CN107032305A - The production system and production method of a kind of hydrogen peroxide - Google Patents

The production system and production method of a kind of hydrogen peroxide Download PDF

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Publication number
CN107032305A
CN107032305A CN201710451995.7A CN201710451995A CN107032305A CN 107032305 A CN107032305 A CN 107032305A CN 201710451995 A CN201710451995 A CN 201710451995A CN 107032305 A CN107032305 A CN 107032305A
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hydrogen
catalyst
outlet
hydrogenation
working solution
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CN107032305B (en
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张建纲
周新良
景辽宁
华柯松
孙国维
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Yangzhou Huitong Chemical Polytron Technologies Inc
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Yangzhou Huitong Chemical Polytron Technologies Inc
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The present invention relates to a kind of production system of hydrogen peroxide and production method, the bottom of working liquid tank is by working liquid pump and working solution supply pipe is connected with the entrance of hydrogenation apparatus, the outlet of hydrogenation apparatus is connected by net hydride outlet pipe with hydrogenation flow container, the bottom for hydrogenating flow container is connected by hydrogenating liquid pump, hydrogenation flow container efferent duct, hydrogenation liquid filter and hydride cooler with the entrance of oxidizing tower, and the outlet of oxidizing tower is connected with oxidation solution efferent duct；The hydride entrance of oxidizing tower upper portion side wall is located above liquid level line, and the bottom of oxidizing tower is provided with air distribution device, and the oxidation tower tray of multiple tracks horizontal circle plate-like is uniformly provided with along the short transverse of oxidizing tower；Uniformly it is densely covered with each oxidation tower tray on multiple air-vents, each layer oxidation tower tray and is respectively equipped with descending liquid mouthful and downspout；The descending liquid mouthful of odd-level is located on the axis of oxidizing tower, and the descending liquid mouth of even level is symmetrical arranged and close to the inwall of oxidizing tower.The hydrogenation of the system, oxidation efficiency are high, invest and take up an area small.

Description

The production system and production method of a kind of hydrogen peroxide
Technical field
The present invention relates to a kind of production system of hydrogen peroxide, the invention further relates to a kind of production of fluid bed hydrogen peroxide Method, belongs to hydrogen peroxide manufacturing equipment technical field.
Background technology
Hydrogen peroxide is a kind of important Inorganic Chemicals, be widely used in papermaking, weaving, medicine, chemical industry, electronics, The fields such as environmental protection.Hydrogen peroxide produces water and oxygen after decomposing, and does not have secondary pollution to environment, meets the reason of green product production Read.
In the prior art, hydrogen peroxide is generally produced by anthraquinone, anthraquinone is the palladium using 2- EAQs as carrier For catalyst, hydrogen peroxide is directly combined to by hydrogen and oxygen, successively will be through processes such as over hydrogenation, oxidation, extraction and post processings. Wherein hydrogenation is general is carried out in fixed bed, anthraquinone working solution in the presence of certain pressure, temperature and palladium catalyst, with Hydrogenation occurs for hydrogen, produces hydrogen anthraquinone.The anthraquinone low production efficiency of fixed bed, unit scale are less than normal, product production Raw material and power unit consumption are high, equipment is heavy, floor space is big, and manufacturing cost is high.
Hydrogen anthraquinone liquid is commonly called as hydride, after filtering and cooling, is admitted to oxidizing tower oxidation.Traditional oxidizing tower is sky Chamber tower body, hydride and air enter in oxidizing tower from bottom simultaneously, stir while up, air bubble is than larger, hydrogen The contact area for changing liquid and air is small, and oxidation efficiency will generally set and be saved in oxidation in section tower, oxidation under tower and oxidation than relatively low Save tower to carry out after repeatedly aoxidizing, extraction process could be entered.Equipment investment is big, and oxidation efficiency is low.
The content of the invention
The primary and foremost purpose of the present invention is that overcoming problems of the prior art, there is provided a kind of production of hydrogen peroxide System, simple and compact device, manufacturing cost is low, and oxidation efficiency is high, and thoroughly, floor space is small, and unit consumption of product is low for oxidation reaction.
To solve above technical problem, a kind of production system of hydrogen peroxide of the invention, including working liquid tank, hydrogenation are anti- Device, hydrogenation flow container and oxidizing tower are answered, the bottom of the working liquid tank is connected with the entrance for the liquid pump that works, the work liquid pump Outlet is connected by working solution supply pipe with the entrance of the hydrogenation apparatus, and the outlet of the hydrogenation apparatus passes through net Hydride outlet pipe is connected with the hydrogenation flow container, and the bottom of the hydrogenation flow container is connected with hydrogenating the entrance of liquid pump, the hydrogen Change liquid pump outlet by hydrogenate flow container efferent duct, hydrogenation liquid filter and hydride cooler and the oxidizing tower entrance phase Even, the outlet of the oxidizing tower is connected with oxidation solution efferent duct, and the top center of the oxidizing tower is provided with oxidizing tower gaseous phase outlet, The upper portion side wall of the oxidizing tower is connected with oxidizing tower hydride entrance, and the oxidizing tower hydride entrance is located at the liquid of oxidizing tower Above bit line, the bottom of the oxidizing tower is provided with air distribution device, the air distribution device and the oxidizing tower on oxidizing tower Total air intake connection, the bottom centre of the oxidizing tower exports provided with oxidizing tower；It is uniformly provided with along the short transverse of oxidizing tower The oxidation tower tray of multiple tracks horizontal circle plate-like；Multiple oxidation tower tray air-vents, each layer oxygen are uniformly densely covered with each oxidation tower tray Change and descending liquid mouthful is respectively equipped with tower tray, each descending liquid mouth is connected to the downspout to next layer of oxidation tower tray extension；From Descending liquid mouthful on upper and lower odd-level oxidation tower tray is located on the axis of oxidizing tower, and the descending liquid mouthful on even level oxidation tower tray is symmetrical Set and close to the inwall of oxidizing tower.
Relative to prior art, the present invention achieves following beneficial effect：Working solution in working liquid tank is by work liquid pump Conveyed by working solution supply pipe to hydrogenation apparatus, the hydride of hydrogenation apparatus production passes through net hydride outlet pipe Kept in into hydrogenation flow container, hydrogenation flow container efferent duct is then pumped into by hydride, removal of impurities is gone in first hydrogenated liquid filter filtering The temperature of hydride is reduced to less than 40 DEG C by matter, hydride cooler, and feeding oxidizing tower is aoxidized, the oxidized liquid of oxidation solution Efferent duct is exported.In oxidizing tower, compressed air is distributed into numerous bubbles by the air distribution device of bottom, flows from bottom to top； Hydrogen anthraquinone liquid enters in oxidizing tower from the oxidizing tower hydride entrance on top, falls first on the oxidation tower tray of top layer, Ran Houcong Periphery is to center flow, after the descending liquid mouthful and downspout at center are fallen, and reaches second layer Ze Cong centers to perimeter, so Successively then advection flows downward.During air flows upwards, minute bubbles are easily mutually collided, assembled, being bonded into larger bubble, When air pocket reaches the lower section of oxidation tower tray, it is oxidized tower tray air-vent and is divided into numerous minute bubbles again, greatly increase The specific surface area of bubble, when hydride flows through oxide regions, is in contact with countless minute bubbles, and contact area is big, mixes good It is good.Air pocket is oxidized tower tray and is divided into tiny bubble again for several times in uphill process, substantially increases oxidation efficiency, only Want an oxidizing tower to be properly completed the oxidation of hydrogen anthraquinone liquid, reduce equipment investment and production cost.Hydrogen anthraquinone liquid is each One side advection on layer oxidation tower tray with the oxygen in bubble while occur oxidation reaction generation hydrogen peroxide, working solution is in air Existing counter-current flow, it is most ozone that working solution, which flows to contacted during oxidation tower bottom, to ensure that oxidation reaction is thoroughly complete Into then from the oxidizing tower outlet outflow of bottom.The descending liquid mouth of adjacent layer oxidation tower tray mutually staggers and makes working solution downward on one side Flowing forms repeatedly turns back on one side in the horizontal direction, extends the flow distance of working solution, also extends working solution and oxygen Time of contact, hydrogen anthraquinone liquid is conducive to turn into hydrogen peroxide by exhaustive oxidation.Oxidizing tower hydride entrance is located above liquid level line Oxidation solution can be prevented to choke in hydrogen anthraquinone liquid pipe road, it is to avoid pollute upper track formation.
As the improvement of the present invention, the hydrogenation apparatus includes hydrogenation reaction cauldron, the bottom of the hydrogenation reaction cauldron Provided with hydriding reactor working solution distribution pipe, the entrance of the hydriding reactor working solution distribution pipe is connected with the working solution supply pipe, institute The lower section for stating hydriding reactor working solution distribution pipe is provided with hydrogen distributor, the main entrance of the hydrogen distributor and fresh hydrogen Supply pipe is connected, and is connected with catalyst adding tube at the top of the hydrogenation reaction cauldron, the upper end of the catalyst adding tube passes through catalyst The outlet that addition valve adds tank with catalyst is connected；The top center of the hydrogenation reaction cauldron is provided with hydriding reactor gaseous phase outlet, described The outlet of at least two reactors is uniformly provided with the middle part circumference of hydrogenation reaction cauldron；The reactor outlet is connected with hydriding reactor and gone out Mouth pipe, the outlet of the hydriding reactor outlet is tangentially connected on the middle part circumference of catalyst preseparator, the catalyst The top circumference of preseparator is exported provided with catalyst preseparator, and the catalyst preseparator outlet is exported with catalyst preseparator Pipe is connected；Be connected with separator hydrogen recovery tube at the top of the catalyst preseparator, the separator hydrogen recovery tube it is upper End upwardly extends and is connected with the gas-phase space on the hydrogenation reaction cauldron top；The bottom of the catalyst preseparator for it is upper it is big under Small taper and it is connected by preseparator catalyst return duct with the lower circumference of the hydrogenation reaction cauldron；The catalyst pre-separation The outlet of device outlet is connected with the centre entrance of triple valve, and the upper outlet of the triple valve and the bottom of catalyst filter enter Mouth is connected, and the top center of the catalyst filter is provided with hydride outlet valve, the outlet of the hydride outlet valve and institute Net hydride outlet pipe is stated to be connected.When hydrogenation apparatus produces hydride, open catalyst addition valve and put into appropriate catalyst Hydrogenation reaction cauldron, while the hydrogenated kettle working solution distribution pipe of fresh working solution distributes the bottom even spray of backward hydrogenation reaction cauldron Go out, hydrogen enters hydrogen distributor from fresh hydrogen supply pipe, hydrogen distributor uniformly discharges multiple tiny hydrogen Bubble, sprays downwards, then hydrogen gas bubbles are floated up from the lower section of fresh working solution, is sufficiently mixed simultaneously with fresh working solution Stirring；Anthraquinone in working solution generates hydrogen anthraquinone, remaining unreacted hydrogen in the presence of powdered palladium catalyst with hydrogen reaction From the hydriding reactor gaseous phase outlet discharge at the top of hydrogenation reaction cauldron.Multiple reactor outlets are connected with the middle part of hydrogenation reaction cauldron, just In the recoil for carrying out catalyst in turn, it is ensured that fluid bed being capable of continuous and stable production.Hydride is together with powder catalyst from hydrogenation Reactor outlet and hydriding reactor outlet in the middle part of kettle are uniformly flowed out, tangentially into the middle part of each catalyst preseparator, hydrogenation Liquid along catalyst preseparator inwall circumference rotation, powder catalyst under the influence of centrifugal force, along the inwall of catalyst preseparator Sedimentation, from the preseparator catalyst return duct of catalyst preseparator bottom returns to hydrogenation reaction cauldron, hydrogen is from catalyst pre-separation The top of device is returned in hydrogenation reaction cauldron through separator hydrogen recovery tube.By means of the flow velocity of hydride itself, catalyst pre-separation Powder catalyst initial gross separation is come out using the method centrifuged, is significantly reduced the filtering load of catalyst filter, made by device Hydroprocessing is easier, reduces the blowback frequency of catalyst filter, saves energy consumption, increases the use time of catalyst filter, Substantially increase production efficiency.The catalyst and hydrogen that initial gross separation goes out all are reclaimed, and reduce further unit consumption of product, drop Low production cost.Most of catalyst filters are normal all in working condition, and now each triple valve switches to lower port closing State, the hydride after pre-separation is flowed up into each catalyst filter through triple valve to be filtered, and catalyst filter will be remained Catalyst retention after, the hydride of cleaning flows out into net hydride outlet from the hydride outlet valve of catalyst filter top Pipe.When accumulating excessive catalyst on the filter core of catalyst filter, the filter capacity of catalyst filter is on the one hand caused to decline, separately On the one hand the concentration of catalyst in hydrogenation reaction cauldron can be reduced, the progress of hydrogenation is influenceed, now by closing in triple valve Portion's passage, makes the catalyst filter stop filtering, while triple valve is in the state communicated up and down, you can smoothly enter recoil State, switches very convenient quick.
As a further improvement on the present invention, hydrogen-cooled condenser is installed at the hydriding reactor gaseous phase outlet, it is described hydrogen-cooled solidifying The top of device is provided with hydriding reactor capturing device, and the top exit of the hydrogen-cooled condenser is connected with reactor hydrogen recovery tube, described The outlet of reactor hydrogen recovery tube and the entrance of hydrogen recycle compressor are connected, the outlet of the hydrogen recycle compressor and hydrogen Gas circulation pipe is connected, and the outlet of the hydrogen circulation pipe is connected with the fresh hydrogen supply pipe；The hydrogen recycle compressor Outlet and the centre entrance of knockout drum connect, the centre exit of the knockout drum and the hydrogen circulation pipe connect Connect, the leakage fluid dram of the gas-liquid separation pot bottom passes through the overhead reflux mouth phase of knockout drum return duct and the hydrogenation reaction cauldron Even.The remaining unreacted hydrogen of hydrogenation reaction cauldron, through hydrogen-cooled condenser condensation reduction temperature, is carried after the discharge of hydriding reactor gaseous phase outlet High density, mitigates the load of hydrogen recycle compressor, and hydriding reactor capturing device falls a small amount of liquid droplet capture, prevents from damaging hydrogen Recycle compressor, after hydrogen recycle compressor compresses the hydrogen of recovery, returns in hydrogenation reaction cauldron through hydrogen circulation pipe and circulates, Whole recyclings of hydrogen are realized, no discharge advantageously reduces hydrogen unit consumption, reduces production cost, improves hydrogenation efficiency. Few quantity of fluid that knockout drum is isolated is from knockout drum return duct returns to hydrogenation reaction cauldron, it is to avoid liquid phase substance enters hydrogen Gas circulation pipe.
As a further improvement on the present invention, the top of the catalyst filter is provided with recoil mouth, and the recoil mouthful is installed There is recoil valve, the entrance of the recoil valve is connected with hydriding reactor working solution recoil tube；The lower part outlet of the triple valve is connected with Catalyst filter flow reversal pipe, the lower end of the catalyst filter flow reversal pipe is connected with the working solution supply pipe；The catalyst mistake The lower end of filter return duct is connected with backflow pipe bend, and the lower end of the backflow pipe bend is inserted in the working solution supply pipe, The outlet of the backflow pipe bend is located at the center of the working solution supply pipe and in the same direction with the flow direction of working solution.Fluid bed Operationally, a catalyst filter is kept to be in recoil state, remaining catalyst filter is in working condition, can both carried High efficiency, improves the yield of hydrogen anthraquinone, can ensure the filter efficiency of each catalyst filter again, it is ensured that in hydrogenation reaction cauldron The concentration of catalyst, makes fluid bed all the time in stable working condition.Triple valve is switched into middle part closing, up and down phase during recoil Logical state, simultaneously closes off hydride outlet valve, opens hydride in recoil valve, hydriding reactor working solution recoil tube from recoil valve Into the catalyst filter, the catalyst for being deposited in cartridge surface is rushed, enters work through triple valve and catalyst filter flow reversal pipe Make liquid supply pipe, follow fresh working solution to return in hydrogenation reaction cauldron, all catalyst are recycled.Each catalyst filtering The catalyst that device recoil is reclaimed is directly injected into the center of working solution supply pipe, profit from the backflow pipe bend of catalyst filter flow reversal pipe The catalyst of backflow is spread apart rapidly in fresh working solution rapidly with the jet action of fresh working solution, play mixed uniformly Effect, it is to avoid catalyst conglomeration enters hydrogenation reaction cauldron.
As a further improvement on the present invention, the catalyst preseparator exit is covered with upper end open lower end closed Preseparator ring-shaped baffle, the lower end of the preseparator ring-shaped baffle is connected to the circumferential wall below the outlet of catalyst preseparator On.The lower end closed of preseparator ring-shaped baffle can avoid the powder catalyst that circumferentially wall is centrifuged from choking into catalyst pre-separation Device is exported, and the hydride after separation catalyst enters in annular recess from the top overflow of preseparator ring-shaped baffle, then from catalyst Preseparator outlet enters catalyst preseparator outlet.
As a further improvement on the present invention, inwall ring of the hydriding reactor working solution distribution pipe along the hydrogenation reaction cauldron The multiple hydriding reactor working solutions that Open Side Down distribution are distributed with around one week, and along the even circumferential of hydriding reactor working solution distribution pipe Hole；The hydrogen distributor includes the hydrogen main being connected with the fresh hydrogen supply pipe, and the hydrogen main is described in The diameter of hydrogenation reaction cauldron is laid, and many hydrogen perpendicular to hydrogen main is uniformly connected with along the length direction of the hydrogen main Gas branch pipe, multiple rows of hydrogen dispensing orifice is evenly distributed with along the length direction of each hydrogen branch pipe, and often row's hydrogen dispensing orifice is in sector It is evenly distributed on the lower half of each hydrogen branch pipe.Fresh working solution is hydrogenated kettle working solution distribution pipe and is evenly distributed on hydrogenation instead Answer on the lower circumference of kettle, be conducive to uniformly mixing with hydrogen, hydrogenation occurs rapidly；Hydriding reactor working solution dispensing orifice is opened Mouthful downwards, it is to avoid fresh working solution directly flows to reactor Way out, it is to avoid do not hydrogenate thoroughly working solution from anti- Answer kettle outlet outflow.The working solution sprayed downwards is flowed up again after being mixed with the hydrogen gas bubbles of lower section so that most fresh work Make liquid to contact with density of hydrogen highest region first, be conducive to improving hydrogenation efficiency.Hydrogen from fresh hydrogen supply pipe first Into hydrogen main, then it is divided into multiple tributaries and respectively enters each hydrogen branch pipe, then split by the hydrogen dispensing orifice of multiple rows of multiple row For tiny bubble hydrogen so that the diameter very little of each bubble hydrogen, the specific surface area of hydrogen is increased, hydrogen and work is expanded The contact surface of liquid, is conducive to improving hydrogenation efficiency.
As a further improvement on the present invention, being provided with below the downspout of odd-level oxidation tower tray makes liquid be spread to surrounding Deflection cone, even level oxidation tower tray downspout lower end closed and lower sides be provided with towards oxidation inner wall of tower downspout Liquid outlet.Liquid flows out from the downspout of odd-level oxidizing tower disk center, falls four to even level oxidation tower tray on deflection cone All uniform diffusions, then next odd-level is dropped down onto from the downspout that tower tray periphery is aoxidized positioned at even level, even level downspout Inwall of the downspout liquid outlet towards oxidizing tower so that liquid is first covered with whole periphery, then again from periphery to the descending liquid at center Mouth flowing, has so successively all flowed through the whole radius of oxidation tower tray so that the flow distance of liquid is most long, to greatest extent land productivity With the space of oxidizing tower.
As a further improvement on the present invention, the inner chamber of the oxidizing tower is provided with inlet bend and the oxidizing tower hydride Entrance is connected, and the lower end outlet of the inlet bend is below the liquid level line of oxidizing tower and close to the inwall of oxidizing tower.Entrance The lower end outlet of bend pipe is located at below liquid level line, forms fluid-tight, hydrogen anthraquinone liquid is after the lower end outlet outflow of inlet bend, along oxygen The inwall for changing tower flows downward, and falls on top layer oxidation tower tray periphery, then from periphery advection to the center outflow of oxidation tower tray, Flow while being aoxidized with air contact, it is ensured that the radius of all hydrogen anthraquinone liquid complete stream peroxidating tower trays, Make oxidation more thorough.
As a further improvement on the present invention, oxidizing tower capturing device, each layer are installed at the oxidizing tower gaseous phase outlet Aoxidize tower tray is respectively arranged below with spiral condenser, and the outer wall of the oxidizing tower is wound with multigroup semicanal condenser, each institute Semicanal condenser is stated respectively to be located between adjacent two layers oxidation tower tray, and using the flow direction of low in and high out.Oxidizing tower capturing device Foam can be caught, it is to avoid drop flies out from oxidizing tower gaseous phase outlet；Because the oxidation reaction of hydrogen anthraquinone liquid is exothermic reaction, Each layer oxidation tower tray is respectively arranged below spiral condenser, and working solution can be cooled down in time；Half and half pipework condensation device Oxidizing tower can paragraph by paragraph be cooled down, make the uniform temperature fields of whole oxidizing tower.
It is another object of the present invention to overcoming problems of the prior art, there is provided a kind of life of hydrogen peroxide Production method, can be achieved the continuous production of hydride, and the production consumption of unit product is low, rationally controls and reduces catalyst filter Blowback frequency, improve the service life of catalyst filter, the production consumption of unit product is low, and production efficiency is high, manufacturing cost It is low.
To solve above technical problem, the present invention uses the method that the production system of hydrogen peroxide produces hydrogen peroxide, according to It is secondary to comprise the following steps, (1) configure hydrogenation solvent；(2) added into above solvent after 2- EAQs and 2- amyl anthraquinones The working solution of hydrogenation is constituted, wherein adding 2- EAQs in every liter of solvent（80~110）Added in g/L, every liter of solvent 2- amyl anthraquinones（60~140）G/L, working solution is placed in working liquid tank；(3) prepare powdered palladium catalyst and be placed in catalyst addition tank In；(4) appropriate catalyst is put into hydrogenation reaction cauldron, while the fresh working solution in working liquid tank is pumped into hydrogenation by working solution The bottom even of reactor sprays downwards；Hydrogen is allocated to multiple tiny hydrogen gas bubbles, from the lower direction of fresh working solution Lower to spray, then hydrogen gas bubbles are floated up, and are sufficiently mixed and are stirred with fresh working solution；(5) the anthraquinone in working solution is in powder With hydrogen reaction generation hydrogen anthraquinone in the presence of shape palladium catalyst；(6) remaining unreacted hydrogen is arranged from the top of hydrogenation reaction cauldron Go out, after condensed and trapping drop, into hydrogen recycle compressor compression, the hydrogen after compression returns to hydrogenation after gas-liquid separation Circulated in reactor；(7) hydride uniformly flows out together with catalyst from the middle part of hydrogenation reaction cauldron, divides in advance tangentially into each catalyst From being centrifuged in the middle part of device, during the powder catalyst of sedimentation returns to hydrogenation reaction cauldron from catalyst preseparator bottom, hydrogen From hydrogenation reaction cauldron is returned at the top of catalyst preseparator；(8) the hydride after pre-separation is justified from the top of catalyst preseparator Week outflow, enters in each catalyst filter through triple valve and filters, after catalyst filter retains the catalyst of residual, the hydrogenation of cleaning Liquid flows out from catalyst filter top and enters hydrogenation flow container；(9) the hydride in hydrogenation flow container is pumped into oxidizing tower by hydride Aoxidized；(10) the hydride of hydride pump discharge is also recoiled to each catalyst filter in turn, and catalyst filter is retained Catalyst punching fall, enter working solution supply pipe through triple valve and catalyst filter flow reversal pipe, follow fresh working solution to return to hydrogenation In reactor；(11) in oxidizing tower, compressed air is allocated to numerous bubbles and flows and successively pass through from oxidizing tower bottom up The air-vent on tower tray is aoxidized, hydride enters from oxidizing tower top, the successively advection since the oxidation tower tray of top layer, then Under drop down onto next layer, each layer aoxidize tower tray on hydride one side advection on one side with bubble oxygen generation oxidation reaction, oxygen Change oxidation solution efferent duct output of the liquid from oxidation tower bottom；The percent by volume of step (1) middle hydrogenation solvent formula one is： Diisobutyl carbinol (DIBC)（45~50）V%, C10 aromatic hydrocarbons（50~55）V%, both volume summations are 100%；Step (1) middle hydrogenation The percent by volume of solvent formula two is：Tetrabutyl urea（12~30）V%, trioctyl phosphate（8~12）V%, C10 aromatic hydrocarbons：（60~ 76）V%, the volume summation of three is 100%.
Relative to prior art, the present invention achieves following beneficial effect：Fresh working solution is evenly distributed on hydrogenation On the lower circumference of reactor, and spray downwards；Hydrogen is divided into numerous tiny bubble hydrogens by densely covered hydrogen dispensing orifice, increases The big contact area of hydrogen and working solution, and most fresh working solution contacts with density of hydrogen highest region first, favorably In hydrogenation occurs rapidly, hydrogenation efficiency is improved.After catalyst flows out with hydride, first by the initial gross separation of catalyst preseparator simultaneously Hydrogenation reaction cauldron is flowed back to, then is retained by catalyst filter, hydrogenation reaction cauldron is returned to by recoiling in turn, passes through the lasting conjunction of catalyst Reason flowing, both ensure that the filter efficiency of catalyst filter, the catalyst concentration in hydrogenation reaction cauldron has been kept again.The present invention is used Catalyst and hydrogen be able to whole recyclings, advantageously reduce unit product production consumption, improve hydrogenation efficiency, reduction life Produce cost.Hydride flows downward repeatedly turns back while being formed in the horizontal direction, extends the flow distance of hydride, The time of contact of hydride and oxygen is extended, is conducive to hydrogen anthraquinone liquid to turn into hydrogen peroxide by exhaustive oxidation.
C10 aromatic hydrocarbons in hydrogenation solvent formula one is used to dissolve 2- EAQs and 2- amyl anthraquinones, diisobutyl Methanol increases the solubility of 2- EAQs and 2- amyl anthraquinones.
C10 aromatic hydrocarbons in hydrogenation solvent formula two mainly dissolves 2- EAQs, 2- amyl anthraquinones and reaction and produced Tetrahydrochysene 2- EAQs, and the 2- ethyl hydrogen anthraquinones and tetrahydrochysene 2- ethyl hydrogen anthraquinones that generate after hydrogenation can not be dissolved；Therefore also The trioctyl phosphate and tetrabutyl urea that can dissolve 2- ethyl hydrogen anthraquinones and tetrahydrochysene 2- EAQs are needed as polar solvent.This hair It is bright that there is higher C10 arene contents, working solution proportion can be avoided to increase, extraction tower operating difficulties is caused；Trioctyl phosphate Have the advantages that high boiling point, non-stimulated taste, dissolved hydrogen anthraquinone ability are strong, but if too high levels, working solution can be caused to glue Degree increase, causes mass transfer difficult；Tetrabutyl urea is transparent or slightly yellowish liquid, and viscosity is slightly bigger than water, has and water The advantages of density contrast is big, surface tension is big, relative to trioctyl phosphate to the molten of 2- ethyl hydrogen anthraquinones and tetrahydrochysene 2- EAQs Solution degree is big, and distribution coefficient of the hydrogen peroxide in two-phase is big.Solvent composition combination and ratio using the present invention so that working solution With volatilization loss it is small, using safety, favourable operating environment, reduction raffinate hydrogen peroxide content, improve the excellent of extract concentration Point, due to being reduced with the stock solubility of water so that the TOC of dioxygen aquatic products（Total organic carbon）Content is greatly reduced, and is conducive to The lifting of product quality.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description, accompanying drawing only provide with reference to Illustrate to use, be not used to the limitation present invention.
Fig. 1 is the flow chart of the production system of hydrogen peroxide of the present invention.
Fig. 2 is the structural representation of middle hydrogenation apparatus.
Fig. 3 is the schematic diagram of catalyst filter flow reversal pipe and second of connection scheme of working solution supply pipe.
Fig. 4 is the upward view of hydriding reactor working solution distribution pipe in Fig. 2.
Fig. 5 is the top view of hydrogen distributor in Fig. 2.
Fig. 6 is the cross-sectional view of hydrogen branch pipe in Fig. 5.
Fig. 7 is the front view of oxidizing tower in Fig. 1.
Fig. 8 is the layout drawing of oxidation tower tray in Fig. 7.
Fig. 9 is the top view of odd-level oxidation tower tray in Fig. 7.
Figure 10 is the top view of even level oxidation tower tray in Fig. 7.
Figure 11 is the structural representation of spiral condenser in Fig. 7.
Figure 12 is the structural representation of air distribution device in Fig. 7.
In figure：1. hydrogenation reaction cauldron；1a. hydriding reactor gaseous phase outlets；2. hydriding reactor working solution distribution pipe；2a. hydriding reactor works Make liquid dispensing orifice；3. hydrogen distributor；3a. hydrogen mains；3b. hydrogen branch pipes；3c. hydrogen dispensing orifices；4. catalyst adds tank； 5. catalyst preseparator；5a. preseparator ring-shaped baffles；6. hydrogen-cooled condenser；6a. hydriding reactor capturing devices；7. hydrogen circulation pressure Contracting machine；8. knockout drum；9. catalyst filter；10. oxidizing tower；10a. oxidizing tower gaseous phase outlets；10b. oxidizing tower hydrides Entrance；The total air intake of 10c. oxidizing towers；10d. oxidizing towers are exported；10e. oxidizing tower capturing devices；10f. inlet bends；10g. Aoxidize tower tray；10g1. aoxidizes tower tray air-vent；10g2. descending liquid mouthful；10h. downspouts；10h1. downspout liquid outlet；10j. snakes Shape pipework condensation device；10k. semicanal condensers；10m. air distribution devices；10m1. air main；10m2. air branch pipe；10m3. Air dispensing orifice；10n. deflection cones；
V1. catalyst adds valve；V2. triple valve；V3. hydride outlet valve；V4. recoil valve；T1. working liquid tank；T2. hydride Tank；L1. liquid filter is hydrogenated；C1. hydride cooler；B1. work liquid pump；B2. liquid pump is hydrogenated；G1. working solution supply pipe； G2. fresh hydrogen supply pipe；G3. catalyst adding tube；G4. reactor hydrogen recovery tube；G5. hydrogen circulation pipe；G6. hydriding reactor goes out Mouth pipe；G7. catalyst preseparator outlet；G8. separator hydrogen recovery tube；G9. preseparator catalyst return duct；G10. net hydrogen Change liquid outlet；G11. hydriding reactor working solution recoil tube；G12. catalyst filter flow reversal pipe；G13. knockout drum return duct；G14. Hydrogenate flow container efferent duct；G15. compressed air hose；G16. oxidation solution efferent duct.
Embodiment
As shown in figure 1, the production system of hydrogen peroxide of the present invention includes working liquid tank T1, hydrogenation apparatus, hydride Tank T2 and oxidizing tower, working liquid tank T1 bottom are connected with the entrance for the liquid pump B1 that works, and work liquid pump B1 outlet passes through work Liquid supply pipe G1 is connected with the entrance of hydrogenation apparatus, the outlet of hydrogenation apparatus by net hydride outlet pipe G10 with Hydrogenate flow container T2 to be connected, hydrogenation flow container T2 bottom is connected with hydrogenating liquid pump B2 entrance, hydrogenation liquid pump B2 outlet passes through hydrogen Change flow container efferent duct G14, hydrogenation liquid filter L1 and hydride cooler C1 with the entrance of oxidizing tower to be connected, the outlet of oxidizing tower It is connected with oxidation solution efferent duct G16.
Working solution in working liquid tank T1 is conveyed from work liquid pump B1 by working solution supply pipe G1 to hydrogenation apparatus, The hydride of hydrogenation apparatus production enters hydrogenation flow container T2 by net hydride outlet pipe G10 and kept in, then by hydride The removal of impurity is gone in pump B2 feeding hydrogenation flow container efferent duct G14, first hydrogenated liquid filter L1 filterings, and filtering accuracy is 1 μ, hydride The temperature of hydride is reduced to less than 40 DEG C by cooler C1, and feeding oxidizing tower is aoxidized, the oxidized liquid efferent duct of oxidation solution G16 is exported.
As shown in Fig. 2 hydrogenation apparatus includes vertical hydrogenation reaction cauldron 1, the bottom of hydrogenation reaction cauldron 1 is provided with hydrogenation Kettle working solution distribution pipe 2, the entrance of hydriding reactor working solution distribution pipe 2 is connected with working solution supply pipe G1, hydriding reactor working solution point The lower section of pipe arrangement 2 is provided with hydrogen distributor 3, and the main entrance of hydrogen distributor 3 is connected with fresh hydrogen supply pipe G2, hydrogenates The top of reactor 1 is connected with catalyst adding tube G3, and catalyst adding tube G3 upper end is added valve V1 by catalyst and added with catalyst The outlet connection of tank 4；The top center of hydrogenation reaction cauldron 1 is provided with hydriding reactor gaseous phase outlet 1a, the middle part circumference of hydrogenation reaction cauldron 1 On be uniformly provided with least two reactors outlet.
Open catalyst addition valve V1 and appropriate catalyst is put into hydrogenation reaction cauldron 1, while the hydrogenated kettle of fresh working solution The bottom even that working solution distribution pipe 2 distributes backward hydrogenation reaction cauldron 1 sprays, and hydrogen enters hydrogen from fresh hydrogen supply pipe G2 Distributor 3, hydrogen distributor 3 uniformly discharges multiple tiny hydrogen gas bubbles, is sprayed downwards from the lower section of fresh working solution Go out, then hydrogen gas bubbles are floated up, be sufficiently mixed and stir with fresh working solution；Anthraquinone in working solution is touched in powdered palladium With hydrogen reaction generation hydrogen anthraquinone in the presence of matchmaker, the working solution now containing hydrogen anthraquinone is referred to as hydride；Remaining unreacted Hydrogen from the hydriding reactor gaseous phase outlet 1a discharges at the top of hydrogenation reaction cauldron 1.The middle part of hydrogenation reaction cauldron 1 is connected with multiple reactions Kettle is exported, and is easy to carry out the recoil of catalyst in turn, it is ensured that fluid bed being capable of continuous and stable production.
Hydrogen-cooled condenser 6 is installed, the top of hydrogen-cooled condenser 6 is provided with hydriding reactor capturing device at hydriding reactor gaseous phase outlet 1a 6a, the top exit of hydrogen-cooled condenser 6 is connected with reactor hydrogen recovery tube G4, reactor hydrogen recovery tube G4 outlet and hydrogen The entrance connection of recycle compressor 7, the outlet of hydrogen recycle compressor 7 is connected with hydrogen circulation pipe G5, hydrogen circulation pipe G5's Outlet is connected with fresh hydrogen supply pipe G2.The remaining unreacted hydrogen of hydrogenation reaction cauldron 1 is discharged from hydriding reactor gaseous phase outlet 1a Afterwards, through hydrogen-cooled condenser 6 condensation reduction temperature, density is improved, mitigates the load of hydrogen recycle compressor 7, hydriding reactor capturing device 6a falls a small amount of liquid droplet capture, prevents from damaging hydrogen recycle compressor 7, hydrogen recycle compressor 7 compresses the hydrogen of recovery Afterwards, return in hydrogenation reaction cauldron 1 and circulate through hydrogen circulation pipe G5, realize whole recyclings of hydrogen, no discharge is conducive to Hydrogen unit consumption is reduced, production cost is reduced, hydrogenation efficiency is improved.
Reactor outlet is connected with hydriding reactor outlet G6, and hydriding reactor outlet G6 outlet is tangentially connected to tactile On the middle part circumference of matchmaker's preseparator 5, the top circumference of catalyst preseparator 5 is exported provided with catalyst preseparator, and catalyst divides in advance It is connected from device outlet with catalyst preseparator outlet G7；The top of catalyst preseparator 5 is connected with separator hydrogen recovery tube G8, separator hydrogen recovery tube G8 upper end upwardly extends and is connected with the gas-phase space on the top of hydrogenation reaction cauldron 1；Catalyst divides in advance Bottom from device 5 is up big and down small taper and passes through the lower circumference of preseparator catalyst return duct G9 and hydrogenation reaction cauldron 1 It is connected.Reactor outlet and hydriding reactor outlet G6 of the hydride together with powder catalyst from the middle part of hydrogenation reaction cauldron 1 are uniformly flowed out, Tangentially into the middle part of each catalyst preseparator 5, inwall circumference rotation of the hydride along catalyst preseparator 5, powder catalyst Under the influence of centrifugal force, settled along the inwall of catalyst preseparator 5, the preseparator catalyst from the bottom of catalyst preseparator 5 Return duct G9 is returned in hydrogenation reaction cauldron 1, and hydrogen returns to hydrogen from the top of catalyst preseparator 5 through separator hydrogen recovery tube G8 Change in reactor 1.By means of the flow velocity of hydride itself, using the method for centrifugation, powder catalyst initial gross separation is come out, The filtering load of catalyst filter 9 is significantly reduced, the frequency of recoil is reduced, substantially increases production efficiency.Initial gross separation The catalyst and hydrogen gone out is all reclaimed, and be reduce further unit consumption of product, is reduced production cost.
Catalyst preseparator outlet G7 outlet is connected with triple valve V2 centre entrance, triple valve V2 upper outlet It is connected with the bottom inlet of catalyst filter 9, the top center of catalyst filter 9 is provided with hydride outlet valve V3, hydride Outlet valve V3 outlet is connected with net hydride outlet pipe G10.Most of catalyst filters 9 are normal all in working condition, this When each triple valve V2 switch to lower port closing state, the hydride after pre-separation flows up into each catalyst through triple valve V2 Filtered in filter 9, after catalyst filter 9 retains the catalyst of residual, the hydrogen of the hydride of cleaning from the top of catalyst filter 9 Change liquid outlet valve V3 and flow out into net hydride outlet pipe G10.When accumulating excessive catalyst on the filter core of catalyst filter 9 When, on the one hand cause the filter capacity of catalyst filter 9 to decline, on the other hand can reduce the concentration of catalyst in hydrogenation reaction cauldron 1, The progress of hydrogenation is influenceed, now by closing triple valve V2 central passage, the catalyst filter 9 is stopped filtering, together When triple valve V2 be in the state communicated up and down, you can smoothly enter recoil state, switch very convenient quick.
The top of catalyst filter 9 is provided with recoil valve V4, recoil valve V4 entrance and hydrogenation provided with recoil mouth, recoil mouth Kettle working solution recoil tube G11 is connected, and outlets of the hydriding reactor working solution recoil tube G11 with hydrogenating liquid pump B2 is connected；Triple valve V2's Lower part outlet is connected with catalyst filter flow reversal pipe G12, catalyst filter flow reversal pipe G12 lower end and working solution supply pipe G1 phases Even.Fluid bed operationally, keeps a catalyst filter 9 to be in recoil state, and remaining catalyst filter 9 is in work shape State, can both improve production efficiency, improve the yield of hydrogen anthraquinone, can ensure the filter efficiency of each catalyst filter 9 again, it is ensured that The concentration of catalyst in hydrogenation reaction cauldron 1, makes fluid bed all the time in stable working condition.Triple valve V2 is switched to during recoil The state that middle part is closed, communicated up and down, simultaneously closes off hydride outlet valve V3, opens recoil valve V4, the recoil of hydriding reactor working solution Hydride in pipe G11 enters the catalyst filter 9 from recoil valve V4, the catalyst for being deposited in cartridge surface is rushed, through threeway Valve V2 and catalyst filter flow reversal pipe G12 enters working solution supply pipe G1, follows fresh working solution to return in hydrogenation reaction cauldron 1, All catalyst are recycled.
A kind of scheme is：It is connected with catalyst filter flow reversal pipe G12 lower end under backflow pipe bend, backflow pipe bend In end insertion working solution supply pipe G1, the outlet of backflow pipe bend positioned at working solution supply pipe G1 center and with the stream of working solution Dynamic direction is in the same direction.Catalyst from catalyst filter flow reversal pipe G12 that each recoil of catalyst filter 9 is reclaimed backflow pipe bend are directly noted Enter to working solution supply pipe G1 center, make the catalyst of backflow rapidly in fresh working solution using the jet action of fresh working solution In spread apart rapidly, play mixed uniformly effect, it is to avoid catalyst conglomeration enter hydrogenation reaction cauldron 1.
As shown in figure 3, another scheme is：The big of taper is connected in catalyst filter flow reversal pipe G12 lower end Hold circumference on, taper be sleeved on working solution supply pipe G1 periphery and with working solution supply pipe G1 coaxial lines, taper Big end seal close, the small end of taper towards hydrogenation reaction cauldron 1 and it is relative with working solution supply pipe G1 connect, the working solution is supplied It is located at the aditus laryngis that the part in taper is provided with reduced diameter to pipe G1, the aditus laryngis stretches to the small end of taper. The catalyst that the recoil of catalyst filter is reclaimed enters in taper from catalyst filter flow reversal pipe G12, and fresh working solution is in work Liquid supply pipe G1 high speed flow forwards, flow velocity is accelerated at aditus laryngis, pressure reduction, is played to entering the catalyst in taper Swabbing action, catalyst is able to be uniformly dispersed rapidly in fresh working solution, it is to avoid catalyst conglomeration enters hydrogenation reaction cauldron 1.
Preseparator ring-shaped baffle 5a of the catalyst preseparator exit covered with upper end open lower end closed, preseparator Ring-shaped baffle 5a lower end is connected in the circumferential wall below the outlet of catalyst preseparator.Preseparator ring-shaped baffle 5a lower end Closing can avoid the powder catalyst that circumferentially wall is centrifuged from choking into the outlet of catalyst preseparator, separate the hydride after catalyst Enter from preseparator ring-shaped baffle 5a top overflow in annular recess, then divide in advance into catalyst from the outlet of catalyst preseparator From device outlet G7.
The outlet of hydrogen recycle compressor 7 is connected with the centre entrance of knockout drum 8, and the middle part of knockout drum 8 goes out Mouth is connected with hydrogen circulation pipe G5, and the leakage fluid dram of the bottom of knockout drum 8 passes through knockout drum return duct G13 and hydrogenation reaction cauldron 1 Overhead reflux mouthful be connected.Few quantity of fluid that knockout drum 8 is isolated returns to hydrogenation reaction cauldron from knockout drum return duct G13 In 1, it is to avoid liquid phase substance enters hydrogen circulation pipe G5.
As shown in figure 4, inner wall surrounding of the hydriding reactor working solution distribution pipe 2 along hydrogenation reaction cauldron 1 one week, and along hydriding reactor work Multiple hydriding reactor working solution dispensing orifice 2a that Open Side Down are distributed with the even circumferential for making liquid distribution pipe 2.Fresh working solution quilt Hydriding reactor working solution distribution pipe 2 is evenly distributed on the lower circumference of hydrogenation reaction cauldron 1, is conducive to uniformly mixing with hydrogen, fast Hydrogenation occurs for speed；Open Side Down by hydriding reactor working solution dispensing orifice 2a, it is to avoid fresh working solution directly goes out to reactor Mouth direction flowing, it is to avoid do not hydrogenate thoroughly working solution and exported from reactor and flowed out.The working solution that sprays downwards and lower section Flowed up again after hydrogen gas bubbles mixing so that most fresh working solution is contacted with density of hydrogen highest region first, favorably In raising hydrogenation efficiency.
As shown in Figure 5, Figure 6, hydrogen distributor 3 includes the hydrogen main 3a being connected with fresh hydrogen supply pipe G2, hydrogen Diameters of the gas main 3a along hydrogenation reaction cauldron 1 is laid, and many are uniformly connected with perpendicular to hydrogen along hydrogen main 3a length direction Gas main 3a hydrogen branch pipe 3b, multiple rows of hydrogen dispensing orifice 3c is evenly distributed with along each hydrogen branch pipe 3b length direction, and often Row's hydrogen dispensing orifice 3c is evenly distributed on each hydrogen branch pipe 3b lower half in sector.Hydrogen from fresh hydrogen supply pipe G2 first Into hydrogen main 3a, then it is divided into multiple tributaries and respectively enters each hydrogen branch pipe 3b, then by the hydrogen dispensing orifice of multiple rows of multiple row 3c is divided into tiny bubble hydrogen so that the diameter very little of each bubble hydrogen, increases the specific surface area of hydrogen, expands hydrogen With the contact surface of working solution, be conducive to improving hydrogenation efficiency.
As shown in Fig. 7 to Figure 12, the top center of oxidizing tower 10 is provided with oxidizing tower gaseous phase outlet 10a, oxidizing tower 10 it is upper Portion side wall is connected with oxidizing tower hydride entrance 10b, and oxidizing tower hydride entrance 10b is located above the liquid level line of oxidizing tower 10, The bottom of oxidizing tower 10 is provided with air distribution device 10m, and air distribution device 10m enters with the total air of oxidizing tower on oxidizing tower 10 Mouth 10c connections, the total air intake 10c of oxidizing tower is connected with compressed air hose G15.The bottom centre of oxidizing tower 10 is provided with oxidizing tower Export 10d；Oxidizing tower outlet 10d is connected with oxidation solution efferent duct G16.Multiple tracks water is uniformly provided with along the short transverse of oxidizing tower 10 The oxidation tower tray 10g of flat round plate-like；Multiple oxidation tower tray air-vent 10g1, each layer oxygen are uniformly densely covered with each oxidation tower tray 10g Change and descending liquid mouthful 10g2 is respectively equipped with tower tray 10g, each descending liquid mouthful 10g2, which is connected to next layer, aoxidizes the drop that tower tray extends Liquid pipe 10h；Descending liquid mouthful on the tower tray of odd-level oxidation from top to bottom is located on the axis of oxidizing tower 10, on even level oxidation tower tray Descending liquid mouth be symmetrical arranged and close to oxidizing tower 10 inwall.
Compressed air is distributed into numerous bubbles by the air distribution device 10m of bottom, flows from bottom to top；Hydrogen anthraquinone liquid from The oxidizing tower hydride entrance 10b on top enter oxidizing tower 10 in, fall first on the oxidation tower tray of top layer, then from periphery to Center flow, after the descending liquid mouthful and downspout 10h at center are fallen, reaches second layer Ze Cong centers to perimeter, so by Then layer advection flow downward.During air flows upwards, minute bubbles are easily mutually collided, assembled, being bonded into larger bubble, when When air pocket reaches oxidation tower tray 10g lower section, it is oxidized tower tray air-vent 10g1 and is divided into numerous minute bubbles again, significantly The specific surface area of bubble is added, when hydride flows through oxide regions, is in contact with countless minute bubbles, contact area is big, is mixed Close good.Air pocket is oxidized tower tray 10g and is divided into tiny bubble again for several times in uphill process, substantially increases oxidation Efficiency, as long as an oxidizing tower can be properly completed the oxidation of hydrogen anthraquinone liquid, reduces equipment investment and production cost.Hydrogen anthraquinone Liquid each layer aoxidize tower tray on one side advection on one side with bubble oxygen occur oxidation reaction generation hydrogen peroxide, hydride and Counter-current flow is presented in air, and contact is most ozone when hydride flows to oxidation tower bottom, to ensure oxidation reaction It is properly completed, then from the oxidizing tower outlet 10d outflows of bottom.The descending liquid mouth of adjacent layer oxidation tower tray mutually staggers and makes hydride Flow downward and repeatedly turned back while being formed in the horizontal direction, extend the flow distance of hydride, also extend hydride With the time of contact of oxygen, be conducive to hydrogen anthraquinone liquid by exhaustive oxidation turn into hydrogen peroxide.Oxidizing tower hydride entrance 10b is located at Oxidation solution can be prevented above liquid level line to choke in hydrogen anthraquinone liquid pipe road, it is to avoid pollute upper track formation.
As shown in Figure 9, Figure 10, being provided with below the downspout of odd-level oxidation tower tray makes the deflection cone that liquid spreads to surrounding 10n, the downspout that the lower end closed and lower sides of the downspout of even level oxidation tower tray are provided with towards the inwall of oxidizing tower 10 goes out Liquid mouthful 10h1.Liquid flows out from the downspout of odd-level oxidizing tower disk center, falls on deflection cone 10n to even level oxidation tower tray Surrounding uniformly spread, then drop down onto next odd-level, even level descending liquid from the downspout that tower tray periphery is aoxidized positioned at even level Inwalls of the downspout liquid outlet 10h1 of pipe towards oxidizing tower 10 so that liquid is first covered with whole periphery, then again from periphery to The descending liquid mouthful flowing at center, has so successively all flowed through the whole radius of oxidation tower tray so that the flow distance of liquid is most long, most It make use of to limits the space of oxidizing tower.
The inner chamber of oxidizing tower is connected provided with inlet bend 10f with oxidizing tower hydride entrance 10b, under inlet bend 10f Mouth is brought out below the liquid level line of oxidizing tower 10 and close to the inwall of oxidizing tower 10.Inlet bend 10f lower end outlet is located at Below liquid level line, form fluid-tight, hydrogen anthraquinone liquid after inlet bend 10f lower end outlet outflow, along oxidizing tower 10 inwall to Lower flowing, and falling on top layer oxidation tower tray periphery, then from periphery advection to the center outflow of oxidation tower tray, flow while Aoxidized with air contact, it is ensured that the radius of all hydrogen anthraquinone liquid complete stream peroxidating tower trays, make oxidation more thorough Bottom.
The aperture for aoxidizing tower tray air-vent 10g1 is that the centre-to-centre spacing between 3~6mm, adjacent oxidation tower tray air-vent 10g1 is 35~40mm.Make bubble that there is very big specific surface area, and each oxidation tower tray air-vent 10g1 can be passed through, with hydride Mixing it is abundant.
Oxidizing tower capturing device 10e is installed at oxidizing tower gaseous phase outlet 10a.Oxidizing tower capturing device 10e can be caught Foam, it is to avoid drop flies out from oxidizing tower gaseous phase outlet 10a.
The outer wall of oxidizing tower 10 is wound with multigroup semicanal condenser 10k, and half and half pipework condensation device 10k is located at adjacent two layers respectively Between oxidation tower tray, and using the flow direction of low in and high out.Half and half pipework condensation device 10k can paragraph by paragraph be cooled down to oxidizing tower 10, Make the uniform temperature fields of whole oxidizing tower.
As shown in Fig. 7, Figure 11, each layer oxidation tower tray is respectively arranged below with spiral condenser 10j.Due to hydrogen anthraquinone liquid Oxidation reaction be exothermic reaction, aoxidizing tower tray in each layer is respectively arranged below spiral condenser 10j, can in time to hydrogen Change liquid to be cooled down.
As shown in figure 12, air distribution device 10m includes the air main being connected with the total air intake 10c of oxidizing tower The diameter extension of 10m1, air main 10m1 along oxidizing tower, is connected to many along air main 10m1 length direction and hangs down Directly in air main 10m1 air branch pipe 10m2, each air branch pipe 10m2 is parallel to each other, uniform intervals and positioned at same flat In face, air main 10m1 and each air branch pipe 10m2 top are uniformly densely covered with least two air-discharging dispensing orifice 10m3 respectively. Air initially enters air main 10m1, is then divided into multiple tributaries and respectively enters each air branch pipe 10m2, then by multiple rows of multiple row Air dispensing orifice 10m3 be divided into tiny air bubble, air dispensing orifice 10m3 aperture is 3~6mm so that each air The diameter very little of bubble, increases the specific surface area of air, expands the contact surface of air and hydride, is conducive to improving oxidation effect Rate.
The production method of hydrogen peroxide of the present invention, in turn includes the following steps, and (1) configures hydrogenation solvent；(2) to the above The working solution that hydrogenation is constituted after 2- EAQs and 2- amyl anthraquinones is added in solvent, wherein adding 2- second in every liter of solvent Base anthraquinone（80~110）2- amyl anthraquinones are added in g/L, every liter of solvent（60~140）G/L, working liquid tank is placed in by working solution In T1；(3) prepare powdered palladium catalyst to be placed in catalyst addition tank 4, the particle diameter volume distributed median of palladium catalyst is：Particle diameter is more than 120 microns Percent by volume be no more than 4%；The percent by volume that particle diameter is less than 80 microns is no more than 4%, and remaining particle diameter is 80~120 micro- Rice；(4) open catalyst addition valve V1 and appropriate catalyst is put into hydrogenation reaction cauldron 1, while the fresh working solution in working liquid tank T1 Working solution supply pipe G1 is sent into by work liquid pump B1, hydrogenated kettle working solution distribution pipe 2 distributes the bottom of backward hydrogenation reaction cauldron 1 It is uniform to spray；Hydrogen evenly distributes into multiple tiny hydrogen gas bubbles by hydrogen distributor 3, from the lower direction of fresh working solution Lower to spray, then hydrogen gas bubbles are floated up, and are sufficiently mixed and are stirred with fresh working solution；(5) the anthraquinone in working solution is in powder With hydrogen reaction generation hydrogen anthraquinone in the presence of shape palladium catalyst, that is, the hydride being commonly called as；(6) remaining unreacted hydrogen is from hydrogenation The top discharge of reactor 1, after hydrogen-cooled condenser 6 is condensed and hydriding reactor capturing device 6a traps drop, circulates into hydrogen and presses Contracting machine 7 compresses, and after the hydrogen after compression is separated through knockout drum 8, is returned to and is followed in hydrogenation reaction cauldron 1 by hydrogen circulation pipe G5 Ring；(7) hydride divides in advance together with catalyst from the uniform outflow in reactor outlet at the middle part of hydrogenation reaction cauldron 1 tangentially into each catalyst From the middle part of device 5, hydride along catalyst preseparator 5 inwall circumference rotation, powder catalyst under the influence of centrifugal force, along touch The inwall sedimentation of matchmaker's preseparator 5, hydrogenation reaction cauldron is returned to from the preseparator catalyst return duct G9 of the bottom of catalyst preseparator 5 In 1, hydrogen is returned in hydrogenation reaction cauldron 1 from the top of catalyst preseparator 5 through separator hydrogen recovery tube G8；(8) each triple valve V2 switches to lower port closing state, and the hydride after pre-separation flows out from the top circumference of catalyst preseparator 5, through triple valve V2 is flowed up into each catalyst filter 9 and filtered, after catalyst filter 9 retains the catalyst of residual, the hydride of cleaning Enter hydrogenation flow container T2 from the outflow of the top of catalyst filter 9 and by net hydride outlet pipe G10；(9) the hydrogen in flow container T2 is hydrogenated Change liquid by hydrogenation liquid pump B2 feeding hydrogenation flow container efferent duct G14, the removal of impurity is gone by the filtering of hydrogenation liquid filter, filtering accuracy is 1 μ, is reduced to less than 40 DEG C, feeding oxidizing tower 10 is aoxidized by hydride cooler C1 by the temperature of hydride again after filtering； (10) the hydride of hydrogenation liquid pump B2 outlets is also carried out instead to each catalyst filter 9 in turn by hydriding reactor working solution recoil tube G11 Punching, switches to the state that middle part is closed, communicated up and down by triple valve V2 during recoil, simultaneously closes off hydride outlet valve V3, open Hydride in recoil valve V4, hydriding reactor working solution recoil tube G11 enters the catalyst filter 9 from recoil valve V4, by catalyst mistake The catalyst punching that filter 9 is retained falls, and enters working solution supply pipe G1 through triple valve V2 and catalyst filter flow reversal pipe, follows fresh work Returned to as liquid in hydrogenation reaction cauldron 1；(11) in oxidizing tower 10, compressed air is allocated to numerous bubbles from oxidizing tower bottom up Flow and successively through the air-vent on oxidation tower tray, hydride enters from oxidizing tower top, since the oxidation tower tray of top layer Successively advection, then drops down onto down next layer, aoxidizes hydride one side advection on tower tray in each layer while being sent out with the oxygen in bubble Raw oxidation reaction, the oxidation solution of the bottom of oxidizing tower 10 is exported from oxidation solution efferent duct G16.
Also contain nitrogen and inert gas, the hydrogen that hydrogen recycle compressor 7 is exported in hydrogenation reaction cauldron 1 in addition to the hydrogen Product percentage composition is 80%, and remaining is nitrogen and inert gas.Hydrogen circulation pipe G5 and the mixed gas of fresh hydrogen supply pipe G2 In body, the volumn concentration of hydrogen is 91%.
Oxygen content and the continuous monitoring of carbon monoxide content must be carried out to the hydrogen that fresh hydrogen supply pipe G2 is provided, its The volumn concentration of middle oxygen have to be lower than 1%, higher than the level, then must bypass hydrogenation reaction cauldron 1.Fresh hydrogen supply pipe Carbon monoxide content in G2 supply hydrogen have to be lower than 1.0ppm, it is to avoid palladium catalyst poisoning.
Reaction temperature in hydrogenation reaction cauldron 1 is 50~65 DEG C, and the working solution residence time is 0.25~0.55 hour, hydrogenation Pressure in reactor 1 is that the pressure of fresh hydrogen in 100~150KPa, fresh hydrogen supply pipe G2 is 0.25~0.35MPa.
Step (1) in hydrogenation solvent can be configured by following percent by volume, diisobutyl carbinol (DIBC)：（45~50） V%, C10 aromatic hydrocarbons：（50~55）V%, both volume summations are 100%.C10 aromatic hydrocarbons is used to dissolve 2- EAQs and 2- amyl groups Anthraquinone, diisobutyl carbinol (DIBC) increases the solubility of 2- EAQs and 2- amyl anthraquinones.
Under the solvent formula, the hydrogenation efficiency that embodiment one~tetra- reaches is as shown in table 1：
Table 1
。
Step (1) in hydrogenation solvent can also be configured by following percent by volume, tetrabutyl urea：（12~30）V%, Trioctyl phosphate：（8~12）V%, C10 aromatic hydrocarbons：（60~76）V%, the volume summation of three is 100%.C10 aromatic hydrocarbons mainly dissolves The tetrahydrochysene 2- EAQs that 2- EAQs, 2- amyl anthraquinones and reaction are produced, and the 2- ethyls generated after hydrogenation can not be dissolved Hydrogen anthraquinone and tetrahydrochysene 2- ethyl hydrogen anthraquinones；Therefore also need to that the tricresyl phosphate of 2- ethyl hydrogen anthraquinones and tetrahydrochysene 2- EAQs can be dissolved Monooctyl ester and tetrabutyl urea are used as polar solvent.The present invention has higher C10 arene contents, and working solution proportion can be avoided to increase Greatly, extraction tower operating difficulties is caused；Trioctyl phosphate has the advantages that high boiling point, non-stimulated taste, dissolved hydrogen anthraquinone ability are strong, But if too high levels, work fluid viscosity can be caused to increase, cause mass transfer difficult；Tetrabutyl urea is transparent or slightly slightly yellow Liquid, viscosity is slightly bigger than water, has the advantages that and water density difference is big, surface tension is big, relative to trioctyl phosphate to 2- The solubility of ethyl hydrogen anthraquinone and tetrahydrochysene 2- EAQs is big, and distribution coefficient of the hydrogen peroxide in two-phase is big.Using the present invention Solvent composition combination and ratio so that working solution have volatilization loss it is small, using safety, favourable operating environment, reduction raffinate Liquid hydrogen peroxide content, the advantage for improving extract concentration, due to being reduced with the stock solubility of water so that dioxygen aquatic products TOC（Total organic carbon）Content is greatly reduced, and is conducive to the lifting of product quality.
Under the solvent formula, the hydrogenation efficiency that embodiment five~eight reaches is as shown in table 2：
。
It the foregoing is only the preferable possible embodiments of the present invention, non-therefore the limitation present invention patent protection model Enclose.In addition to the implementation, the present invention can also have other embodiment, and the direction of such as left and right can be exchanged, all uses etc. With the technical scheme replaced or equivalent transformation is formed, all fall within the protection domain of application claims.The present invention is without description Technical characteristic can be realized by or using prior art, will not be repeated here.

Claims (10)

1. a kind of production system of hydrogen peroxide, including working liquid tank, hydrogenation apparatus, hydrogenation flow container and oxidizing tower, described The bottom of working liquid tank is connected with the entrance for the liquid pump that works, and the outlet of the work liquid pump passes through working solution supply pipe and the hydrogen The entrance for changing reaction unit is connected, and the outlet of the hydrogenation apparatus passes through net hydride outlet pipe and the hydrogenation flow container phase Even, the bottom of the hydrogenation flow container is connected with hydrogenating the entrance of liquid pump, and the outlet of the hydrogenation liquid pump is exported by hydrogenating flow container Pipe, hydrogenation liquid filter and hydride cooler are connected with the entrance of the oxidizing tower, and the outlet connection of the oxidizing tower is aerobic Change liquid efferent duct, it is characterised in that：The top center of the oxidizing tower is provided with oxidizing tower gaseous phase outlet, the top of the oxidizing tower Side wall is connected with oxidizing tower hydride entrance, and the oxidizing tower hydride entrance is located above the liquid level line of oxidizing tower, the oxygen The bottom for changing tower is provided with air distribution device, and the air distribution device is connected with the total air intake of the oxidizing tower on oxidizing tower, The bottom centre of the oxidizing tower exports provided with oxidizing tower；Multiple tracks horizontal circle plate-like is uniformly provided with along the short transverse of oxidizing tower Aoxidize tower tray；Uniformly it is densely covered with multiple oxidation tower tray air-vents, each layer oxidation tower tray and is respectively equipped with each oxidation tower tray Descending liquid mouthful, each descending liquid mouth is connected to the downspout to next layer of oxidation tower tray extension；Odd-level is aoxidized from top to bottom Descending liquid mouthful on tower tray is located on the axis of oxidizing tower, and the descending liquid mouth on even level oxidation tower tray is symmetrical arranged and close to oxidizing tower Inwall.
2. the production system of hydrogen peroxide according to claim 1, it is characterised in that：The hydrogenation apparatus includes hydrogen Change reactor, the bottom of the hydrogenation reaction cauldron is provided with hydriding reactor working solution distribution pipe, the hydriding reactor working solution distribution pipe Entrance is connected with the working solution supply pipe, and the lower section of the hydriding reactor working solution distribution pipe is provided with hydrogen distributor, described The main entrance of hydrogen distributor is connected with fresh hydrogen supply pipe, and catalyst addition is connected with the top of the hydrogenation reaction cauldron Pipe, the upper end of the catalyst adding tube is connected by the outlet that catalyst adds valve with catalyst adds tank；The hydrogenation reaction cauldron Top center is provided with hydriding reactor gaseous phase outlet, and being uniformly provided with least two reactors on the middle part circumference of the hydrogenation reaction cauldron goes out Mouthful；Reactor outlet is connected with hydriding reactor outlet, and the outlet of the hydriding reactor outlet is tangentially connected to tactile On the middle part circumference of matchmaker's preseparator, the top circumference of the catalyst preseparator is exported provided with catalyst preseparator, described to touch The outlet of matchmaker's preseparator is connected with catalyst preseparator outlet；Separator hydrogen is connected with the top of the catalyst preseparator Recovery tube, the upper end of the separator hydrogen recovery tube upwardly extend and with the gas-phase space phase on the hydrogenation reaction cauldron top Even；The bottom of the catalyst preseparator is for up big and down small taper and anti-by preseparator catalyst return duct and the hydrogenation The lower circumference of kettle is answered to be connected；The outlet of the catalyst preseparator outlet is connected with the centre entrance of triple valve, and described three The upper outlet of port valve is connected with the bottom inlet of catalyst filter, and the top center of the catalyst filter is provided with hydride Outlet valve, the outlet of the hydride outlet valve is connected with the net hydride outlet pipe.
3. the production system of hydrogen peroxide according to claim 2, it is characterised in that：Pacify at the hydriding reactor gaseous phase outlet Equipped with hydrogen-cooled condenser, the top of the hydrogen-cooled condenser is provided with hydriding reactor capturing device, and the top exit of the hydrogen-cooled condenser is connected There is reactor hydrogen recovery tube, the outlet of the reactor hydrogen recovery tube and the entrance of hydrogen recycle compressor are connected, described The outlet of hydrogen recycle compressor is connected with hydrogen circulation pipe, the outlet of the hydrogen circulation pipe and the fresh hydrogen supply pipe Connection；The outlet of the hydrogen recycle compressor and the centre entrance of knockout drum are connected, the middle part of the knockout drum Outlet is connected with the hydrogen circulation pipe, and the leakage fluid dram of the gas-liquid separation pot bottom passes through knockout drum return duct and the hydrogenation The overhead reflux mouthful of reactor is connected.
4. the production system of hydrogen peroxide according to claim 2, it is characterised in that：Set at the top of the catalyst filter There is recoil mouth, the recoil mouthful is provided with recoil valve, and the entrance of the recoil valve is connected with hydriding reactor working solution recoil tube；It is described The lower part outlet of triple valve is connected with catalyst filter flow reversal pipe, lower end and the working solution of the catalyst filter flow reversal pipe Supply pipe is connected；The lower end of the catalyst filter flow reversal pipe is connected with backflow pipe bend, and the lower end of the backflow pipe bend is inserted Enter in the working solution supply pipe, the outlet of the backflow pipe bend is positioned at the center of the working solution supply pipe and and working solution Flow direction it is in the same direction.
5. the production system of hydrogen peroxide according to claim 2, it is characterised in that：The catalyst preseparator exit Preseparator ring-shaped baffle covered with upper end open lower end closed, the lower end of the preseparator ring-shaped baffle is connected to catalyst In circumferential wall below preseparator outlet.
6. the production system of hydrogen peroxide according to claim 2, it is characterised in that：The hydriding reactor working solution distribution pipe Along the inner wall surrounding one week of the hydrogenation reaction cauldron, and multiple openings are distributed with along the even circumferential of hydriding reactor working solution distribution pipe Downward hydriding reactor working solution dispensing orifice；The hydrogen that the hydrogen distributor includes being connected with the fresh hydrogen supply pipe is done Pipe, diameter of the hydrogen main along the hydrogenation reaction cauldron is laid, and is uniformly connected with along the length direction of the hydrogen main The many hydrogen branch pipes perpendicular to hydrogen main, multiple rows of hydrogen dispensing orifice is evenly distributed with along the length direction of each hydrogen branch pipe, And often row's hydrogen dispensing orifice is evenly distributed on the lower half of each hydrogen branch pipe in sector.
7. the production system of hydrogen peroxide according to claim 1, it is characterised in that：Odd-level aoxidizes the downspout of tower tray Lower section is provided with the deflection cone that liquid spreads to surrounding is made, and the lower end closed and lower sides of the downspout of even level oxidation tower tray are set There is the downspout liquid outlet towards oxidation inner wall of tower.
8. the production system of hydrogen peroxide according to claim 1, it is characterised in that：The inner chamber of the oxidizing tower be provided with into Mouth bend pipe is connected with the oxidizing tower hydride entrance, and the lower end outlet of the inlet bend is below the liquid level line of oxidizing tower And close to the inwall of oxidizing tower.
9. the production system of hydrogen peroxide according to claim 1, it is characterised in that：Pacify at the oxidizing tower gaseous phase outlet Equipped with oxidizing tower capturing device, each layer oxidation tower tray is respectively arranged below with spiral condenser, and the outer wall of the oxidizing tower is twined Be wound with multigroup semicanal condenser, each semicanal condenser is located between adjacent two layers oxidation tower tray respectively, and using it is low enter height The flow direction gone out.
10. a kind of production system of the hydrogen peroxide any one of use claim 1 to 9 produces the side of hydrogen peroxide Method, it is characterised in that in turn include the following steps, (1) configures hydrogenation solvent；(2) 2- ethyl anthracenes are added into above solvent The working solution of hydrogenation is constituted after quinone and 2- amyl anthraquinones, wherein adding 2- EAQs in every liter of solvent（80~110）g/ 2- amyl anthraquinones are added in L, every liter of solvent（60~140）G/L, working solution is placed in working liquid tank；(3) prepare powdered palladium to touch Matchmaker is placed in catalyst addition tank；(4) appropriate catalyst is put into hydrogenation reaction cauldron, at the same the fresh working solution in working liquid tank by The bottom even that working solution is pumped into hydrogenation reaction cauldron sprays downwards；Hydrogen is allocated to multiple tiny hydrogen gas bubbles, from new The lower section of fresh working solution is sprayed downwards, and then hydrogen gas bubbles are floated up, and is sufficiently mixed and is stirred with fresh working solution；(5) work Make the anthraquinone in liquid and generate hydrogen anthraquinone with hydrogen reaction in the presence of powdered palladium catalyst；(6) remaining unreacted hydrogen is from hydrogenation After the top discharge of reactor, condensed and trapping drop, into hydrogen recycle compressor compression, the hydrogen after compression is through gas-liquid Return in hydrogenation reaction cauldron and circulate after separation；(7) hydride uniformly flows out together with catalyst from the middle part of hydrogenation reaction cauldron, tangentially It is centrifuged in the middle part of into each catalyst preseparator, the powder catalyst of sedimentation returns to hydrogenation from catalyst preseparator bottom In reactor, hydrogen at the top of catalyst preseparator from hydrogenation reaction cauldron is returned to；(8) the hydride after pre-separation is pre- from catalyst The top circumference outflow of separator, enters in each catalyst filter through triple valve and filters, catalyst filter cuts the catalyst of residual After staying, the hydride of cleaning flows out from catalyst filter top and enters hydrogenation flow container；(9) the hydride in hydrogenation flow container is by hydrogen Change liquid pump feeding oxidizing tower to be aoxidized；(10) the hydride of hydride pump discharge also recoils to each catalyst filter in turn, The catalyst punching that catalyst filter is retained falls, and enters working solution supply pipe through triple valve and catalyst filter flow reversal pipe, follows new Fresh working solution is returned in hydrogenation reaction cauldron；(11) in oxidizing tower, compressed air be allocated to numerous bubbles from oxidation tower bottom to Upper to flow and successively pass through the air-vent on oxidation tower tray, hydride enters from oxidizing tower top, opened from the oxidation tower tray of top layer Begin successively advection, and next layer is then dropped down onto down, hydride one side advection on each layer oxidation tower tray while with the oxygen in bubble Generation oxidation reaction, oxidation solution efferent duct output of the oxidation solution from oxidation tower bottom；Step (1) middle hydrogenation solvent formula one Percent by volume be：Diisobutyl carbinol (DIBC)（45~50）V%, C10 aromatic hydrocarbons（50~55）V%, both volume summations are 100%；Step Suddenly the percent by volume of (1) middle hydrogenation solvent formula two is：Tetrabutyl urea（12~30）V%, trioctyl phosphate（8~12） V%, C10 aromatic hydrocarbons：（60~76）V%, the volume summation of three is 100%.
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CN201686492U (en) * 2010-04-29 2010-12-29 扬州惠通化工技术有限公司 Hydrogenation system for producing hydrogen peroxide
CN103964394A (en) * 2014-05-07 2014-08-06 无锡安竣化学工程科技有限公司 Hydrogenation system for hydrogen peroxide production
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998028225A1 (en) * 1996-12-23 1998-07-02 Kvaerner Process Systems A/S Method for the production of hydrogen peroxide by hydrating a chinone solution and arrangement for performing the methods
CN1817838A (en) * 2006-02-17 2006-08-16 黎明化工研究院 Hydrogenation process of hydrogen peroxide fluidized bed by anthraquinone
CN101037189A (en) * 2007-03-06 2007-09-19 黑龙江黑化集团有限公司 Modified apparatus and method for preparing 35 percent hydrogen peroxide by using hydrogen with low purity of 90 percent
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