CN106430108A - System and method for preparing hydrogen peroxide through anthraquinone method under supergravity condition - Google Patents
System and method for preparing hydrogen peroxide through anthraquinone method under supergravity condition Download PDFInfo
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- CN106430108A CN106430108A CN201610883802.0A CN201610883802A CN106430108A CN 106430108 A CN106430108 A CN 106430108A CN 201610883802 A CN201610883802 A CN 201610883802A CN 106430108 A CN106430108 A CN 106430108A
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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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Abstract
The invention provides a system and method for preparing hydrogen peroxide through an anthraquinone method under the supergravity condition. The system comprises a supergravity rotating packed bed, a gas conveying device, a liquid conveying device, a first preheating device and a second preheating device. The supergravity rotating packed bed comprises a shell, a reactor and a rotating device. The reactor is located in the shell, the wall of the reactor is filled with a catalyst, through holes are formed in the wall of the reactor, and the reactor is communicated with the shell through the through holes. The rotating device is connected with the reactor and used for driving the reactor to rotate. The system and method for preparing hydrogen peroxide through the anthraquinone method have the advantages of being short in reaction time, high in hydrogenation efficiency and mass transfer efficiency, easy to operate, small in equipment size, low in investment and the like when used for preparing hydrogen peroxide.
Description
Technical field
The invention belongs to technical field prepared by hydrogen peroxide, was prepared using anthraquinone under the conditions of being related to a kind of hypergravity
Under the conditions of the system and method for hydrogen oxide, more particularly to a kind of hypergravity using what anthraquinone derivative hydrogenation prepared hydrogen peroxide it is
System and method.
Background technology
Hydrogen peroxide is important industrial chemicals and fine chemical product, as which is only given birth to during chemical reaction is participated in
Cheng Shui and active oxygen, therefore hydrogen peroxide there is non-secondary pollution, be referred to as " green chemical ", be widely used in
Papermaking, weaving, chemicals synthesis, electronics, food processing, medicine, environment are protected.The numerous areas such as shield.It is that over nearly 10 years, consumption increases
One of most fast chemicals of length.At present the yield of whole world hydrogen peroxide is increased with annual 6% speed, device year total productive capacity
About 2800kt (in terms of 100%), is concentrated mainly on some major companies of foreign countries.In recent years, domestic hydrogen peroxide manufacture
Development is very fast, and market demand is also continuously increased, and in 2009, the production capacity of China and yield all leapt to the whole world first, are
The nearly twice in the U.S..With increasingly raising of the country to environmental requirement, the range of application of hydrogen peroxide and demand are also increasingly expanding
Greatly, and the chemicals for having severe contamination to environment are progressively instead of in some fields.
At present, the production method of hydrogen peroxide has isopropanol method, electrolysis, hydrogen-oxygen direct synthesis technique, negative electrode sun in the world
Pole reducing process, vacuum concentration method and anthraquinone etc., with production cost and the impact of environmental conservation, a lot of methods all gradually by
Eliminate, and anthraquinone to become at present both at home and abroad production hydrogen peroxide most main due to its mild condition, safe, technical maturity
The method that wants.Anthraquinone employing anthraquinone obtains hydrogen peroxide as working material by operations such as hydrogenation, oxidation, extractions.Wherein hydrogen
Chemical industry sequence is the core of whole technical process, and hydrogenation process is at present with palladium catalyst catalyst, fixed-bed process as main flow.
Although anthraquinone technique tends to ripe substantially through updating, the method also comes with some shortcomings it all the time
Place, most of fixed-bed palladium catalysts technique is all formed using spherical or bar shaped supported carrier active component palladium, but this
A little catalyst are solid construction, increase surface area and are restricted, and catalysis activity and selectivity are difficult to improve further, actual work
In industry application, solid catalyst heap density is big, causes beds load big, also result in catalyst bed in reaction after filling
The increase of resistance;On the other hand, present fixed bed reactors technique is all to adopt vertical reactor, hydrogen and working solution from fixation
Bed reactor head charging, in this feeding manner reactor, gas phase is continuous phase, liquid phase from top spray, under gravity
Drip shape is become to decline in fixed bed, referred to as trickle bed, gas phase hydrogen will participate in reaction, need to get to catalyst by mass transfer in liquid phase
Surface, the resistance to mass tranfer of gas phase hydrogen is big, is unfavorable for the carrying out of hydrogenation reaction, simultaneously because liquid phase axle, radial distribution uneven phenomenon,
Cause reactor locally by inefficiency, beds local hydriding excessively cause caking, be further exacerbated by bias current so that
The rapid rising of bed resistance and cannot production operation.Therefore, strengthen the improvement to reactor, the mass transfer that strengthens between gas-liquid is conducive to this anti-
The carrying out that answers.
Scientific worker has done substantial amounts of work in the exploration of hydrogenation process and the design aspect of reactor both at home and abroad, rationally
Design can effectively improve gas liquid interfacial area, control time of contact, play reinforcing gas-to-liquid contact mixed effect, and then improve and set
Standby production capacity.Such as:
A kind of method of process for prepairng hydrogen peroxide by anthraquinone that CN101229915A is announced and GB 2334028A and JP-Kokai
143216 announce to hydrogenating trickle bed improved method, after improvement, working solution and hydrogen cocurrent be from bed top downwards or from bed bottom simultaneously
Stream is flowed up, by adjusting liquid-gas ratio and Hydrogen Vapor Pressure, working solution and hydrogen voluntarily shape in the case of no any foam device
Become foam mixture, cocurrent flows through beds, gas-liquid mass transfer is enhanced, but consersion unit volume is larger, while existing high
The breakable shortcoming of catalyst under flow velocity.
Cross_flow rotating packed bed reactor is a kind of new heat and mass equipment, with small volume, mass tranfer coefficient height
Advantage.So-called hypergravity refers to the power under the environment more much bigger than terrestrial gravitation acceleration suffered by material, hypergravity
Technology is to reach the purpose of simulation Elevated Gravity by the effect of centrifugal force field.The technological core is for transmittance process
With the very big reinforcing of micro mixing, thus it is for the complex process for needing to strengthen alternate transmittance process and needs
In the interior or plan of phase is homogeneous, the mixing of microring array reinforcing is significant with course of reaction.Cross_flow rotating packed bed can be very big
Ground reinforcing gas-liquid mass transfer contact effect, except in the case of high-speed rotation formed super gravity field in addition to, it is important that relevant with filler, often
The cross_flow rotating packed bed that sees mostly is the structured packing such as ripple silk net filler, fin filler with filler.
CN 102764627A discloses a kind of cross_flow rotating packed bed consersion unit.By the revolving bed in housing, housing
Reative cell, integral drive mechanism composition.Rotation bed wall is provided with hole, is fixed on the feed tube of case top and air inlet pipe is positioned over
Inside revolving bed, integral drive mechanism is fixedly installed on the bottom of revolving bed, and the rotation bed wall is porous aggregate layer, revolving bed
Inwall be netted structure, described filler layer thickness be 5-20 layer;The bottom of the revolving bed is non-porous or has pore structure.
At present, rectification, extraction, absorption and the preparation of superfine powder, such as CN are applied to high-gravity technology more
101774895SA discloses a kind of technique and device for being prepared guaiacol by the continuously hydrolyzing diazonium salt of o-aminoanisole,
React for liquid-liquid reactions, core apparatus of this invention include the hydrolysis reactor of cross_flow rotating packed bed and coil pipe composition, have
Beneficial effect:The generation of by-product can be reduced, yield brings up to more than 90%, reduce the discharge of the three wastes, production cost is reduced,
And equipment volume is little, the driving and parking time is short, installation operation is easy to maintenance.CN 101462933A discloses a kind of catalysis oxidation
The method and apparatus of synthesis hydroxy benzaldehyde, reaction is related to gas-liquid two-phase, after using high-gravity technology, the conversion of paracresol
Rate is high, product yield and purity is high, simple to operate, equipment volume is little.CN 1539743A discloses a kind of hypergravity reactive crystallization
The method that method prepares nano-zinc sulfide, reaction is related to gas-liquid-solid three-phase, and with zinc nitrate and hydrogen sulfide gas as raw material, prepared by this method
Nano-zinc sulfide lower than prior art cost, uniform particle sizes, narrow particle size distribution, crystal formation is more complete.But it is described above
Filler is inertia structured packing, filler no catalysis characteristicses itself.
Up to the present, also there is not high-gravity technology and combine bulk catalyst filler answering in hydrogen peroxide preparation field
Patent report.And the raw material in the anthraquinone raw material for preparing hydrogen peroxide and process conditions and method described above and work
Skill condition difference, cross_flow rotating packed bed is applied to the anthraquinone result for preparing hydrogen peroxide can not expect, and technique
Condition is also required to further research.
Content of the invention
Pass for being existed using the method for catalysis oxidation synthesis hydrogen peroxide with 2-ethyl-anthraquinone as raw material in prior art
Matter efficiency is low, equipment volume is big, production capacity is low, the low problem of catalyst efficiency, it is an object of the invention to provide a kind of super
Using the anthraquinone system and method for preparing hydrogen peroxide under gravity condition, the anthraquinone system for preparing hydrogen peroxide for
Prepare hydrogen peroxide and have that the response time is short, hydrogenation efficiency is high, mass-transfer efficiency is high, simple to operate, equipment volume is little and investment
Little the advantages of.
For reaching this purpose, the present invention is employed the following technical solutions:
An object of the present invention is to provide a kind of for the anthraquinone system for preparing hydrogen peroxide, and the system includes
Cross_flow rotating packed bed, air transporting arrangement, liquid transporting apparatus, the first preheating device and the second preheating device;
Cross_flow rotating packed bed includes housing, reactor and rotary apparatuss, and reactor is located in housing, the wall of reactor
In be filled with catalyst, and the wall of the reactor arranges through hole, and reactor is connected with housing by the through hole;Rotating dress
Put and be connected with reactor, for driving reactor to rotate;
Air transporting arrangement is connected with the gas feed for arranging on reactor and/or housing by gas transfer pipeline, and
And the first preheating device is set on gas transfer pipeline;
Liquid transporting apparatus are connected with the liquid-inlet for arranging on reactor by liquid transmission pipeline, and liquid conveying
Second preheating device is set on pipeline;
Gas outlet and liquid outlet are set on the housing.
As well known to those skilled in the art, the system also includes oxidation furnaces, extraction equipment and equipment for purifying etc., and these set
Standby is equipment commonly used in the art, and therefore not to repeat here.Those skilled in the art are also known, and the cross_flow rotating packed bed is worked as
When liquid-inlet, liquid outlet, gas feed and gas outlet all seal, which is integrally sealing, and reactor rotor is only
Connected with housing by the through hole for arranging on wall, to ensure that gas and liquid come in by entrance point, it is necessary to through reactor rotor
Participate in reaction to discharge.
Described high-gravity rotating bed for horizontal or vertical, preferably horizontal.
Preferably, network structure is set in the through hole.
Preferably, the cancellated material any one in metal, silica gel or macromolecular material or at least
Two kinds of combination, preferably reinforcing bar, typical but non-limiting combination such as metal and silica gel, metal and macromolecular material, silica gel
With macromolecular material etc..The through hole and the cancellated design in through hole cause the catalyst resistance of the reactor
Substantially reduce.In traditional reactor, as the pressure of pump is relatively low, in liquid distribution pipe, trickle horizontal initial rate is little, leads
Cause can not radially incident beds, the wettability power of catalyst is relatively low, and based on this kind of consideration, the wall of reactor arranges logical
Hole, and network structure is set in through-holes, compared to the design percent opening increase of traditional slit, it is easy to the circulation of working solution.
Preferably, the through hole have multiple, between adjacent through-holes at intervals of 1mm-100cm, such as 2mm, 3mm, 5mm,
8mm, 10mm, 30mm, 50mm, 100mm, 500mm, 1cm, 3cm, 5cm, 8cm, 15cm, 30cm, 50cm, 80cm or 90cm etc..
Preferably, the through hole is circle.
Preferably, the reactor is hollow cylinder, arranges through hole on the wall of the cylinder.
Preferably, the wall thickness of the cylinder be 5-50mm, such as 8mm, 10mm, 15mm, 18mm, 20mm, 30mm, 40mm or
45mm etc..
Preferably, the radius of the cylinder be 5-50mm, such as 8mm, 10mm, 15mm, 18mm, 20mm, 30mm, 40mm or
45mm etc..
Preferably, the housing be shaped as hollow cylinder, the radius of the housing is 5-500mm, such as 10mm,
20mm, 50mm, 80mm, 100mm, 150mm, 200mm, 300mm, 400mm or 450mm etc..
The liquid transporting apparatus include work liquid storage tank and pump, and the work liquid storage tank is by pump and liquid-inlet phase
Even.
Preferably, the air transporting arrangement includes that hydrogen-holder and nitrogen storage tank, hydrogen-holder and nitrogen storage tank all lead to
Cross the first preheating device to be connected with gas feed.
Preferably, the system also includes condensing units and product storage tank, the import of the condensing units and liquid outlet
It is connected;The product storage tank is connected with the liquid outlet of condensing units and the liquid outlet of housing.
Preferably, the system also includes spray equipment, and the spray equipment is connected with liquid transporting apparatus, the spray
Device is used for working solution to be sprayed onto the wall of reactor, is more beneficial for the haptoreaction of working solution and hydrogen.
Preferably, the spray equipment includes feed tube, the feed tube one end open, and the other end is closed, feed tube
Opening is connected with liquid transporting apparatus, and the blind end of feed tube is stretched in reactor, and stretches into the wall of the feed tube of reactor
Upper setting through hole, for working solution to be sprayed onto the wall of reactor.
The system arranges two gas feeds and the sealing piston for matching, and described two gas feeds one are located at shell
On body, another is located on reactor.Described two gas feeds and the setting of sealing piston facilitate implementation hydrogen with working solution
Following current or counter current contacting, than during if desired for hydrogen with working solution co-current contact, with sealing piston by the gas feed on housing
Block.
Used as preferred technical scheme, the system includes the cross_flow rotating packed bed of at least two series connection, previous super
The rotary packed bed liquid outlet of gravity is connected with the liquid-inlet of a rear cross_flow rotating packed bed;Air transporting arrangement is respectively
It is connected with the air inlet at least two cross_flow rotating packed bed.It is preferred that the system includes the hypergravity of 1-100 series connection
Rotary packed bed, the system may include 2,10,30,50,60,70,80 or 90 hypergravity rotary fillings
Material bed.The rotary packed bed number, those skilled in the art can determine according to actual needs.The hypergravity rotates filler
Bed can used aloned, it is also possible to multiple use that are together in series, so as to control its hydrogen effect 1-20g.
The second object of the present invention is to provide a kind of method for preparing hydrogen peroxide using system as above.
Used as preferred technical scheme, methods described comprises the steps:
(1) in the wall of cross_flow rotating packed bed reactor load hydrogenation catalyst, make cross_flow rotating packed bed with
0-3000r/min speed rotation, such as 10r/min, 50r/min, 100r/min, 300r/min, 500r/min, 800r/min,
1000r/min, 2000r/min, 2300r/min, 2500r/min or 2800r/min etc.;
(2) hydrogen after preheating and hydraulic fluid are all introduced in the reactor, or, hydrogen and working solution are drawn respectively
Enter in the housing and reactor of cross_flow rotating packed bed;Pressure during adults power is rotary packed bed is 0.1-10MPa, such as
0.15MPa, 0.2MPa, 0.3MPa, 0.5MPa, 1.0MPa, 2MPa, 5MPa, 7MPa, 8MPa or 9MPa etc. so that hydrogen and work
Make liquid in the reaction of catalyst surface cocurrent, cross-flow or counter current contacting, the liquid-phase reaction product for obtaining and gas phase reaction product, and warp
Through hole flows out, and liquid-phase reaction product is post-treated, obtains hydrogen peroxide product.
The method of the anthraquinone legal system hydrogen peroxide that the present invention is provided, by traditional vertical or horizontal reactor replacement be mainly
Supergravity reactor.Wherein, the reaction that anthraquinone hydrogenation generates hydrogen anthraquinone is that the working solution containing anthraquinone is passed through with hydrogen and is filled with
In the cross_flow rotating packed bed reactor of hydrogenation catalyst so that the anthraquinone in working solution in the presence of catalyst with hydrogen
Generation hydrogenation reaction generates hydrogen anthraquinone, and the hydrogenated work liquid containing hydrogen anthraquinone for obtaining after reaction is derived from reactor, just may be used
To carry out next step oxidation, the step such as extraction, obtain hydrogen peroxide product.
The preparation method of the hydrogen peroxide that the present invention is provided is by the working solution containing anthraquinone with hydrogen respectively from liquid
Import and gas feed are passed in cross_flow rotating packed bed, carry out adverse current, cross-flow or cocurrent reaction.
Working solution with the course of reaction of hydrogen adverse current is:Hydrogen introduces reactor exocoel, enters under gas pressure effect
Arrive in the filler full of catalyst;After working solution is introduced in reactor, under the action of the centrifugal force, circumferential speed increases, working solution
Gradually it is distributed on the inwall of reactor.Whole process, the working solution containing anthraquinone is disperseed by catalyst filling, crushing-type poling
Infinitesimal that is big, constantly updating, tortuous runner has been further exacerbated by the renewal at interface.Working solution containing anthraquinone high dispersive,
High turbulent flow, strong mixing and interface are inversely contacted with great relative velocity with hydrogen in the case of rapidly updating, greatly by force
Mass transport process is changed.Then, the working solution containing anthraquinone and hydrogen anthraquinone is thrown to after shell collects by reactor and leaves through liquid outlet
Cross_flow rotating packed bed, hydrogen leaves cross_flow rotating packed bed through gas outlet, completes whole course of reaction.
Working solution with the course of reaction of hydrogen cocurrent is:Hydrogen all introduces reactor inner chamber with working solution, in rotary course
In, gas-liquid circumferential speed increases, and working solution is gradually distributed to reactor wall, in the process, gas-liquid cocurrent in packing layer
Contact, then hydride and hydrogen realize gas-liquid separation together after the condensed pipe liquor separator of gas liquid outlet.
The present invention provide process for prepairng hydrogen peroxide by anthraquinone method, mainly to the utilization gravitational field in conventional art come
Carry out the operation of the hydrogenation technique in the hydrogenation reactor of mass transfer to be changed, traditional vertical reactor is replaced with hypergravity
Rotary packed bed, its effect that brings is that more traditional trickle bed hydrogenation efficiency is obviously improved.In the method for the invention, control
The continuous phase that reactant is entered in reactor by liquid-inlet is the working solution containing anthraquinone, and hydrogen enters into reaction by gas feed
In device, both carry out disperseing, mix and haptoreaction under the influence of centrifugal force.Wherein, when hydrogen runs into catalyst granules
When, as catalyst is constantly updated, catalyst surface moment is exposed and contacts with hydrogen, adsorb;When the working solution containing anthraquinone is met
During to catalyst granules, as catalyst surface liquid film is constantly updated, catalyst surface moment of adsorbed hydrogen exposed and with contain
The working solution contact of anthraquinone, this catalyst surface gas phase and the instantaneous of liquid phase alternately update, and in the presence of strong centrifugal force, pass
Matter and hydrogenation reaction are able at a high speed, efficiently while carrying out.In reactor, gas-liquid renewal speed is fast, so hardly there is hydrogenation
The phenomenon that excessively lumps.
The loadings control of step (1) catalyst in 20-200mL, such as 30mL, 40mL, 50mL, 70mL, 80mL,
90mL, 100mL, 120mL, 130mL, 150mL or 180mL etc..
Preferably, step (1) catalyst is that load type palladium catalyst, the carrier in the load type palladium catalyst is
Any one in aspheric pelleted substrate with hollow-core construction, preferably Raschig ring, Wheel ring packing, porous bar or porous ring
Kind or at least two combination, more preferably Raschig ring.The aspheric pelleted substrate of the hollow-core construction refers to carry
Appropriate space (regular or irregular) is formed with for reducing heap ratio, expanding external surface area in body body, such as Raschig ring, car
The shape such as torus, porous bar or porous ring.The concrete size Selection of the catalyst granules selected by the present invention can be according to actual work
The specific condition such as process conditions, production capacity in industry application and determine.
Preferably, in the load type palladium catalyst palladium load capacity be 0.01-1wt%, such as 0.05wt%, 0.1wt%,
0.3wt%, 0.5wt%, 0.7wt% or 0.9wt% etc..According to specific embodiment, the catalyst in the super-gravity device
Can be the hydrogenation catalyst of conventional all size, the granular load type palladium catalyst such as generally spherical or bar shaped, and
And the carrier of catalyst is usually the aluminium oxide of solid spherical or bar shaped.The preferred catalyst carrier of the present invention is Raschig ring
The mixed carrier of shape aluminium oxide, silicon oxide or aluminium oxide and silicon oxide, load type palladium catalysis obtained from dipping active component palladium
Agent (loading of palladium is 0.01wt%-1wt%).
Preferably, step (1) catalyst is alumina composite Pd black catalyst, described alumina composite palladium black catalysis
In agent, the weight/mass percentage composition of palladium black is preferably 0.1%-5%, such as 0.3%, 0.5%, 1%, 2%, 3% or 4% etc..
Preferably, the alumina composite Pd black catalyst for 1-100mm diameter spherical (as a diameter of 2mm, 3mm,
5mm, 10mm, 20mm, 30mm, 50mm, 70mm or 80mm etc.), draw ratio is 1:1-1:10 (if draw ratio is 1:2、1:3、1:4、
1:5、1:6、1:7、1:8 or 1:9 etc.), a diameter of 1-100mm (as a diameter of 2mm, 3mm, 5mm, 10mm, 20mm, 30mm,
50mm, 70mm or 80mm etc.) Raschig ring type, or the trifolium-shaped of same size.
The incorporation way of step (2) working solution and hydrogen is:Working solution is sprayed the reaction for being sprinkled upon rotation by feed tube
On device inwall, hydrogen axle phase or radially flow through catalyst in reactor wall, on the reactor wall both following currents, cross-flow or
Counter current contacting.
Preferably, the hydrogen flowing quantity is 1-100L/min, such as 2L/min, 5L/min, 8L/min, 10L/min, 20L/
Min, 30L/min, 50L/min, 70L/min or 90L/min etc., working solution flow is 1-100L/min, such as 2L/min, 5L/
Min, 8L/min, 10L/min, 20L/min, 30L/min, 50L/min, 70L/min or 90L/min etc..
Preferably, in step (2) cross_flow rotating packed bed, hydrogen is 10 with the volume ratio of working solution:1-15:1,
As 12:1、11:1、13:1、14:1 or 14.5:1 etc..
Preferably, step (2) working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and heavy aromatics
Volume ratio with trioctyl phosphate is 75:25-80:20, such as 76:24、77:23、78:22 or 79:21;The concentration of heavy aromatics is
660-680mL/L, such as 662mL/L, 665mL/L, 668mL/L, 670mL/L, 672mL/L, 675mL/L or 678mL/L etc.;Phosphoric acid
The concentration of three monooctyl esters be 210-230mL/L, such as 212mL/L, 215mL/L, 218mL/L, 220mL/L, 222mL/L, 225mL/L,
228mL/L or 229mL/L etc.;The concentration of 2-ethyl-anthraquinone is 110-130g/L, such as 112g/L, 115g/L, 118g/L, 120g/
L, 122g/L, 123g/L, 125g/L or 127g/L etc..
Preferably, after step (2) preheating hydrogen and the temperature of working solution are 55-75 DEG C, such as 56 DEG C, 57 DEG C, 58 DEG C, 59
DEG C, 60 DEG C, 62 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 72 DEG C or 74 DEG C etc..
Preferably, step (2) reaction is carried out under the conditions of 20-100 DEG C, such as 25 DEG C, 26 DEG C, 28 DEG C, 30 DEG C, 35
DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C or 90 DEG C etc..
Preferably, step (2) also carries out reduction activation process to catalyst before introducing hydrogen and working solution, specially:
Cross_flow rotating packed bed is heated to 50-80 DEG C, such as 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 78 DEG C etc., is passed through hydrogen also
After former activation 1-24h, such as 2h, 3h, 5h, 8h, 10h, 12h, 15h, 18h or 20h etc., are drained with nitrogen.
Preferably, step (2) post processing includes:Liquid-phase reaction product is aoxidized, extraction, purification, obtained
Oxidation hydrogen production;Condensation gas phase reaction product, obtains gas phase and liquid phase, and liquid phase is mixed with liquid-phase reaction product, and gas is emptied.
Preferably, the liquid-phase reaction product return to step (1) that step (2) is obtained is mixed with working solution, or, step (2)
Working solution of the liquid-phase reaction product for arriving as next cross_flow rotating packed bed.The liquid-phase reaction product for obtaining can be followed
Ring reaction or the next cross_flow rotating packed bed of entrance, carry out hydrogenation, again to reach preferable hydrogenation efficiency and space-time
Yield.
Used as preferred technical scheme, methods described comprises the steps:
(1) catalyst is packed in the wall of cross_flow rotating packed bed reactor, cross_flow rotating packed bed is heated
To 80 DEG C, after being passed through hydrogen reducing activation 8h, drained with nitrogen;Cross_flow rotating packed bed is made with the speed of 0-3000r/min
Rotation;
(2) working solution by temperature for 55-75 DEG C is sprinkled upon on the reactor wall of rotation by feed tube ejection, and temperature is
55-75 DEG C of hydrogen axle phase or radially flow through catalyst in reactor wall, on the reactor wall both following currents, cross-flow or
Counter current contacting is reacted;Wherein, hydrogen flowing quantity is 1-100L/min, and working solution flow is 1-100L/min;Hydrogen and working solution
Volume ratio is 10:1-15:1;Working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and heavy aromatics and phosphoric acid
The volume ratio of three monooctyl esters is 75:25-80:20;The concentration of heavy aromatics is 660-680mL/L;The concentration of trioctyl phosphate is 210-
230mL/L;The concentration of 2-ethyl-anthraquinone is 110-130g/L;Reaction temperature is 20-100 DEG C;Adults power in course of reaction
Pressure in rotary packed bed is 0.1-10MPa;The liquid-phase reaction product for obtaining and gas phase reaction product, and via through holes outflow;
(3) liquid-phase reaction product is collected, which is aoxidized, extraction, obtain hydrogen peroxide product;Condensation gas phase reaction product
Thing, obtains gas and liquid phase, and gas is emptied, and liquid phase is mixed with liquid-phase reaction product.
The present invention provide hydrogen peroxide preparation method with 2-ethyl-anthraquinone and hydrogen as raw material, with heavy aromatics and phosphoric acid
Three monooctyl esters are solvent, with particulate supported type palladium catalyst as catalyst, at 20-100 DEG C, carry out hydrogen under 0.1-10MPa pressure
Change reaction.
The anthraquinone concrete course of reaction for preparing hydrogen peroxide is as follows:
After reaction terminates, hydride feeding oxidation furnaces are aoxidized, the reaction of generation is:
Liquid after oxidation obtains hydrogen peroxide product through extraction process.In the process, can be to hydride sampling point
Analysis, calculates hydrogenation efficiency.
In sum, the described method of the present invention be produced by cross_flow rotating packed bed reactor high-speed rotation
Catalytic hydrogenation synthesis hydrogen anthraquinone under the conditions of hypergravity, the oxidizing process of hydrogen anthraquinone is consistent with traditional method, most after prepared through extraction
Hydrogen peroxide.
In addition, except preparing hydrogen peroxide using 2-ethyl-anthraquinone for raw material, using 2- tert-butyl group anthraquinone, 2- tertiary pentyl anthracene
Quinone or 2- isobutyl group anthraquinone prepare hydrogen peroxide and also can carry out in the system that the present invention is provided.
Compared with prior art, beneficial effects of the present invention are:
Cross_flow rotating packed bed in the anthraquinone system for preparing hydrogen peroxide that the present invention is provided is to prepare peroxidating
The nucleus equipment of hydrogen production:Synthesis hydrogen anthraquinone is that liquid film becomes using the centrifugal force field produced by cross_flow rotating packed bed rotation
Thin, drop diminishes, and reaches nanometer, micron order, produces huge boundary;The renewal speed of liquid film is also greatly improved;Make
The contact for obtaining between gas-liquid is more abundant, so as to greatly enhance the hydrogenation process, makes reactor production capacity improve 30%
More than, and bed resistance is little, simultaneously because the time of staying is little, is not in over-hydrogenation and caking phenomenon, and side reaction is strictly controlled
System.
The method of the process for prepairng hydrogen peroxide by anthraquinone that the present invention is provided, compared with traditional handicraft, can effectively improve reactor
Efficiency, makes full use of catalyst, so as to improve the productivity ratio of hydrogen peroxide.
Cross_flow rotating packed bed and prepare the method response time of hydrogen peroxide than fixing using which that the present invention is provided
Bed reactor shorten 50%, hydrogenation efficiency can reach 6g/L, mass-transfer efficiency can improve 50%-200%, cost be only fixed bed anti-
The 10% of device is answered, and floor space is obviously reduced, simple to operate and small investment.
Description of the drawings
Fig. 1 is the system schematic of the process for prepairng hydrogen peroxide by anthraquinone of the offer of embodiment 2.
In the process for prepairng hydrogen peroxide by anthraquinone technique that Fig. 2 is provided for one embodiment of the present invention, urge for anthraquinone hydrogenation
Change the structural representation of the cross_flow rotating packed bed of the adverse current of reaction.
In the process for prepairng hydrogen peroxide by anthraquinone technique that Fig. 3 is provided for one embodiment of the present invention, urge for anthraquinone hydrogenation
Change the structural representation of the cross_flow rotating packed bed of the cocurrent of reaction.
Fig. 4 is the hydrogenation efficiency of the different circulation time hydrides of the offer of embodiment 11 and space-time yield.
Wherein, in Fig. 1:1- mass flow controller;The first preheating furnace of 2-, 3- tee ball valve, 4- hypergravity rotates filler
Bed, the second preheating furnace of 5-;6- condenser, 7- product storage tank, 8- liquid taking port, 9- air relief valve, 10- pressure gauge, 11- pump, 12- works
Liquid storage tank, 13- setting-out mouth;
In Fig. 2:21- feed tube, 22- gas outlet, 23- gas feed, 24- housing, 25- reactor, 26- drop, 27-
Filler, 28- liquid outlet, 29- bearing, 210- motor;
In Fig. 3:31- feed tube, 32- gas feed, 33- housing, 34- reactor, 35- drop, 36- filler, 37- gas-liquid
Outlet, 38- bearing, 39- motor.
Specific embodiment
Technical scheme is further illustrated below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
A kind of anthraquinone system for preparing hydrogen peroxide, the system includes that a cross_flow rotating packed bed 4, gas is defeated
Send device, liquid transporting apparatus, the first preheating furnace 2, the second preheating furnace 5, condenser 6, product storage tank and feed tube;
Cross_flow rotating packed bed 4 includes housing, reactor and rotary apparatuss, and reactor is located in housing, reactor
Hydrogenation catalyst being filled with wall, and the wall of the reactor arranging through hole, reactor is connected with housing by the through hole;
Rotary apparatuss are connected with reactor, for driving reactor to rotate;
The through hole for circle and has multiple;Metal gauze is provided with the through hole;Between adjacent through-holes at intervals of
1mm;The reactor is hollow cylinder;The wall thickness of the cylinder is 21mm;The radius of the cylinder is 73mm;Institute
The hollow cylinder that is shaped as of housing is stated, the radius of the housing is 100mm;
The reactor head of cross_flow rotating packed bed 4 arranges liquid-inlet, and housing bottom arranges liquid outlet;Hypergravity
The top of rotary packed bed 4 housing and reactor is respectively provided with gas feed;The gas outlet can be incorporated in liquid outlet
Together or it is arranged on housing or reactor;
Air transporting arrangement includes hydrogen-holder and nitrogen storage tank, hydrogen-holder and nitrogen storage tank respectively by valve and gas
One end of body transfer pipeline is connected, and the other end of gas transfer pipeline is connected with each gas feed by valve, the first preheating
Stove 2 is arranged on gas transfer pipeline;
The liquid transporting apparatus include work liquid storage tank 12 and pump, and the work liquid storage tank 12 passes through liquid transmission pipeline
Connect with the liquid-inlet for arranging on reactor, pump and the second preheating furnace 5 are set on the liquid transmission pipeline;
The feed tube one end open, the other end is closed, and the opening of feed tube is connected with work liquid storage tank by pump, is entered
The blind end of liquid pipe stretches into reactor central authorities, and arranges slit on the wall of the feed tube for stretching into reactor, for spraying working solution
To on the inwall of reactor;
The import of the condenser 6 is connected with gas outlet;The liquid outlet of the product storage tank and condenser 6 and housing
Liquid outlet is connected.
The method for hydrogen peroxide being prepared using system as above comprises the steps:
(1) catalyst is packed in the wall of cross_flow rotating packed bed reactor, cross_flow rotating packed bed is heated
To 50-80 DEG C, after being passed through hydrogen reducing activation 1-24h, drained with nitrogen;Cross_flow rotating packed bed is made with 0-3000r/min
Speed rotation;
(2) working solution by temperature for 55-75 DEG C is sprinkled upon on the reactor wall of rotation by feed tube ejection, and temperature is
55-75 DEG C of hydrogen axle phase or radially flow through catalyst in reactor wall, on the reactor wall both following currents, cross-flow or
Counter current contacting is reacted;Wherein, hydrogen flowing quantity is 1-100L/min, and working solution flow is 1-100L/min;Hydrogen and working solution
Volume ratio is 10:1-15:1;Working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and heavy aromatics and phosphoric acid
The volume ratio of three monooctyl esters is 75:25-80:20;The concentration of heavy aromatics is 660-680mL/L;The concentration of trioctyl phosphate is 210-
230mL/L;The concentration of 2-ethyl-anthraquinone is 110-130g/L;Reaction temperature is 20-100 DEG C;Adults power in course of reaction
Pressure in rotary packed bed is 0.1-10MPa;The liquid-phase reaction product for obtaining and gas phase reaction product, and via through holes outflow;
(3) liquid-phase reaction product is collected, which is aoxidized, extraction, obtain hydrogen peroxide product;Condensation gas phase reaction product
Thing, obtains gas and liquid phase, and gas is emptied, and liquid phase is mixed with liquid-phase reaction product.
Embodiment 2
A kind of for the anthraquinone blood circulation for preparing hydrogen peroxide, as shown in Figure 1.The system except product storage tank also with
Outside work liquid storage tank 12 is connected, remaining is identical with the system described in embodiment 1.
The method for hydrogen peroxide being prepared using system as above comprises the steps:
(1) catalyst is packed in the wall of cross_flow rotating packed bed reactor, cross_flow rotating packed bed is heated
To 50-80 DEG C, after being passed through hydrogen reducing activation 1-24h, drained with nitrogen;Cross_flow rotating packed bed is made with 0-3000r/min
Speed rotation;
(2) working solution by temperature for 55-75 DEG C is sprinkled upon on the reactor wall of rotation by feed tube ejection, and temperature is
55-75 DEG C of hydrogen axle phase or radially flow through catalyst in reactor wall, on the reactor wall both following currents, cross-flow or
Counter current contacting is reacted;Wherein, hydrogen flowing quantity is 1-100L/min, and working solution flow is 1-100L/min;Hydrogen and working solution
Volume ratio is 10:1-15:1;Working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and heavy aromatics and phosphoric acid
The volume ratio of three monooctyl esters is 75:25-80:20;The concentration of heavy aromatics is 660-680mL/L;The concentration of trioctyl phosphate is 210-
230mL/L;The concentration of 2-ethyl-anthraquinone is 110-130g/L;Reaction temperature is 20-100 DEG C;Adults power in course of reaction
Pressure in rotary packed bed is 0.1-10MPa;The liquid-phase reaction product for obtaining and gas phase reaction product, and via through holes outflow;
(3) liquid-phase reaction product is mixed with working solution, proceeds step (1) and step (2), will be anti-for final liquid phase
Product is answered to aoxidize, extraction, obtain hydrogen peroxide product;Condensation gas phase reaction product, obtains gas and liquid phase, and gas is emptied, liquid
Mix with liquid-phase reaction product.
The cross_flow rotating packed bed also only can arrange a gas feed and a gas outlet, as Fig. 2 and Fig. 3 institute
Show.Fig. 2 be process for prepairng hydrogen peroxide by anthraquinone technique in, for the cross_flow rotating packed bed of the adverse current of anthraquinone hydrogenation catalytic reaction
Structural representation, wherein, gas feed 23 is arranged on housing 24, and gas outlet 22 is arranged on reactor 25;Fig. 3 is anthracene
In quinone method production hydrogen peroxide process, for the structural representation of the cross_flow rotating packed bed of the cocurrent of anthraquinone hydrogenation catalytic reaction
Figure, wherein, gas feed 32 is arranged on reactor 34, and gas outlet shares a mouth gas liquid outlet with liquid outlet
37, which is arranged on housing 33.
Embodiment 3
A kind of for the anthraquinone reaction of high order system for preparing hydrogen peroxide, the system includes three hypergravity rotary fillings
Material bed 4 (the first cross_flow rotating packed bed, the second cross_flow rotating packed bed and the 3rd cross_flow rotating packed bed), gas are defeated
Send device, liquid transporting apparatus, the first preheating furnace 2, the second preheating furnace 5, condenser 6, product storage tank and feed tube;
Each cross_flow rotating packed bed 4 includes housing, reactor and rotary apparatuss, and reactor is located in housing, reaction
Hydrogenation catalyst being filled with the wall of device, and the wall of the reactor arranging through hole, reactor is by the through hole and housing
Connection;Rotary apparatuss are connected with reactor, for driving reactor to rotate;
The through hole for circle and has multiple;Metal gauze is provided with the through hole;Between adjacent through-holes at intervals of
1mm;The reactor is hollow cylinder;The wall thickness of the cylinder is 21mm;The radius of the cylinder is 73mm;Institute
The hollow cylinder that is shaped as of housing is stated, the radius of the housing is 100mm;
The reactor head of each cross_flow rotating packed bed 4 arranges liquid-inlet, and housing bottom arranges liquid outlet;Per
The top of 4 housing of individual cross_flow rotating packed bed and reactor is respectively provided with gas feed;The gas outlet can be with liquid discharge
Mouth is combined or is arranged on housing or reactor;
The liquid outlet of cross_flow rotating packed bed is connected with the liquid-inlet of cross_flow rotating packed bed;Hypergravity rotates
The liquid outlet of packed bed is connected with the liquid-inlet of the 3rd liquid filler bed;
Air transporting arrangement includes hydrogen-holder and nitrogen storage tank, hydrogen-holder and nitrogen storage tank respectively by valve and gas
One end of body transfer pipeline is connected, the other end of gas transfer pipeline with by valve and each cross_flow rotating packed bed 4
Gas feed is connected, and the first preheating furnace 2 is arranged on gas transfer pipeline;
The liquid transporting apparatus include work liquid storage tank 12 and pump, and the work liquid storage tank 12 passes through liquid transmission pipeline
Connect with the liquid-inlet for arranging on cross_flow rotating packed bed reactor, setting pump and second pre- on the liquid transmission pipeline
Hot stove 5;
The feed tube has three, feed tube one end open, and the other end is closed, and the opening of feed tube is by pump and work
Liquid storage tank is connected, and the blind end of feed tube is respectively protruding into reactor central authorities, and arranges on the wall of the feed tube for stretching into reactor narrow
Seam, for working solution to be sprayed onto the inwall of reactor;
The import of the condenser 6 is connected with the liquid outlet of each cross_flow rotating packed bed 4;The product storage tank with
The liquid outlet of condenser 6 is connected with the liquid outlet of cross_flow rotating packed bed housing.
The method for hydrogen peroxide being prepared using system as above comprises the steps:
(1) in the wall of three cross_flow rotating packed bed reactors, catalyst is packed into, by three hypergravity rotary fillings
Material bed is heated to 50-80 DEG C, after being passed through hydrogen reducing activation 1-24h, is drained with nitrogen;Make three cross_flow rotating packed bed with
The speed rotation of 0-3000r/min;
(2) working solution by temperature for 55-75 DEG C is sprinkled upon the rotation of the first cross_flow rotating packed bed by feed tube ejection
On reactor wall, temperature for 55-75 DEG C of hydrogen axle phase or radially flows through catalyst in reactor wall, in reactor
Both following currents, cross-flow or counter current contacting reaction on wall;Wherein, hydrogen flowing quantity is 1-100L/min, and working solution flow is 1-100L/
min;Hydrogen is 10 with the volume ratio of working solution:1-15:1;Working solution is by heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone group
Become, and heavy aromatics is 75 with the volume ratio of trioctyl phosphate:25-80:20;The concentration of heavy aromatics is 660-680mL/L;Phosphoric acid
The concentration of three monooctyl esters is 210-230mL/L;The concentration of 2-ethyl-anthraquinone is 110-130g/L;Reaction temperature is 20-100 DEG C;Instead
Pressure during adults power is rotary packed bed during answering is 0.1-0.56MPa;The first liquid-phase reaction product for obtaining and
One gas phase reaction product, and via through holes outflow;
(3) the first liquid-phase reaction product is sprayed the reactor for being sprinkled upon the rotation of the second cross_flow rotating packed bed by feed tube
On inwall, temperature for 55-75 DEG C of hydrogen axle phase or radially flows through catalyst in reactor wall, and on the reactor wall two
Person's following current, cross-flow or counter current contacting reaction;Wherein, hydrogen flowing quantity is 1-100L/min, and working solution flow is 1-100L/min;Hydrogen
Gas is 10 with the volume ratio of working solution:1-15:1;Working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and
Heavy aromatics is 75 with the volume ratio of trioctyl phosphate:25-80:20;The concentration of heavy aromatics is 660-680mL/L;Trioctyl phosphate
Concentration be 210-230mL/L;The concentration of 2-ethyl-anthraquinone is 110-130g/L;Reaction temperature is 20-100 DEG C;Course of reaction
Pressure in the second cross_flow rotating packed bed of middle control is 0.1-10MPa;The second liquid phase product for obtaining and the second gas
Phase reaction product, and via through holes outflow;
(4) second liquid phase product is sprayed the reactor for being sprinkled upon the rotation of the 3rd cross_flow rotating packed bed by feed tube
On inwall, temperature for 55-75 DEG C of hydrogen axle phase or radially flows through catalyst in reactor wall, and on the reactor wall two
Person's following current, cross-flow or counter current contacting reaction;Wherein, hydrogen flowing quantity is 1-100L/min, and working solution flow is 1-100L/min;Hydrogen
Gas is 10 with the volume ratio of working solution:1-15:1;Working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and
Heavy aromatics is 75 with the volume ratio of trioctyl phosphate:25-80:20;The concentration of heavy aromatics is 660-680mL/L;Trioctyl phosphate
Concentration be 210-230mL/L;The concentration of 2-ethyl-anthraquinone is 110-130g/L;Reaction temperature is 20-100 DEG C;Course of reaction
Pressure in the 3rd cross_flow rotating packed bed of middle control is 0.1-0.56MPa;The 3rd liquid-phase reaction product for obtaining and the 3rd
Gas phase reaction product, and via through holes outflow;
(7) the 3rd liquid-phase reaction product is aoxidized, extraction, after purification, obtains hydrogen peroxide product.
Embodiment 4
Catalytic hydrogenation reaction is carried out using the system described in embodiment 1, methods described comprises the steps:
(1) 50mL Raschig ring Pd/Al is packed in the packing cavity of 4 reactor of cross_flow rotating packed bed2O3Catalyst
(Φ 5 × 3 × 2mm, Φ refer to diameter);Cross_flow rotating packed bed 4 is heated to 80 DEG C, after being passed through hydrogen reducing activation 8h, is used
Nitrogen is drained;
(2) hydrogen that temperature is 55 DEG C and hydraulic fluid are introduced housing and the reaction of cross_flow rotating packed bed 4 respectively
In device;Wherein, working solution is entered in reactor by being arranged at the liquid-inlet at reactor head center;Hydrogen and working solution
Volume ratio is 12:1;The working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and heavy aromatics and tricresyl phosphate
The volume ratio of monooctyl ester is 78:22;The concentration of heavy aromatics is 670mL/L;The concentration of trioctyl phosphate is 220mL/L;2- ethyl anthracene
The concentration of quinone is 120g/L;Liquid air speed 12h-1, hydrogen gas space velocity 120h-1;
(3) cross_flow rotating packed bed 4 is made to rotate with the speed of 900r/min, and in adults power rotary packed bed 4
Pressure be 0.3MPa so that hydrogen and working solution are reacted in catalyst surface counter current contacting, the liquid-phase reaction product (hydrogen for obtaining
Change liquid) and gas phase reaction product, and via through holes outflow.
After the completion of hydrogenation reaction, hydride from liquid reactor outlet discharge, proceed to oxidation furnaces (oxidizing tower) continue into
Row oxidation reaction, generates anthraquinone and hydrogen peroxide.Oxidation product carries out hydrogen peroxide and anthraquinone working solution in extraction equipment
Separate, through purified treatment, obtain hydrogen peroxide product.Isolated anthraquinone working solution can then continue cycling through use.Institute
State oxidation, extraction, purification, working solution process all identical with existing technology with circulate operation, do not repeat.
The process conditions and process of control methods are identical, and difference is only and for cross_flow rotating packed bed 4 to replace with biography
The vertical reactor that unites by gravity mass transfer.
The measure of hydrogenation efficiency:
5mL hydride is taken in 500mL separatory funnel with pipet, the phosphoric acid of 20mL aromatic hydrocarbons and 10mL10% is added,
Gas dispersion tube is inserted, logical oxygen about 15 minutes.With distilled water extraction hydrogen peroxide therein, each 20mL, it is total to
Extraction 4 times, lower aqueous solution is put in conical flask, until without hydrogen peroxide in extract.20mL sulphuric acid is added
State in extract, titrated with potassium permanganate titer, until solution shows blush, 30 seconds colour-fast as terminals.
Hydrogenation efficiency (abbreviation hydrogen effect) is calculated by existing publicity:
B=17CV/5
In formula:B is hydrogenation efficiency, unit g/L;C is potassium permanganate concentration of standard solution mol/L;V consumes permanganic acid for titration
Volume mL of potassium.
It is 4.2g/L hydrogen effect to be measured using traditional vertical reactor;Using the method described in embodiment 4, in hypergravity bar
React under part, it is 6.2g/L to measure gained hydrogenation liquid hydrogen effect, and hydrogen effect increases by 45.2%.
Embodiment 5
A kind of anthraquinone method for preparing hydrogen peroxide, methods described is entered from the gas feed of reactor head except hydrogen
Outside reactor, remaining is identical with the method described in embodiment 4.
The process conditions and process of control methods are identical, and difference is only and for cross_flow rotating packed bed 4 to replace with biography
The vertical reactor that unites by gravity mass transfer.
In methods described, hydrogen is contacted in catalyst surface with working solution cocurrent and is reacted, using same as Example 4
It is 5.5g/L, slightly below embodiment 1 that hydrogen effect assay method measures hydrogen effect.
Embodiment 6
A kind of anthraquinone method for preparing hydrogen peroxide, except the catalyst for using is Pd/Al2O3(Φ refers to directly 2 × 5mm of Φ
Footpath) bar, the temperature that hydrogen is reacted with working solution is for, outside 60 DEG C, remaining is identical with the method described in embodiment 4.
The process conditions and process of control methods are identical, and difference is only and for cross_flow rotating packed bed 4 to replace with biography
The vertical reactor that unites by gravity mass transfer.
Measured using hydrogen effect assay method same as Example 4:Traditional vertical reactor hydrogen effect is 3.4g/L;Utilize
Method described in embodiment 6, hydrogen effect is 4.7g/L, and compared with traditional vertical reactor, hydrogen effect increases by 38.2%.
Embodiment 7
A kind of anthraquinone method for preparing hydrogen peroxide, except the catalyst for using is spherical Pd/SiO2, (Φ refers to directly Φ 2mm
Footpath), the temperature that hydrogen is reacted with working solution is outer for 55 DEG C, and remaining is identical with the method described in embodiment 4.
The process conditions and process of control methods are identical, and difference is only and for cross_flow rotating packed bed 4 to replace with biography
The vertical reactor that unites by gravity mass transfer.
Measured using hydrogen effect assay method same as Example 4:Traditional vertical reactor hydrogen effect is 3.5g/L;Utilize
Method described in embodiment 7, hydrogen effect is 4.4g/L, and compared with traditional vertical reactor, hydrogen effect increases by 25.7%.
Embodiment 8
A kind of anthraquinone method for preparing hydrogen peroxide, methods described comprises the steps:
(1) catalyst is packed in the wall of cross_flow rotating packed bed reactor, cross_flow rotating packed bed is heated
To 50 DEG C, after being passed through hydrogen reducing activation 24h, drained with nitrogen;Cross_flow rotating packed bed is made to revolve with the speed of 3000r/min
Turn;
(2) working solution that temperature is 55 DEG C is sprayed by feed tube and is sprinkled upon on the reactor wall of rotation, temperature is 75 DEG C
Hydrogen axle mutually flow through catalyst in reactor wall, both following currents, cross-flow or counter current contacting reaction on the reactor wall;
Wherein, hydrogen flowing quantity is 100L/min, and working solution flow is 1L/min;Working solution is by heavy aromatics, trioctyl phosphate and 2- ethyl
Anthraquinone constitutes, and heavy aromatics is 77 with the volume ratio of trioctyl phosphate:23;The concentration of heavy aromatics is 675mL/L;Tricresyl phosphate is pungent
The concentration of ester is 225mL/L;The concentration of 2-ethyl-anthraquinone is 115g/L;Reaction temperature is 20 DEG C;Adults in course of reaction
Pressure during power is rotary packed bed is 0.1MPa;The liquid-phase reaction product for obtaining and gas phase reaction product, and via through holes outflow;
(3) liquid-phase reaction product is collected, which is aoxidized, extraction, obtain hydrogen peroxide product;Condensation gas phase reaction product
Thing, obtains gas and liquid phase, and gas is emptied, and liquid phase is mixed with liquid-phase reaction product.
The process conditions and process of control methods are identical, and difference is only and for cross_flow rotating packed bed 4 to replace with biography
The vertical reactor that unites by gravity mass transfer.
Measured using hydrogen effect assay method same as Example 4:Traditional vertical reactor hydrogen effect is 6g/L;Using reality
The method described in example 8 is applied, hydrogen effect is 8g/L, compared with traditional vertical reactor, hydrogen effect increases by 25%.
Embodiment 9
A kind of anthraquinone method for preparing hydrogen peroxide, methods described comprises the steps:
(1) catalyst is packed in the wall of cross_flow rotating packed bed reactor, cross_flow rotating packed bed is heated
To 80 DEG C, after being passed through hydrogen reducing activation 1h, drained with nitrogen;Cross_flow rotating packed bed is made to revolve with the speed of 1000r/min
Turn;
(2) working solution that temperature is 75 DEG C is sprayed by feed tube and is sprinkled upon on the reactor wall of rotation, temperature is 55 DEG C
Hydrogen radially flow through catalyst in reactor wall, both following current, cross-flow haptoreactions on the reactor wall;Wherein,
Hydrogen flowing quantity is 100L/min, and working solution flow is 1L/min;Working solution is by heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone group
Become, and heavy aromatics is 80 with the volume ratio of trioctyl phosphate:20;The concentration of heavy aromatics is 660mL/L;Trioctyl phosphate dense
Spend for 230mL/L;The concentration of 2-ethyl-anthraquinone is 110g/L;Reaction temperature is 100 DEG C;Adults power rotation in course of reaction
Pressure in packed bed is 10MPa;The liquid-phase reaction product for obtaining and gas phase reaction product, and via through holes outflow;
(3) liquid-phase reaction product is collected, which is aoxidized, extraction, obtain hydrogen peroxide product;Condensation gas phase reaction product
Thing, obtains gas and liquid phase, and gas is emptied, and liquid phase is mixed with liquid-phase reaction product.
The process conditions and process of control methods are identical, and difference is only and for cross_flow rotating packed bed 4 to replace with biography
The vertical reactor that unites by gravity mass transfer.
Measured using hydrogen effect assay method same as Example 4:Traditional vertical reactor hydrogen effect is 5g/L;Using reality
The method described in example 9 is applied, hydrogen effect is 9g/L, compared with traditional vertical reactor, hydrogen effect increases by 80%.
Embodiment 10
A kind of anthraquinone method for preparing hydrogen peroxide, methods described comprises the steps:
(1) catalyst is packed in the wall of cross_flow rotating packed bed reactor, cross_flow rotating packed bed is heated
To 60 DEG C, after being passed through hydrogen reducing activation 12h, drained with nitrogen;Cross_flow rotating packed bed is made to rotate with the speed of 5r/min;
(2) working solution that temperature is 60 DEG C is sprayed by feed tube and is sprinkled upon on the reactor wall of rotation, temperature is 60 DEG C
Hydrogen axle mutually flow through catalyst in reactor wall, both counter current contacting reactions on the reactor wall;Wherein, hydrogen stream
Measure as 50L/min, working solution flow be;Working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and
And heavy aromatics is 75 with the volume ratio of trioctyl phosphate:25;The concentration of heavy aromatics is 680mL/L;The concentration of trioctyl phosphate is
210mL/L;The concentration of 2-ethyl-anthraquinone is 130g/L;Reaction temperature is 70 DEG C;Adults power rotation filler in course of reaction
Pressure in bed is 5MPa;The liquid-phase reaction product for obtaining and gas phase reaction product, and via through holes outflow;
(3) liquid-phase reaction product is collected, which is aoxidized, extraction, obtain hydrogen peroxide product;Condensation gas phase reaction product
Thing, obtains gas and liquid phase, and gas is emptied, and liquid phase is mixed with liquid-phase reaction product.
The process conditions and process of control methods are identical, and difference is only and for cross_flow rotating packed bed 4 to replace with biography
The vertical reactor that unites by gravity mass transfer.
Measured using hydrogen effect assay method same as Example 4:Traditional vertical reactor hydrogen effect is 6g/L;Using reality
The method described in example 10 is applied, hydrogen effect is 8g/L, compared with traditional vertical reactor, hydrogen effect increases by 33%.
Embodiment 11
Hydrogen peroxide is prepared in the blood circulation described in embodiment 2, process conditions technique bar as described in Example 4
Part, the hydrogenation efficiency of different circulation time hydrides is with space-time yield as shown in figure 4, it can be seen that hypergravity rotation
Packed bed is not in the case of operation is circulated, and with very high space-time yield, but hydrogenation efficiency (hydrogen effect) is relatively low, and we pass through
Increase circulation time, although hydrogen effect can be improved, but space-time yield can find to be decreased obviously.In addition, supergravity reactor
Space-time yield (27.9g (H2O2)/L (cat.) h) it is far above fixed bed reactors space-time yield (12.7-16.5g (H2O2)/L
(cat.) h), wherein, cat. refers to catalyst.Therefore, the cross_flow rotating packed bed of the not circulate operation of continuous series is not only
The space-time yield in technique productions can be improved and also ensured that and obtain rational hydrogen effect.
Applicant states, the foregoing is only the specific embodiment of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and take off in the present invention
In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and open within the scope of.
Claims (10)
1. a kind of for the anthraquinone system for preparing hydrogen peroxide, it is characterised in that the system includes hypergravity rotation filler
Bed, air transporting arrangement, liquid transporting apparatus, the first preheating device and the second preheating device;
Cross_flow rotating packed bed includes housing, reactor and rotary apparatuss, and reactor is located in housing, is filled in the wall of reactor
Catalyst is filled with, and the wall of the reactor arranges through hole, reactor is connected with housing by the through hole;Rotary apparatuss with
Reactor is connected, for driving reactor to rotate;
Air transporting arrangement is connected with the gas feed for arranging on reactor and/or housing by gas transfer pipeline, and gas
First preheating device is set on body transfer pipeline;
Liquid transporting apparatus are connected with the liquid-inlet for arranging on reactor by liquid transmission pipeline, and liquid transmission pipeline
The second preheating device of upper setting;
Gas outlet and liquid outlet are set on the housing.
2. system according to claim 1, it is characterised in that described high-gravity rotating bed for horizontal or vertical, preferably
Horizontal;
Preferably, network structure is set in the through hole;
Preferably, the cancellated material is selected from any one in metal, silica gel or macromolecular material or at least two
Combination, preferably reinforcing bar;
Preferably, the through hole have multiple, between adjacent through-holes at intervals of 1mm-100cm;
Preferably, the through hole is circle;
Preferably, the reactor is hollow cylinder, arranges through hole on the wall of the cylinder;
Preferably, the wall thickness of the cylinder is 5-50mm;
Preferably, the radius of the cylinder is 5-50mm;
Preferably, the housing be shaped as hollow cylinder, the radius of the housing is 50-500mm.
3. system according to claim 1 and 2, it is characterised in that the liquid transporting apparatus include work liquid storage tank and
Pump, the work liquid storage tank is connected with liquid-inlet by pump;
Preferably, the air transporting arrangement includes hydrogen-holder and nitrogen storage tank, hydrogen-holder and nitrogen storage tank all by
One preheating device is connected with gas feed;
Preferably, the system also includes condensing units and product storage tank, and the import of the condensing units is connected with liquid outlet;
The product storage tank is connected with the liquid outlet of condensing units and the liquid outlet of housing;
Preferably, the system also includes spray equipment, and the spray equipment is connected with liquid transporting apparatus, the spray equipment
For working solution to be sprayed onto the wall of reactor;
Preferably, the spray equipment includes feed tube, the feed tube one end open, and the other end is closed, the opening of feed tube
End is connected with liquid transporting apparatus, and the blind end of feed tube is stretched in reactor, and is set on the wall of the feed tube for stretching into reactor
Put through hole.
4. the system according to one of claim 1-3, it is characterised in that the system arranges two gas feeds and matching
The sealing piston of conjunction, described two gas feeds one are located on housing, and another is located on reactor.
5. the system according to one of claim 1-4, it is characterised in that the system includes the overweight of at least two series connection
Power is rotary packed bed, the liquid-inlet phase of the liquid outlet of previous cross_flow rotating packed bed and a rear cross_flow rotating packed bed
Even;Air transporting arrangement is connected with the air inlet at least two cross_flow rotating packed bed respectively, and preferably the system includes
The cross_flow rotating packed bed of 1-100 series connection.
6. a kind of anthraquinone method for preparing hydrogen peroxide, it is characterised in that methods described usage right requires that one of 1-5 is described
System carry out the hydrogenation reaction of anthraquinone.
7. method according to claim 6, it is characterised in that methods described comprises the steps:
(1) hydrogenation catalyst being loaded in the wall of cross_flow rotating packed bed reactor, makes cross_flow rotating packed bed with 0-
The speed rotation of 3000r/min;
(2) hydrogen after preheating and hydraulic fluid are all introduced in the reactor, or, hydrogen and working solution are introduced respectively super
In gravity rotary packed bed housing and reactor;Pressure during adults power is rotary packed bed is 0.1-10MPa so that hydrogen
Gas is reacted in catalyst surface cocurrent, cross-flow or counter current contacting with working solution, and the liquid-phase reaction product for obtaining and gas phase reaction are produced
Thing, and via through holes outflow, liquid-phase reaction product is post-treated, obtains hydrogen peroxide product.
8. method according to claim 7, it is characterised in that the loadings of step (1) catalyst control in 20-
200mL;
Preferably, step (1) catalyst be load type palladium catalyst, the carrier in the load type palladium catalyst be with
In the aspheric pelleted substrate of hollow-core construction, preferably Raschig ring, Wheel ring packing, porous bar or porous ring any one or
At least two combination, more preferably Raschig ring;
Preferably, in the load type palladium catalyst, the load capacity of palladium is 0.01-1wt%;
Preferably, step (1) catalyst is alumina composite Pd black catalyst, in the alumina composite Pd black catalyst
The weight/mass percentage composition of palladium black is preferably 0.1%-5%;
Preferably, the alumina composite Pd black catalyst is the spherical of 1-100mm diameter, and draw ratio is 1:1-1:10th, diameter
For the Raschig ring type of 1-100mm, or the trifolium-shaped of same size.
9. the method according to claim 7 or 8, it is characterised in that the incorporation way of step (2) working solution and hydrogen
For:Working solution is sprayed by feed tube and is sprinkled upon on the reactor wall of rotation, hydrogen axle phase or is radially flowed through in reactor wall
Catalyst, both following currents, cross-flow or counter current contacting on the reactor wall;
Preferably, the hydrogen flowing quantity is 1-100L/min, and working solution flow is 1-100L/min;
Preferably, in step (2) cross_flow rotating packed bed, hydrogen is 10 with the volume ratio of working solution:1-15:1;
Preferably, step (2) working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and heavy aromatics and phosphorus
The volume ratio of sour three monooctyl esters is 75:25-80:20;The concentration of heavy aromatics is 660-680mL/L;The concentration of trioctyl phosphate is
210-230mL/L;The concentration of 2-ethyl-anthraquinone is 110-130g/L;
Preferably, after step (2) preheating hydrogen and the temperature of working solution are 55-75 DEG C;
Preferably, step (2) reaction is carried out under the conditions of 20-100 DEG C;
Preferably, step (2) also carries out reduction activation process to catalyst before introducing hydrogen and working solution, specially:Will be super
Gravity is rotary packed bed to be heated to 50-80 DEG C, after being passed through hydrogen reducing activation 1-24h, is drained with nitrogen;
Preferably, step (2) post processing includes:Liquid-phase reaction product is aoxidized, extraction, purification, obtain peroxidating
Hydrogen production;Condensation gas phase reaction product, obtains gas phase and liquid phase, and liquid phase is mixed with liquid-phase reaction product, and gas is emptied;
Preferably, the liquid-phase reaction product return to step (1) that step (2) is obtained is mixed with working solution, or, what step (2) was obtained
Working solution of the liquid-phase reaction product as next cross_flow rotating packed bed.
10. the method according to one of claim 6-9, it is characterised in that methods described comprises the steps:
(1) catalyst is packed in the wall of cross_flow rotating packed bed reactor, cross_flow rotating packed bed is heated to 50-
80 DEG C, after being passed through hydrogen reducing activation 1-24h, drained with nitrogen;Cross_flow rotating packed bed is made with the speed of 0-3000r/min
Rotation;
(2) working solution by temperature for 55-75 DEG C is sprinkled upon on the reactor wall of rotation by feed tube ejection, and temperature is 55-75
DEG C hydrogen axle phase or radially flow through catalyst in reactor wall, both following currents, cross-flow or adverse current on the reactor wall
Haptoreaction;Wherein, hydrogen flowing quantity is 1-100L/min, and working solution flow is 1-100L/min;The volume of hydrogen and working solution
Than for 10:1-15:1;Working solution is made up of heavy aromatics, trioctyl phosphate and 2-ethyl-anthraquinone, and heavy aromatics is pungent with tricresyl phosphate
The volume ratio of ester is 75:25-80:20;The concentration of heavy aromatics is 660-680mL/L;The concentration of trioctyl phosphate is 210-
230mL/L;The concentration of 2-ethyl-anthraquinone is 110-130g/L;Reaction temperature is 20-100 DEG C;Adults power in course of reaction
Pressure in rotary packed bed is 0.1-10MPa;The liquid-phase reaction product for obtaining and gas phase reaction product, and via through holes outflow;
(3) liquid-phase reaction product is collected, which is aoxidized, extraction, obtain hydrogen peroxide product;Condensation gas phase reaction product,
Gas and liquid phase is obtained, gas is emptied, liquid phase is mixed with liquid-phase reaction product.
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106841507A (en) * | 2017-03-27 | 2017-06-13 | 中触媒新材料股份有限公司 | The evaluating apparatus and evaluation method of a kind of anthraquinone producing hydrogen peroxide hydrogenation catalyst |
CN107473188A (en) * | 2017-09-25 | 2017-12-15 | 北京化工大学 | It is a kind of to use the anthraquinone production technology for preparing hydrogen peroxide |
CN108854931A (en) * | 2018-07-06 | 2018-11-23 | 中北大学 | A kind of device and method preparing metallic catalyst |
CN109569251A (en) * | 2019-01-17 | 2019-04-05 | 北京化工大学 | A kind of utilize contains SO2The device and method of flue gas dilute sulfuric acid |
CN110441465A (en) * | 2019-07-22 | 2019-11-12 | 鲁西催化剂有限公司 | A kind of anthraquinone hydrogenation catalyst selective evaluation device and evaluation method |
CN112337139A (en) * | 2019-08-09 | 2021-02-09 | 北京化工大学 | In-situ heat-supplementing supergravity devolatilization device and application |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102218291A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Chemical reaction method |
US20120027667A1 (en) * | 2009-03-27 | 2012-02-02 | Solvay Sa | Method for the production of hydrogen peroxide |
CN102764627A (en) * | 2012-08-11 | 2012-11-07 | 侯晓峰 | Rotating packed bed reaction device |
CN103145103A (en) * | 2013-03-21 | 2013-06-12 | 天津大学 | Novel circulation flow extraction section device for preparing oxydol through anthraquinone method |
CN104368301A (en) * | 2013-08-14 | 2015-02-25 | 中国石油化工股份有限公司 | Hyper-gravity reactor and reaction method |
-
2016
- 2016-10-10 CN CN201610883802.0A patent/CN106430108B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120027667A1 (en) * | 2009-03-27 | 2012-02-02 | Solvay Sa | Method for the production of hydrogen peroxide |
CN102218291A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Chemical reaction method |
CN102764627A (en) * | 2012-08-11 | 2012-11-07 | 侯晓峰 | Rotating packed bed reaction device |
CN103145103A (en) * | 2013-03-21 | 2013-06-12 | 天津大学 | Novel circulation flow extraction section device for preparing oxydol through anthraquinone method |
CN104368301A (en) * | 2013-08-14 | 2015-02-25 | 中国石油化工股份有限公司 | Hyper-gravity reactor and reaction method |
Non-Patent Citations (1)
Title |
---|
吕昀祖 等: "超重力技术在蒽醌法制双氧水生产上的应用", 《中国化学会第30届学术年会摘要集-第十一分会:应用化学》 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN107473188A (en) * | 2017-09-25 | 2017-12-15 | 北京化工大学 | It is a kind of to use the anthraquinone production technology for preparing hydrogen peroxide |
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CN108854931B (en) * | 2018-07-06 | 2024-02-09 | 中北大学 | Device and method for preparing metal catalyst |
CN109569251A (en) * | 2019-01-17 | 2019-04-05 | 北京化工大学 | A kind of utilize contains SO2The device and method of flue gas dilute sulfuric acid |
CN110441465A (en) * | 2019-07-22 | 2019-11-12 | 鲁西催化剂有限公司 | A kind of anthraquinone hydrogenation catalyst selective evaluation device and evaluation method |
CN112337139A (en) * | 2019-08-09 | 2021-02-09 | 北京化工大学 | In-situ heat-supplementing supergravity devolatilization device and application |
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