solid particle is less than 1g/cm3, grain
Footpath is 40~300 microns.
Described catalyst solid particle includes active ingredient and carrier, the percentage by weight of active ingredient for 1%~
3%th, the percentage by weight of carrier is 97%~99%, and the two is combined together by infusion process load technology；
Described active ingredient is palladium；
Described carrier is sodium silicoaluminate；
Described carrier, particle mean size is 70~300 microns, average pore size(angstrom), specific surface area be 80~
200 meters squared per grams, 0.6~0.8mL/g of pore volume.
Described anthraquinone working solution, is passed through in fluidized-bed reactor again after being heated to 35~60 DEG C.
(2) vent gas treatment：After hydrogenation terminates, unreacted hydrogen-containing gas is discharged at the top of fluidized-bed reactor, and
Increase progress hydrogenation reaction in laggard fluidized bed reactor again by circulating air compressor after purification to follow so as to be formed
Ring utilizes
(3) hydrogeneous anthraquinone working solution post processing：The hydrogen anthraquinone working solution formed after hydrogenation reaction carries out gas-liquid through filter
Separate, filter out contained catalyst, then enter after cooling and oxidation reactor progress is prepared to enter into hydride degassing tank instead
Should, most of liquid phase returns to through the heat exchanger heat exchange Posterior circle under filter and carries out hydrogenation reaction in fluidized-bed reactor again, follows
Ring gas phase after supercooling collect obtaining the solvent containing a small amount of anthraquinone；
In the present embodiment, using this method, production efficiency 30 can be improved on existing domestic fixed bed hydrogenation Process ba- sis
~50%, because being complete acid operating mode technique, the hazards in the substantially solution production of production principle and technique
(traditional hydrogen peroxide process production process has the outer science and engineering skill of alkali, and hydrogen peroxide meets caustic digestion).In the present embodiment, product design is
43%, the present invention can make product design improve more than 40%, and product quality leading indicator such as organic carbon content by 30%,
Non-volatile content etc. is better than the product that fixed-bed process is produced.
Examples detailed above simply to illustrate technical concept of the present utility model and technical characterstic, can not limit this reality with this
With new protection domain.All equivalent transformations done according to essence of the present utility model or modification, should all cover in this reality
Within new protection domain.
Claims (7)
1. a kind of hydrogenation apparatus of hydrogeneous anthraquinone working solution, including hydrogenation liquid preparing system and nitrogen hydrogen mixed tail gas processing system,
It is characterized in that：Described hydrogenation liquid preparing system includes fluid bed (6), hydride head tank (8), the hydride being sequentially connected
Grade one filter (9), hydride cooler (12), hydride groove (13), hydride circulating pump (14), hydride secondary filtration
Device (15) and security filter (16), raw material carries out reacting obtained working solution in fluid bed eventually passes through security filter mistake
Flowed into after filter in deoxidation tower；Described nitrogen hydrogen mixed tail gas processing system include be sequentially connected recycle hydrogen condenser (4), follow
Ring hydrogen liquid/gas separator (3), circulating hydrogen filter (2) and circulating hydrogen press (1), the air inlet and stream of recycle hydrogen condenser
The circulating air outlet for changing bed is connected, and the exhaust outlet of circulating hydrogen press is connected with the circulating air import of fluid bed, fluid bed
The tail gas formed after interior reaction enter recycle hydrogen condenser in sequentially pass through processing after fluid bed is back to by circulating hydrogen press
In recycle.
2. hydrogenation apparatus according to claim 1, it is characterised in that：Described fluid bed (6) is that gas-liquid-solid three-phase is followed certainly
Loop reactor, including reactor shell (61) and internals, wherein：
The bottom of described reactor shell (61) is provided with working solution import (62), newly reaction hydrogen inlet (63), circulation fluid enter
Mouth B (66), bottom is distributed endless tube (610), circulating air import (64), circulation fluid import A (65) with one heart provided with cyclic nitrogen hydrogen, on
Portion is provided with circulation fluid outlet (67), and top is provided with circulating air outlet (68)；
Working solution import (62) and the tube side of the shell and tube film blender (69) positioned at housing bottom in reactor shell bottom
Connection, newly reacts hydrogen inlet (63) and is connected with the shell side of shell and tube film blender；The membrane tube of described shell and tube film blender
Tube side is connected with inside reactor, and the outlet of membrane tube tube side is provided with anti-settling poly- device；
The frid (611) of annular is fixed with along inwall in reactor internal upper part, frid bottom is provided with 8~20 outages, frid
It is provided with above medium design gas passage, the passage above umbellate form baffle plate (612), umbellate form baffle plate and is provided with demister (613),
The flushing liquor distribution apparatus (614) of anti-anthraquinone condensation is provided with above demister；
Described circulation fluid outlet (67) is located at the lower section of frid (611), and circulation fluid import B (66) is located at shell and tube film blender
(69) lower section, circulation fluid import A is located at shell and tube film blender, cyclic nitrogen hydrogen and is distributed with one heart between endless tube；
Endless tube is distributed with one heart provided with described cyclic nitrogen hydrogen above described shell and tube film blender；
It is conversion zone that described cyclic nitrogen hydrogen is distributed between endless tube (610), frid (611) with one heart, and conversion zone is built with catalysis
Agent.
3. hydrogenation apparatus according to claim 2, it is characterised in that：The outside of described fluid bed (6), which is also equipped, urges
Agent feeder (5), is connected by the feeding tube conversion zone internal with fluid bed (6).
4. hydrogenation apparatus according to claim 1 or 2, it is characterised in that：Described working solution import (62) is with providing work
The device for making liquid is connected, and newly reacts hydrogen inlet (63) and is connected with providing the device of hydrogen, circulating air import (64) is with following
The exhaust outlet of ring hydrogen press (1) is connected, and circulating air outlet (68) is connected with the air inlet of recycle hydrogen condenser (4)；Institute
Working solution preheater (7) is connected between the device of the offer working solution stated, working solution import.
5. hydrogenation apparatus according to claim 1 or 2, it is characterised in that：Hydride head tank (8), middle part is provided with import
A, bottom is provided with broken spigot and provided with outlet A；Import A is connected by pipeline with the circulation fluid outlet (67) of fluid bed (6)；Go out
A points of mouth is two-way：The import B with hydride grade one filter (9) is connected all the way, all the way with the circulation fluid import B of fluid bed
(66) it is connected, valve or road valve is fitted with two-way.
6. hydrogenation apparatus according to claim 1 or 2, it is characterised in that：Hydride grade one filter (9), middle part is provided with
Import B, top are provided with reaction solution outlet (615), bottom provided with outlet B；Import B is connected with the outlet A of hydride head tank,
Outlet B is connected by circulation fluid cooler (10) with the circulation fluid import A (65) of fluid bed；Reaction solution outlet (615) is divided into
Two-way, all the way import with hydride cooler (12) is connected, and anti-purge pump (11) and blind controller system are connected with all the way,
The entrance of anti-purge pump is connected with hydride groove (13).
7. hydrogenation apparatus according to claim 1, it is characterised in that：Described hydride head tank (8), hydride one-level
Filter (9) constitutes outer circulation and discharging equipment, and the outer circulation and discharging that shell Ligation in vitro 6-12 of fluid bed (6) is described are set
It is standby.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629622A (en) * | 2017-03-02 | 2017-05-10 | 中触媒新材料股份有限公司 | Hydrogenation method and hydrogenation device for oxanthranol-containing working solution |
| CN108892108A (en) * | 2018-09-03 | 2018-11-27 | 江山市双氧水有限公司 | A kind of process system of hydride storage tank involved in the dilute product process units of hydrogen peroxide |
| CN109110324A (en) * | 2018-09-04 | 2019-01-01 | 江山市双氧水有限公司 | Hydride separates storage hydride storage tank in a kind of dilute product process units of hydrogen peroxide |
| CN111714922A (en) * | 2019-03-22 | 2020-09-29 | 中国石油化工股份有限公司 | Emergency treatment device and hydrogen peroxide production device comprising same |
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2017
- 2017-03-02 CN CN201720194905.6U patent/CN206616014U/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629622A (en) * | 2017-03-02 | 2017-05-10 | 中触媒新材料股份有限公司 | Hydrogenation method and hydrogenation device for oxanthranol-containing working solution |
| CN106629622B (en) * | 2017-03-02 | 2019-02-22 | 中触媒新材料股份有限公司 | A kind of method for hydrogenation and hydrogenation apparatus of hydrogeneous anthraquinone working solution |
| CN108892108A (en) * | 2018-09-03 | 2018-11-27 | 江山市双氧水有限公司 | A kind of process system of hydride storage tank involved in the dilute product process units of hydrogen peroxide |
| CN109110324A (en) * | 2018-09-04 | 2019-01-01 | 江山市双氧水有限公司 | Hydride separates storage hydride storage tank in a kind of dilute product process units of hydrogen peroxide |
| CN111714922A (en) * | 2019-03-22 | 2020-09-29 | 中国石油化工股份有限公司 | Emergency treatment device and hydrogen peroxide production device comprising same |
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