CN107473188A - It is a kind of to use the anthraquinone production technology for preparing hydrogen peroxide - Google Patents
It is a kind of to use the anthraquinone production technology for preparing hydrogen peroxide Download PDFInfo
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- CN107473188A CN107473188A CN201710872590.0A CN201710872590A CN107473188A CN 107473188 A CN107473188 A CN 107473188A CN 201710872590 A CN201710872590 A CN 201710872590A CN 107473188 A CN107473188 A CN 107473188A
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- anthraquinone
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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 discloses a kind of using the anthraquinone production technology for preparing hydrogen peroxide, comprise the following steps：It is sequentially connected in series hydrogenation supergravity reactor, oxidation supergravity reactor and extraction supergravity reactor；Hydrogen and the solution containing anthraquinone are inputted into progress gas-liquid two-phase in feed cavity efficiently to mix, gas-liquid mixture is formed and carries out hydrogenation reaction, obtain the working solution containing hydrogen anthraquinone；Oxygen and the working solution containing hydrogen anthraquinone are inputted into progress gas-liquid two-phase in feed cavity efficiently to mix, gas-liquid mixture is formed and carries out oxidation reaction, obtain the working solution containing hydrogen peroxide and anthraquinone；Working solution containing hydrogen peroxide and anthraquinone and deionized water are entered into extraction supergravity reactor to be extracted；Separated after extraction, obtain hydrogen peroxide；The production technology can make slightly solubility hydrogen reach supersaturation in liquid phase dissolved degree, efficiently using reductive hydrogen, strengthen gas-liquid-solid phase mass transfer；The Jia hydrogen Xiao Shuai≤13g/L of the inventive method, oxidation reaction Zhuanization Shuai≤95%.
Description
Technical field
The invention belongs to catalytic hydrogenation reaction technical field, the anthraquinone hydrogen peroxide for preparing is used more particularly, to a kind of
Production technology.
Background technology
Hydrogen peroxide is (also referred to as：Hydrogen peroxide) it is important petrochemical materials and fine chemical product, as green oxidation
Agent, bleaching agent, disinfectant, papermaking, medicine, chemicals synthesis, electronics, food processing, weaving, environment have been widely used in it
The numerous areas such as protection.China's large-scale production hydrogen peroxide is started late, but production capacity rapid development, from 1984 annual productions only
There are 2.8 ten thousand tons to 2014 annual productions up to 9,000,000 tons.
Hydrogen peroxide application is very extensive, and has the advantages of many unique, therefore the demand of hydrogen peroxide is very big always, with
Some new opplications of hydrogen peroxide and from environmental angle, according to statistics, the demand of whole world hydrogen peroxide is at one section from now on
Time will continue to rise.At present, the production method of hydrogen peroxide has isopropanol method, electrolysis, hydrogen-oxygen directly to synthesize in the world
Method, cathode anode reducing process, vacuum concentration method and anthraquinone etc., with production cost and the influence of environmental protection, many methods
All gradually it is eliminated, and anthraquinone was produced both at home and abroad at present because its mild condition, safe, technical maturity become
The most important method of hydrogen oxide.It is anthraquinone using anthraquinone as working material, by hydrogenating, aoxidizing, extracting, the process such as post-processing
Obtain hydrogen peroxide.
It is described it is anthraquinone prepare hydrogen peroxide specific course of reaction it is as follows：
(1), hydrogenation reaction：
(2), oxidation reaction：
Domestic anthraquinone hydrogenation technique is based on fixed bed, though palladium catalyst fixed-bed process is simple to operate, catalyst
Without separation, but there is also open defect, such as each several part reaction is uneven, easily forms short circuit, causes hot localised points, easily production
Raw working solution degraded, catalyst is crushed, lumpd, utilization rate is low, and reaction speed is extended influence by hydrogen, domestic widely used solid
Fixed bed hydrogenation efficiency is (with H2O2Meter) 6g/L-7g/L is generally, compared with the fluidized-bed hydrogenation efficiency that foreign countries use, exist huge
Gap.But whether fixed-bed process or fluidized-bed process, in addition to hydrogenation reactor is different, the basic phase of other parts
Together.
Anthraquinone hydrogenation reaction is gas-liquid-solid phase reaction.No matter with fixed bed reactors or fluidized-bed reactor, hydrogen
Participate in reacting, catalyst surface need to be got to by liquid phase mass transfer, liquid-solid phase mass transfer.If the resistance to mass tranfer of liquid phase
Big or liquid-solid phase resistance to mass tranfer is big, and reaction rate is more than mass transfer rate, and reaction rate is by mass transport limitation, and it is anti-to be unfavorable for hydrogenation
The progress answered.Simultaneously because liquid phase axial direction, radial distribution uneven phenomenon, cause reactor low locally by efficiency, catalyst
Bed local hydriding excessively causes to lump, and is further exacerbated by bias current so that bed resistance rises rapidly and can not production operation.Cause
This, it is desirable to improve the efficiency of hydrogenation reaction, strengthen improvement to reactor, it is necessary to strengthen mass transfer between gas-liquid and liquid it is solid between biography
Matter.
The oxidation of hydride at present is carried out in the oxidizing tower with disperser, and existing mode of oxidizing and oxidation are set
It is standby that there is following shortcoming：Air flow method is uneven, and gas-liquid contact is insufficient, and mass transfer effect is poor, air utilization ratio and oxidation
Efficiency is low；It is incomplete to hydrogenate liquid oxidation, has aggravated the burden of subsequent handling, operation is unstable；Inhomogeneous cooling is even, and hydrogen peroxide easily divides
Solution.Therefore oxidizing process is all the biography between mass transfer, the liquid that must strengthen between gas-liquid are consolidated as hydrogenation process problems faced
Matter, so as to improve the efficiency of hydrogenation reaction.
High-gravity technology obtains more impressive progress, CN103102942A in the application study of field of chemical engineering in recent years
Feedstock oil is successfully passed through the supergravity reactor equipped with non-precious metal catalyst, desulfurization is carried out with hydrogen counter current contacting, takes off
Nitrogen and part aromatic hydrocarbons saturated reaction, but by the way of catalyst is loaded, operating process is difficult, and course of reaction pressure drop is larger, urges
Agent easily inactivates；Metal-polymer catalyst is fixed on the rotor of rotating packed bed reactor by CN104419454A,
Drippolene and hydrogen carry out selective hydrogenation reaction by the beds being rotating, but not specific proposition monoblock type is urged
The raw material proportioning and fixing means of agent fixation procedure.If reacting anthraquinone hydrogenation using traditional supergravity reactor, hydrogen exists
What is dissolved in solution is not that a lot, the reaction is still by mass transfer and limit, therefore, it is desirable to improve the efficiency of hydrogenation reaction, strengthen
Improvement to reactor, it is necessary to strengthen mass transfer between gas-liquid and liquid it is solid between mass transfer.
The content of the invention
The anthraquinone production technology for preparing hydrogen peroxide is used the technical problem to be solved in the present invention is to provide a kind of.The life
The reactor that production. art uses can make slightly solubility hydrogen reach supersaturation in liquid phase dissolved degree, efficiently using reductive hydrogen, by force
Change gas-liquid-solid phase mass transfer；The Jia hydrogen Xiao Shuai≤13g/L of the inventive method, oxidation reaction Zhuanization Shuai≤95%.
In order to solve the above technical problems, invention adopts the following technical scheme that：
It is a kind of using the anthraquinone production technology for preparing hydrogen peroxide, comprise the following steps：
S1, selection supergravity reactor
It is sequentially connected in series hydrogenation supergravity reactor, oxidation supergravity reactor and extraction supergravity reactor；The hydrogenation
Supergravity reactor and oxidation supergravity reactor include motor, main shaft, rotor, housing and liquid distribution trough；The motor is defeated
The main shaft for going out end is extend into housing through housing bottom, and the rotor is fixed on main shaft top；The super-gravity device also wraps
Include secondary axes, speed increaser, output shaft of the speed increaser and feed cavity；The feed cavity is arranged on the top of housing, and the bottom of feed cavity connects
Connect liquid distribution trough；The main shaft is fixedly connected by secondary axes with speed increaser, and the output shaft of the speed increaser passes through feed cavity bottom
It extend into feed cavity；The feed cavity inside points of the output shaft of the speed increaser are provided with agitator；The feed cavity is provided with the
One gas access, liquid inlet and catalyst inlet, the lower housing portion are provided with gas liquid outlet；The housing upper is provided with gas
Gateway, the housing side are provided with second gas entrance；
S2, hydrogenation supergravity reactor is started, speed increaser rotation is driven, so as to drive the agitator ultrahigh speed in feed cavity
Rotation；Hydrogen and the solution containing anthraquinone are inputted into progress gas-liquid two-phase in feed cavity efficiently to mix, make slightly solubility hydrogen in anthracene
Be dispersed into quinone solution it is substantial amounts of receive micron bubble, solubility of the hydrogen in the solution containing anthraquinone reaches supersaturation, formed
Gas-liquid mixture；Gas-liquid mixture is delivered into the rotor containing hydrogenation catalyst by liquid distribution trough and be hydrogenated with instead
Should, obtain the working solution containing hydrogen anthraquinone；
S3, oxidation supergravity reactor motor is started, speed increaser rotation is driven, so as to drive the agitator in feed cavity to surpass
Rotate at a high speed；Oxygen and the working solution containing hydrogen anthraquinone are inputted into progress gas-liquid two-phase in feed cavity efficiently to mix, make slightly solubility
Oxygen be dispersed into the working solution containing hydrogen anthraquinone it is substantial amounts of receive micron bubble, oxygen is in the working solution containing hydrogen anthraquinone
Solubility reaches supersaturation, forms gas-liquid mixture；Gas-liquid mixture is delivered into containing oxidation instead by liquid distribution trough
Answer and oxidation reaction is carried out in the rotor of catalyst, obtain the working solution containing hydrogen peroxide and anthraquinone；
S4, extraction supergravity reactor motor is started, by the working solution containing hydrogen peroxide and anthraquinone and deionized water one
Rise by liquid distribution trough deliver into extract supergravity reactor extracted, working solution after being extracted；
Working solution is separated through oil water separator again after S5, extraction；Wherein water layer is dioxygen aquatic products, is located after organic layer
Posterior circle is managed to use.
As the further improvement of technical scheme, the speed increasing ratio of the speed increaser is 1：5-1:10000.
As the further improvement of technical scheme, the material of the agitator include titanium alloy, chromium-base alloy, dual phase steel or
Ceramics etc..
As the further improvement of technical scheme, in step S2, the hydrogenation catalyst is load type palladium catalyst；Carrier
For the pelleted substrate with hollow-core construction, the graininess includes annular spherical, Rasching ring, wheel, porous bar shaped, three leaves
One or more in careless type or porous annular.
Preferably, the carrier is aluminum oxide.
Preferably, the loading of palladium is 0.01wt%-1wt% in the load type palladium catalyst.
It is highly preferred that the load type palladium catalyst is Pd/Al2O3Catalyst, it is the spheric granules of 1-10mm diameters, or
Draw ratio is 1:1-1:10th, a diameter of 1-10mm Raschig ring type particle or trifolium-shaped particle.
As the further improvement of technical scheme, in step S2, the solution containing anthraquinone is by 1,3,5- trimethylbenzene, phosphorus
The volume ratio of sour three monooctyl esters and 2- EAQs composition, 1,3,5- trimethylbenzene and trioctyl phosphate is 75:25-80:20；The 2-
The concentration of EAQ is 90-120g/L.
As the further improvement of technical scheme, in step S2, the volume ratio of the hydrogen and the solution containing anthraquinone is
10:1-15:1。
Preferably, the hydrogenation reaction of the hydrogenation supergravity reactor is carried out under the conditions of 20-100 DEG C.
As the further improvement of technical scheme, in step S2, also to urging before inputting hydrogen and solution containing anthraquinone
Agent carries out reduction activation processing, is specially：Hydrogenation supergravity reactor is heated to 50-80 DEG C, is passed through hydrogen reducing activation
After 1-20h, drained with nitrogen.
As the further improvement of technical scheme, in step S3, the oxidation reaction catalyst is aminated compounds.
As the further improvement of technical scheme, in step S3, the volume of the oxygen and the working solution containing hydrogen anthraquinone
Than for 10:1-15:1.
Preferably, in step S3, the oxidation reaction in the oxidation supergravity reactor is carried out under the conditions of 20-100 DEG C.
As the further improvement of technical scheme, in step S5, by obtained organic layer through drying regeneration and alkali sedimentation system
Used after system in return to step S2 with the solution mixing circulation containing anthraquinone.Cost can be reduced well.
Any scope described in the present invention includes any numerical value and end value or end value between end value and end value
Between any subrange for being formed of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention
The conventional equipment in art or the prior art with reference to art can be used to carry out.
Compared with prior art, the present invention has the advantages that：
1) bubble in the liquid phase grow by existence time：Common gas-liquid is simply mixed after bubble produces in the liquid phase in device, meeting
Rapidly rise to liquid phase surface and rupture disappearance, existence time is very short；And pass through micro-nano caused by gas liquid high-efficiency pre-mixing apparatus
Rice bubble is once generation, and the rate of climb in water is slower, and the course from producing rupture generally reaches tens seconds even rather
Clock, and volume is constantly shunk in uphill process and final dissolving disappears in water, and volume smaller gas ducks in drink
The rate of climb is slower；
2) gas-liquid mass transfer efficiency high, when bubble diameter is smaller, the surface tension of microbubble interface is to Bubble Characteristics
The more notable of performance is influenceed, surface tension at this moment produces compression to internal gas so that micron bubble was rising
Constantly shunk in journey and show itself supercharging.With the unlimited diminution of bubble diameter, the specific surface area of bubble interface is also therewith
Unlimited increase, finally because itself pressurized effect causes air pressure inside to increase to infinity.Therefore, have so that more gases
It is dissolved into through gas-liquid interface in water, may be such that mass-transfer efficiency persistently strengthens at gas-liquid interface, and micro- gas that this characteristic makes
Even if the gas content of bubble in the liquid phase reaches supersaturated condition, it may continue to carry out the mass transport process of gas and keep efficient
Mass-transfer efficiency.Reaction and the dissolving of gas are simultaneous, and while vapor-phase reactant is consumed, micron bubble of receiving crushes
Dissolving and macroscopical gas phase the mass transfer dissolving into liquid phase are carried out simultaneously, and gas can be supplemented within the very first time；
3) in terms of reducing reaction pressure：As improved hydrogen using the method for improving pressure mostly in hydrogenation plant at this stage
The dissolving of gas in the solution, such as reached before entering the reactor using the gas liquid high-efficiency mixing arrangement of the present invention, liquid phase
Supersaturation, and due to high efficient gas and liquid mixing arrangement Gas content in liquid phase can be made to may be up to 90%, micron even nano bubble
The redissolution for carrying out gas phase is crushed in the liquid phase, therefore the partial pressure of hydrogen can be reduced suitably in actual reactor, reduce investment
Cost；
4) flow is simplified, it is not necessary to circulating hydrogen compressor, reduces investment and energy consumption, the production cost of device substantially drop
It is low；
5) supergravity reactor can greatly strengthen gas-liquid/liquid-liquid mass transfer, improve the solubility of hydrogen, fortifying catalytic hydrogenation
Reaction and oxidation reaction, reaction velocity is high, reactor volume is small；
6) reaction temperature rising is small, hot localised points is not present in reactor, catalyst is not easy coking；
7) catalyst has preferable stability and selectivity under the conditions of Continuous Liquid Phase hydrogen addition technology, can meet industrial length
The needs of period run；
In summary, the Jia hydrogen Xiao Shuai≤13g/L of the inventive method, oxidation reaction Zhuanization Shuai≤95%.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings
Fig. 1 shows supergravity reactor structural representation of the present invention；
Fig. 2 shows that the present invention uses the anthraquinone production technological process for preparing hydrogen peroxide.
Embodiment
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, and this should not be limited with this
The protection domain of invention.
Narration is intended merely to using noun of locality " upper and lower, left and right " etc. conveniently, those skilled in the art can in the present invention
Know, these orientation are relative, may be changed by modes such as rotations.
Hydrogenation supergravity reactor and oxidation supergravity reactor shown in Figure 1, being used in the present invention, including motor
1st, main shaft 2, rotor 3, housing 4 and liquid distribution trough 14；The main shaft 2 of the motor output end extend into housing through housing bottom
In 4, the rotor 3 is fixed on the top of main shaft 2；The supergravity reactor also includes secondary axes 17, speed increaser 15, speed increaser output
Axle 6 and feed cavity 7；The feed cavity 7 is arranged on the top of housing 4, the bottom connection liquid distribution trough 14 of feed cavity 7；It is described
Main shaft 2 is fixedly connected by secondary axes 17 with speed increaser 15, and the output shaft of the speed increaser 6 extend into charging through the bottom of feed cavity 7
In chamber 7；The feed cavity inside points of the output shaft of the speed increaser 6 are provided with agitator 11；The feed cavity 7 is provided with first gas
Entrance 10, liquid inlet 8 and catalyst inlet 9, the bottom of housing 4 are provided with gas liquid outlet 16；The top of housing 4 is provided with gas
Body gateway 12, the housing side are provided with second gas entrance 13；Sealing 5 is provided between rotor 3 and housing 4；
Fig. 2 shows that the present invention uses the anthraquinone production technological process for preparing hydrogen peroxide.
The implication that each several part represents in figure as：
101- hydrogen gas cylinders；102- hydrogen gas cylinders；103- pressure-regulating valves；104- head tanks；105- mass flowmenters；
106- coolers；107- is hydrogenated with supergravity reactor；108- fluid reservoirs；109- charge pumps；110- oxygen bottles；
111- aoxidizes supergravity reactor；112- fluid reservoirs；113- extractant tanks；114- extracts supergravity reactor；
115- oil water separators；116- clarifiers；117- driers；118- caustic settlers.
It is a kind of using the anthraquinone production technology for preparing hydrogen peroxide, comprise the following steps：
S1, selection supergravity reactor
It is sequentially connected in series hydrogenation supergravity reactor 107, oxidation supergravity reactor 111 and extraction supergravity reactor 114；
S2, the hydrogenation motor of supergravity reactor 107 is started, drive speed increaser 15 to rotate, so as to drive stirring in feed cavity 7
Mix the rotation of the ultrahigh speed of the wing 11；Hydrogen and the interior gas-liquid two-phase that carries out of solution input feed cavity 7 containing anthraquinone are efficiently mixed, make difficulty
Dissolubility hydrogen be dispersed into anthraquinone solution it is substantial amounts of receive micron bubble, solubility of the hydrogen in the solution containing anthraquinone reaches
Supersaturation, form gas-liquid mixture；Gas-liquid mixture is delivered into by liquid distribution trough 14 and turned containing hydrogenation catalyst
Hydrogenation reaction is carried out in son 3, obtains the working solution containing hydrogen anthraquinone；
S3, the oxidation motor of supergravity reactor 111 is started, drive speed increaser 15 to rotate, so as to drive stirring in feed cavity 7
Mix the rotation of the ultrahigh speed of the wing 11；Hydrogen and the interior gas-liquid two-phase that carries out of working solution input feed cavity 7 containing hydrogen anthraquinone are efficiently mixed,
Make slightly solubility hydrogen be dispersed into the working solution containing hydrogen anthraquinone it is substantial amounts of receive micron bubble, hydrogen is in the work containing hydrogen anthraquinone
Make the solubility in liquid and reach supersaturation, form gas-liquid mixture；Gas-liquid mixture is delivered into by liquid distribution trough 14
Oxidation reaction is carried out in rotor containing oxidation reaction catalyst, obtains the working solution containing hydrogen peroxide and anthraquinone；
S4, the extraction motor of supergravity reactor 114 is started, by hydrogen, the working solution containing hydrogen peroxide and anthraquinone and gone
Ionized water delivers into extraction supergravity reactor 114 by liquid distribution trough 14 together and extracted, and is worked after being extracted
Liquid；
Working solution is separated through oil water separator 115 again after S5, extraction；Wherein water layer is dioxygen aquatic products, organic layer
Posterior circle is post-processed to use.
In certain embodiments of the present invention, the speed increasing ratio of the speed increaser 15 is 1：5-1:10000, or 1：5-1:
9500, or 1：5-1:9000, or 1：5-1:8500, or 1：5-1:8000, or 1：5-1:7500, or 1：5-1:7000, or 1：5-
1:6500, or 1：5-1:6000, or 1：5-1:5500, or 1：5-1:5000, or 1：5-1:4500, or 1：5-1:4000, or 1：
5-1:3500, or 1：5-1:3000, or 1：5-1:2500, or 1：5-1:2000, or 1：5-1:1500, or 1：5-1:1000, or
1：5-1:500,1：100-1:10000, or 1：100-1:9500, or 1：100-1:9000, or 1：100-1:8500, or 1：100-
1:8000, or 1：100-1:7500, or 1：100-1:7000, or 1：100-1:6500, or 1：100-1:6000, or 1：100-1:
5500, or 1：100-1:5000, or 1：100-1:4500, or 1：100-1:4000, or 1：100-1:3500, or 1：100-1:
3000, or 1：100-1:2500, or 1：100-1:2000, or 1：100-1:1500, or 1：100-1:1000
By the regulation to speed increaser, it can make it that the bubble in feed cavity 7 in the liquid phase grow by existence time：Common gas-liquid
It is simply mixed after bubble produces in the liquid phase in device, liquid phase surface can be rapidly risen to and rupture disappearance, existence time is very short；
And it is slower once generation, the rate of climb in water by micro-nano bubble caused by gas liquid high-efficiency pre-mixing apparatus, from generation
Course to rupture generally reaches tens seconds even a few minutes, and volume is constantly shunk and final in water in uphill process
Dissolving disappears, and the rate of climb that the smaller gas of volume ducks in drink is slower.
When bubble diameter is smaller, the surface tension of microbubble interface influences the more aobvious of performance to Bubble Characteristics
Write, surface tension at this moment produces compression to internal gas so that micron bubble is constantly shunk in uphill process and table
Reveal itself supercharging；With the unlimited diminution of bubble diameter, the specific surface area also unlimited increase therewith of bubble interface, finally due to
Itself pressurized effect causes air pressure inside to increase to infinity；Therefore, have so that more gases dissolve through gas-liquid interface
Into water, may be such that mass-transfer efficiency persistently strengthens at gas-liquid interface, even and if this characteristic microbubble that makes in the liquid phase
When gas content reaches supersaturated condition, it may continue to carry out the mass transport process of gas and keep efficient mass-transfer efficiency.Reaction
Dissolving with gas is simultaneous, while vapor-phase reactant is consumed, the broken dissolving of micron bubble of receiving and macroscopical gas phase
Into liquid phase, mass transfer dissolving is carried out simultaneously, and gas can be supplemented within the very first time；
The dissolving of hydrogen in the solution is improved using the method for improving pressure mostly in hydrogenation plant at this stage, and adopted
With gas liquid high-efficiency mixing arrangement (motor 1, main shaft 2, secondary axes 17, speed increaser 15, output shaft of the speed increaser 6, the agitator of the present invention
11st, feed cavity 7 etc. is collectively referred to as), liquid phase has reached supersaturation before rotor is entered, and micron even nano bubble is in liquid phase
In crush the redissolution for carrying out gas phase, therefore the partial pressure of hydrogen can be reduced suitably in actual reactor, reduce cost of investment.
In certain embodiments of the present invention, the material of the agitator includes titanium alloy, chromium-base alloy, dual phase steel or pottery
Porcelain etc..
In certain embodiments of the present invention, in step S2, the hydrogenation catalyst is load type palladium catalyst；Carrier is
Pelleted substrate with hollow-core construction, the graininess include annular spherical, Rasching ring, wheel, porous bar shaped, clover
One or more in type or porous annular.
In some preferred embodiments of the present invention, the carrier is aluminum oxide.
In certain embodiments of the present invention, the loading of palladium is 0.01wt%- in the load type palladium catalyst
1wt%, or 0.05-1wt%, or 0.05-0.8wt%, or 0.05-0.6wt%, or 0.05-0.4wt%, or 0.05-
0.2wt%, or 0.05-0.1wt%, or 0.1-1wt%, or 0.1-0.8wt%, or 0.1-0.6wt%, or 0.1-0.4wt%,
Or 0.1-0.2wt%.
In some preferred embodiments of the present invention, the load type palladium catalyst is Pd/Al2O3Catalyst, it is 1-10mm
The spheric granules of diameter, or draw ratio are 1:1-1:10th, a diameter of 1-10mm Raschig ring type particle or trifolium-shaped particle.
The present invention some preferred embodiments in, in step S2, the solution containing anthraquinone by 1,3,5- trimethylbenzene,
Trioctyl phosphate and 2- EAQs composition；The volume ratio of wherein trioctyl phosphate and 1,3,5- trimethylbenzenes is 75:25-80:2.
In some preferred embodiments of the present invention, in step S2, the volume ratio of the hydrogen and the solution containing anthraquinone
For 10:1-15:1, the concentration of the 2- EAQs is 90-120g/L.
In some preferred embodiments of the present invention, the hydrogenation reaction of the hydrogenation supergravity reactor is in 20-100 DEG C of bar
Carried out under part；Preferably, hydrogenation reaction is carried out under the conditions of 60 DEG C.
It is also right before inputting hydrogen and solution containing anthraquinone in step S2 in some preferred embodiments of the present invention
Catalyst carries out reduction activation processing, is specially：Hydrogenation supergravity reactor is heated to 50-80 DEG C, is passed through hydrogen reducing work
After changing 1-20h, drained with nitrogen.
In some preferred embodiments of the present invention, in step S3, the oxidation reaction catalyst is aminated compounds.
In some preferred embodiments of the present invention, in step S3, the body of the oxygen and the working solution containing hydrogen anthraquinone
Product is than being 10:1-15:1.
Preferably, in step S3, the oxidation reaction in the oxidation supergravity reactor is carried out under the conditions of 20-100 DEG C；
Preferably, hydrogenation reaction is carried out under the conditions of 60 DEG C.
In some preferred embodiments of the present invention, in step S5, obtained organic layer is settled through drying regeneration and alkali
Used after system in return to step S2 with the solution mixing circulation containing anthraquinone.Cost can be reduced well.
In some preferred embodiments of the present invention, the micron bubble size Control of receiving is at 30nm-300 μm, or 30nm-
250 μm, or 30nm-200 μm, or 30nm-150 μm, or 30nm-100 μm, or 30nm-50 μm, or 30nm-10 μm, or 30nm-1
μm, or 100nm-300 μm, or 100nm-250 μm, or 100nm-200 μm, or 100nm-100 μm, or 100nm-1 μm.
In some preferred embodiments of the present invention, the rotating speed of supergravity reactors at different levels can be controlled in 200-2800rpm,
Or 200-2500rpm, or 200-2000rpm, or 200-1500rpm, or 200-1000rpm, or 200-500rpm, or 400-
2500rpm, or 400-2000rpm, or 400-1500rpm, or 400-1000rpm；Liquid phase residence time in rotor is controllable
System is in 50-2000ms.
Embodiment 1
As shown in Fig. 2 it is a kind of using the anthraquinone production technology for preparing hydrogen peroxide, comprise the following steps：
(1) by Pd/Al2O3Catalyst packing pours into the solution containing anthraquinone in the rotor of hydrogenation supergravity reactor
In head tank, charge pump feed pump is opened so that liquid circulation, fully soak catalyst；
The solution containing anthraquinone is made up of 1,3,5- trimethylbenzenes, trioctyl phosphate and 2- EAQs；1,3,5- tri-
The volume ratio of toluene and trioctyl phosphate is 75:25；The concentration of 1,3,5- trimethylbenzenes is 660mL/L；The concentration of trioctyl phosphate
For 220mL/L；；The concentration of 2- EAQs is 120g/L.
(2) it is passed through nitrogen purging hydrogenation rotating packed bed reactor；After being passed through hydrogen reducing activation 1-24h, nitrogen is used
Drain；Hypergravity hydrogenation reactor is opened, regulation hypergravity hydrogenation reactor rotating speed is 1000r/min, the solution containing anthraquinone
By feed tube spray be sprinkled upon on the reactor wall of rotation, on the reactor wall the following current of both hydrogen and the solution containing anthraquinone or
Counter current contacting is reacted；
(3) hydrogenation process conditions：60 DEG C of reaction temperature, reaction pressure 0.2MPa；
(4) working solution containing hydrogen anthraquinone obtained after hydrogenation reaction is entered into oxidation supergravity reactor by charge pump
It is interior, it is passed through oxygen；Hypergravity hydrogenation reactor is opened, regulation rotating speed is 600r/min, oxygen and the working solution containing hydrogen anthraquinone
Both following currents or counter current contacting reaction；
(5) oxidation process conditions：65 DEG C of reaction temperature, reaction pressure 0.3MPa；
(6) working solution containing hydrogen peroxide and anthraquinone enters with deionized water cocurrent extracts high-gravity rotating bed, unlatching
High-gravity rotating bed, regulation rotating speed is 800r/min, and the working solution containing hydrogen peroxide and anthraquinone is sprayed by feed tube is sprinkled upon rotation
On the reactor wall turned, deionized water extracts with aoxidizing both working solution following currents or counter current contacting on the reactor wall；
(7) liquid to be extracted enters oil water separator, and extract goes out at the top of separator, into purification utensil, obtained
To product hydrogen peroxide；Raffinate goes out from separator bottom, obtains regenerating the solution containing anthraquinone by drier, caustic settler and follows
Ring uses.
After testing, the hydrogenation efficiency of the inventive method is 14g/L, and oxidation reaction conversion ratio is 98.5%
Comparative example 1
Hydrogenation supergravity reactor and oxidation supergravity reactor replace with traditional supergravity reactor, such as
The reactor that CN106430108A is used, under identical operating conditions, hydrogenation efficiency 6.2g/L.
Embodiment 2
As shown in Fig. 2 it is a kind of using the anthraquinone production technology for preparing hydrogen peroxide, comprise the following steps：
(1) by Pd/Al2O3Catalyst packing pours into the solution containing anthraquinone in the rotor of hydrogenation supergravity reactor
In head tank, charge pump feed pump is opened so that liquid circulation, fully soak catalyst；
The solution containing anthraquinone is made up of 1,3,5- trimethylbenzenes, trioctyl phosphate and 2- EAQs；Wherein 1,3,
The volume ratio of 5- trimethylbenzenes and trioctyl phosphate is 80:25；The concentration of 1,3,5- trimethylbenzenes is 760mL/L；Trioctyl phosphate
Concentration is 240mL/L；；The concentration of 2- EAQs is 110g/L；
(2) it is passed through nitrogen purging hydrogenation rotating packed bed reactor；After being passed through hydrogen reducing activation 1-24h, nitrogen is used
Drain；Hydrogen supergravity reactor is opened, regulation rotating packed bed reactor rotating speed is 900r/min, the solution containing anthraquinone
By feed tube spray be sprinkled upon on the reactor wall of rotation, on the reactor wall the following current of both hydrogen and the solution containing anthraquinone or
Counter current contacting is reacted；
(3) hydrogenation process conditions：60 DEG C of reaction temperature, reaction pressure 0.2MPa；
(4) working solution containing hydrogen anthraquinone obtained after hydrogenation reaction is entered into oxidation supergravity reactor by charge pump
It is interior, it is passed through oxygen；Rotating packed bed reactor is opened, regulation rotating speed is 500r/min, oxygen and the work containing hydrogen anthraquinone
The following current of both liquid or counter current contacting reaction；
(5) oxidation process conditions：65 DEG C of reaction temperature, reaction pressure 0.3MPa；
(6) working solution containing hydrogen peroxide and anthraquinone enters in extraction supergravity reactor with deionized water cocurrent, opens
Rotating packed bed reactor is opened, regulation revolving bed rotating speed is 700r/min, and the working solution containing hydrogen peroxide and anthraquinone is by entering
Liquid pipe, which sprays, to be sprinkled upon on the reactor wall of rotation, and deionized water is with aoxidizing both working solution following current or adverse current on the reactor wall
Contact extraction；
(7) liquid to be extracted enters oil water separator, and extract goes out at the top of separator, into purification utensil, obtained
To product hydrogen peroxide；Raffinate goes out from separator bottom, obtains regenerating the solution containing anthraquinone by drier, caustic settler and follows
Ring uses.
After testing, the hydrogenation efficiency of the inventive method is 13.5g/L, and oxidation reaction conversion ratio is 97.2%.
Comparative example 2
Hydrogenation supergravity reactor and oxidation supergravity reactor replace with traditional supergravity reactor, such as CN
The reactor that CN103102942A is used, under identical operating conditions, hydrogenation efficiency 5.9g/L.
Embodiment 3
As shown in Fig. 2 it is a kind of using the anthraquinone production technology for preparing hydrogen peroxide, comprise the following steps：
(1) by Pd/Al2O3Catalyst packing pours into the solution containing anthraquinone in the rotor of hydrogenation supergravity reactor
In head tank, charge pump is opened so that liquid circulation, fully soak catalyst；
The solution containing anthraquinone is made up of 1,3,5- trimethylbenzenes, trioctyl phosphate and 2- EAQs；Wherein 1,3,
The volume ratio of 5- trimethylbenzenes and trioctyl phosphate is 80:20；The concentration of 1,3,5- trimethylbenzenes is 800mL/L；Trioctyl phosphate
Concentration is 200mL/L；；The concentration of 2- EAQs is 110g/L.
(2) it is passed through nitrogen purging hydrogenation rotating packed bed reactor；After being passed through hydrogen reducing activation 1-24h, nitrogen is used
Drain；Hydrogen supergravity reactor is opened, regulation rotating packed bed reactor rotating speed is 800r/min, the solution containing anthraquinone
By feed tube spray be sprinkled upon on the reactor wall of rotation, on the reactor wall the following current of both hydrogen and the solution containing anthraquinone or
Counter current contacting is reacted；
(3) hydrogenation process conditions：60 DEG C of reaction temperature, reaction pressure 0.2MPa；
(4) working solution containing hydrogen anthraquinone obtained after hydrogenation reaction is entered into oxidation supergravity reactor by charge pump
It is interior, it is passed through oxygen；Rotating packed bed reactor is opened, regulation rotating speed is 400r/min, oxygen and the work containing hydrogen anthraquinone
The following current of both liquid or counter current contacting reaction；
(5) oxidation process conditions：65 DEG C of reaction temperature, reaction pressure 0.3MPa；
(6) working solution containing hydrogen peroxide and anthraquinone enters in extraction supergravity reactor with deionized water cocurrent, opens
Rotating packed bed reactor is opened, regulation revolving bed rotating speed is 600r/min, and the working solution containing hydrogen peroxide and anthraquinone is by entering
Liquid pipe, which sprays, to be sprinkled upon on the reactor wall of rotation, and deionized water is with aoxidizing both working solution following current or adverse current on the reactor wall
Contact extraction；
(7) liquid to be extracted enters oil water separator, and extract goes out at the top of separator, into purification utensil, obtained
To product hydrogen peroxide；Raffinate goes out from separator bottom, obtains regenerating the solution containing anthraquinone by drier, caustic settler and follows
Ring uses.
After testing, the hydrogenation efficiency of the inventive method is 13.3g/L, and oxidation reaction conversion ratio is 96%.
Comparative example 3
Hydrogenation supergravity reactor and oxidation supergravity reactor replace with traditional supergravity reactor, such as CN
The reactor that CN104419454A is used, under identical operating conditions, hydrogenation efficiency 5.5g/L.
Embodiment 4
As shown in Fig. 2 it is a kind of using the anthraquinone production technology for preparing hydrogen peroxide, comprise the following steps：
(1) by Pd/Al2O3Catalyst packing pours into the solution containing anthraquinone in the rotor of hydrogenation supergravity reactor
In head tank, charge pump is opened so that liquid circulation, fully soak catalyst；
The solution containing anthraquinone is made up of 1,3,5- trimethylbenzenes, trioctyl phosphate and 2- EAQs；Wherein 1,3,
The volume ratio of 5- trimethylbenzenes and trioctyl phosphate is 80:20；The concentration of 1,3,5- trimethylbenzenes is 800mL/L；Trioctyl phosphate
Concentration is 200mL/L；；The concentration of 2- EAQs is 110g/L.
(2) it is passed through nitrogen purging hydrogenation rotating packed bed reactor；After being passed through hydrogen reducing activation 1-24h, nitrogen is used
Drain；Hydrogen supergravity reactor is opened, regulation rotating packed bed reactor rotating speed is 700r/min, the solution containing anthraquinone
By feed tube spray be sprinkled upon on the reactor wall of rotation, on the reactor wall the following current of both hydrogen and the solution containing anthraquinone or
Counter current contacting is reacted；
(3) hydrogenation process conditions：60 DEG C of reaction temperature, reaction pressure 0.2MPa；
(4) working solution containing hydrogen anthraquinone obtained after hydrogenation reaction is entered into oxidation supergravity reactor by charge pump
It is interior, it is passed through oxygen；Rotating packed bed reactor is opened, regulation rotating speed is 300r/min, oxygen and the work containing hydrogen anthraquinone
The following current of both liquid or counter current contacting reaction；
(5) oxidation process conditions：65 DEG C of reaction temperature, reaction pressure 0.3MPa；
(6) working solution containing hydrogen peroxide and anthraquinone enters in extraction supergravity reactor with deionized water cocurrent, opens
Rotating packed bed reactor is opened, regulation revolving bed rotating speed is 500r/min, and the working solution containing hydrogen peroxide and anthraquinone is by entering
Liquid pipe, which sprays, to be sprinkled upon on the reactor wall of rotation, and deionized water is with aoxidizing both working solution following current or adverse current on the reactor wall
Contact extraction；
(7) liquid to be extracted enters oil water separator, and extract goes out at the top of separator, into purification utensil, obtained
To product hydrogen peroxide；Raffinate goes out from separator bottom, obtains regenerating the solution containing anthraquinone by drier, caustic settler and follows
Ring uses.
After testing, the hydrogenation efficiency of the inventive method is 13.1g/L, and oxidation reaction conversion ratio is 95.6%
Comparative example 3
Hydrogenation supergravity reactor and oxidation supergravity reactor replace with traditional supergravity reactor, such as CN
The reactor that CN104419454A is used, under identical operating conditions, hydrogenation efficiency 6.1g/L.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms.Here all embodiments can not be exhaustive.It is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (10)
1. a kind of use the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that comprises the following steps：
S1, selection supergravity reactor
It is sequentially connected in series hydrogenation supergravity reactor, oxidation supergravity reactor and extraction supergravity reactor；The hydrogenation is overweight
Power reactor and oxidation supergravity reactor include motor, main shaft, rotor, housing and liquid distribution trough；The motor output end
Main shaft extend into through housing bottom in housing, the rotor is fixed on main shaft top；The super-gravity device also includes secondary
Axle, speed increaser, output shaft of the speed increaser and feed cavity；The feed cavity is arranged on the top of housing, the bottom connection liquid of feed cavity
Body distributor；The main shaft is fixedly connected by secondary axes with speed increaser, and the output shaft of the speed increaser stretches into through feed cavity bottom
Into feed cavity；The feed cavity inside points of the output shaft of the speed increaser are provided with agitator；The feed cavity is provided with the first gas
Body entrance, liquid inlet and catalyst inlet, the lower housing portion are provided with gas liquid outlet；The housing upper comes in and goes out provided with gas
Mouthful, the housing side is provided with second gas entrance；
S2, hydrogenation supergravity reactor is started, speed increaser rotation is driven, so as to drive the agitator ultrahigh speed in feed cavity to revolve
Turn；Hydrogen and the solution containing anthraquinone are inputted into progress gas-liquid two-phase in feed cavity efficiently to mix, make slightly solubility hydrogen in anthraquinone
Be dispersed into solution it is substantial amounts of receive micron bubble, solubility of the hydrogen in the solution containing anthraquinone reaches supersaturation, forms gas
Liquid mixture；Gas-liquid mixture is delivered into the rotor containing hydrogenation catalyst by liquid distribution trough and be hydrogenated with instead
Should, obtain the working solution containing hydrogen anthraquinone；
S3, oxidation supergravity reactor motor is started, speed increaser rotation is driven, so as to drive the agitator ultrahigh speed in feed cavity
Rotation；Oxygen and the working solution containing hydrogen anthraquinone are inputted into progress gas-liquid two-phase in feed cavity efficiently to mix, make slightly solubility oxygen
Be dispersed into the working solution containing hydrogen anthraquinone it is substantial amounts of receive micron bubble, dissolving of the oxygen in the working solution containing hydrogen anthraquinone
Degree reaches supersaturation, forms gas-liquid mixture；Gas-liquid mixture is delivered into by liquid distribution trough and urged containing oxidation reaction
Oxidation reaction is carried out in the rotor of agent, obtains the working solution containing hydrogen peroxide and anthraquinone；
S4, extraction supergravity reactor motor is started, the working solution containing hydrogen peroxide and anthraquinone and deionized water are led to together
Cross liquid distribution trough deliver into extraction supergravity reactor extracted, working solution after being extracted；
Working solution is separated through oil water separator again after S5, extraction；Wherein water layer is dioxygen aquatic products, after organic layer post processing
Recycle.
2. according to claim 1 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：The speed increaser
Speed increasing ratio be 1：5-1:10000, or 1：5-1:9500, or 1：5-1:9000, or 1：5-1:8500, or 1：5-1:8000, or
1：5-1:7500, or 1：5-1:7000, or 1：5-1:6500, or 1：5-1:6000, or 1：5-1:5500, or 1：5-1:5000,
Or 1：5-1:4500, or 1：5-1:4000, or 1：5-1:3500, or 1：5-1:3000, or 1：5-1:2500, or 1：5-1:
2000, or 1：5-1:1500, or 1：5-1:1000, or 1：5-1:500,1：100-1:10000, or 1：100-1:9500, or 1：
100-1:9000, or 1：100-1:8500, or 1：100-1:8000, or 1：100-1:7500, or 1：100-1:7000, or 1：
100-1:6500, or 1：100-1:6000, or 1：100-1:5500, or 1：100-1:5000, or 1：100-1:4500, or 1：
100-1:4000, or 1：100-1:3500, or 1：100-1:3000, or 1：100-1:2500, or 1：100-1:2000, or 1：
100-1:1500, or 1：100-1:1000.
3. according to claim 1 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：The agitator
Material include titanium alloy, chromium-base alloy, dual phase steel or ceramics.
4. according to claim 1 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：In step S2,
The hydrogenation catalyst is load type palladium catalyst；Carrier is the pelleted substrate with hollow-core construction, and the graininess includes
Spherical, Rasching ring, wheel be annular, porous bar shaped, the one or more in trifolium-shaped or porous annular.
5. according to claim 4 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：The support type
The loading of palladium is 0.01wt%-1wt% in palladium catalyst, or 0.05-1wt%, or 0.05-0.8wt%, or 0.05-
0.6wt%, or 0.05-0.4wt%, or 0.05-0.2wt%, or 0.05-0.1wt%, or 0.1-1wt%, or 0.1-
0.8wt%, or 0.1-0.6wt%, or 0.1-0.4wt%, or 0.1-0.2wt%.
6. according to claim 4 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：The support type
Palladium catalyst is Pd/Al2O3Catalyst, Pd/Al2O3Catalyst is the spheric granules of 1-10mm diameters, or draw ratio is 1:1-1:
10th, a diameter of 1-10mm Raschig ring type particle or trifolium-shaped particle.
7. according to claim 1 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：In step S2,
The solution containing anthraquinone is made up of 1,3,5- trimethylbenzenes, trioctyl phosphate and 2- EAQs；Wherein, 1,3,5- trimethylbenzenes
Volume ratio with trioctyl phosphate is 75:25-80:20；The concentration of the 2- EAQs is 90-120g/L.
8. according to claim 1 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：In step S2,
The volume ratio of the hydrogen and the solution containing anthraquinone is 10:1-15:1；
Preferably, the hydrogenation reaction of the hydrogenation supergravity reactor is carried out under the conditions of 20-100 DEG C；Preferably, hydrogenation reaction
Carried out under the conditions of 60 DEG C.
9. according to claim 1 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：In step S3,
The oxidation reaction catalyst is aminated compounds；
Preferably, in step S3, the volume ratio of the oxygen and the working solution containing hydrogen anthraquinone is 10:1-15:1.
10. according to claim 1 using the anthraquinone production technology for preparing hydrogen peroxide, it is characterised in that：In step S3,
Oxidation reaction in the oxidation supergravity reactor is carried out under the conditions of 20-100 DEG C；Preferably, hydrogenation reaction is in 50 DEG C of bars
Carried out under part.
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| CN108503519A (en) * | 2018-03-27 | 2018-09-07 | 北京化工大学 | A kind of technique that catalysis oxidation prepares 2,3,5- trimethyl 1,4-benzoquinone |
| CN110433676A (en) * | 2019-07-19 | 2019-11-12 | 中北大学 | A kind of hypergravity micro bubble generation device and application method |
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| US20030180212A1 (en) * | 2002-03-25 | 2003-09-25 | Harold A. Huckins | Method for producing hydrogen peroxide from hydrogen and oxygen |
| CN102009960A (en) * | 2010-11-18 | 2011-04-13 | 清华大学 | Hydrogenation method for production of hydrogen peroxide by anthraquinone process |
| CN102009961A (en) * | 2010-11-18 | 2011-04-13 | 清华大学 | Oxidation method for preparing hydrogen peroxide by anthraquinone method |
| CN104549100A (en) * | 2013-10-16 | 2015-04-29 | 北京化工大学 | Novel passive super-gravity rotary bed device |
| CN106430108A (en) * | 2016-10-10 | 2017-02-22 | 中国石油大学(北京) | System and method for preparing hydrogen peroxide through anthraquinone method under supergravity condition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030180212A1 (en) * | 2002-03-25 | 2003-09-25 | Harold A. Huckins | Method for producing hydrogen peroxide from hydrogen and oxygen |
| CN102009960A (en) * | 2010-11-18 | 2011-04-13 | 清华大学 | Hydrogenation method for production of hydrogen peroxide by anthraquinone process |
| CN102009961A (en) * | 2010-11-18 | 2011-04-13 | 清华大学 | Oxidation method for preparing hydrogen peroxide by anthraquinone method |
| CN104549100A (en) * | 2013-10-16 | 2015-04-29 | 北京化工大学 | Novel passive super-gravity rotary bed device |
| CN106430108A (en) * | 2016-10-10 | 2017-02-22 | 中国石油大学(北京) | System and method for preparing hydrogen peroxide through anthraquinone method under supergravity condition |
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| CN108503519A (en) * | 2018-03-27 | 2018-09-07 | 北京化工大学 | A kind of technique that catalysis oxidation prepares 2,3,5- trimethyl 1,4-benzoquinone |
| CN110433676A (en) * | 2019-07-19 | 2019-11-12 | 中北大学 | A kind of hypergravity micro bubble generation device and application method |
| CN110433676B (en) * | 2019-07-19 | 2021-11-16 | 中北大学 | Hypergravity microbubble generation device and use method |
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