CN104926630B - A kind of method for oxidation of alkyl anthrahydroquinone and a kind of method for producing hydrogen peroxide - Google Patents
A kind of method for oxidation of alkyl anthrahydroquinone and a kind of method for producing hydrogen peroxide Download PDFInfo
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- CN104926630B CN104926630B CN201410108219.3A CN201410108219A CN104926630B CN 104926630 B CN104926630 B CN 104926630B CN 201410108219 A CN201410108219 A CN 201410108219A CN 104926630 B CN104926630 B CN 104926630B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
Abstract
Injected the invention provides a kind of method for oxidation of alkyl anthrahydroquinone, including by oxygen by average pore size for the hole of nano-scale in the solution of the anthrahydroquinone containing alkyl, obtain oxygen-containing solution；Under oxidation reaction condition, make the oxygen-containing solution in a manner of flowing up by the inner space of tubular reactor.Present invention also offers a kind of method for producing hydrogen peroxide, it is included under the conditions of hydrogenation, solution containing raw material and hydrogen are contacted with the catalyst with catalytic hydrogenation, obtain the mixture containing alkyl anthrahydroquinone, the raw material is alkyl-anthraquinone and/or alkyl hydrides anthraquinone；Alkyl anthrahydroquinone in the mixture containing alkyl anthrahydroquinone is aoxidized using method provided by the invention；Hydrogen peroxide is isolated in the mixture obtained from oxidation.The oxidation effectiveness that the method for oxidation of the present invention can also obtain under relatively low oxidizer, feed stock conversion is high and the selectivity of hydrogen peroxide is good.
Description
Technical field
The present invention relates to a kind of method for oxidation of alkyl anthrahydroquinone, the invention further relates to a kind of side for producing hydrogen peroxide
Method.
Background technology
Hydrogen peroxide is one of main basic chemical in the world, can be used as oxidant, bleaching agent, disinfectant, polymerization
Initiator and crosslinking agent, it is widely used in papermaking, weaving, chemicals synthesis, electronics, military project, food processing, medicine, cosmetics
With the numerous areas such as metallurgy.Hydrogen peroxide only produces water and oxygen after decomposing, and to environment non-secondary pollution, belongs to Green Chemistry
Product.As the development of social demand, especially ecological environmental protection are increasingly paid attention to, opened more for the application of hydrogen peroxide
For wide market.
Anthraquinone is the prevailing technology for producing in the world hydrogen peroxide, and it includes hydrogenation, oxidation, extraction and post processing and waited
Journey, wherein oxidation reaction are automatic reaction, are the important steps in anthraquinone producing hydrogen peroxide, the process to improving oxidation efficiency,
The stability and security for keeping the reaction have significant impact.
At present, the tower equipment of the oxidizing process generally use of domestic hydrogen peroxide manufacture device is realized, in tower equipment
In the oxidation reaction carried out, oxidizing process is slow, residence time of material length, in turn results in that oxidation efficiency is low, and equipment volume is big；
Phenomena such as wall stream and axial backmixing be present in tower simultaneously, reduce mass-transfer efficiency.
Therefore, it is badly in need of developing efficient method for oxidation to solve existing for existing anthraquinone legal system hydrogen peroxide process not
Foot.
The content of the invention
It is an object of the invention to overcome existing for the method for oxidation of existing anthraquinone legal system hydrogen peroxide process it is above-mentioned not
Foot, there is provided a kind of alkyl anthrahydroquinone method for oxidation and a kind of method for producing hydrogen peroxide, this method can obtain high oxidation
Efficiency.
According to the first aspect of the invention, the invention provides a kind of method for oxidation of alkyl anthrahydroquinone, this method bag
Include and inject oxygen in the solution of the anthrahydroquinone containing alkyl for the hole of nano-scale by average pore size, obtain oxygen-containing solution；In oxygen
Change under reaction condition, make the oxygen-containing solution in a manner of flowing up by the inner space of tubular reactor.
According to the second aspect of the invention, the invention provides a kind of method for producing hydrogen peroxide, this method to include：
Under the conditions of hydrogenation, the solution containing raw material and hydrogen are contacted with the catalyst with catalytic hydrogenation, contained
The mixture of alkyl anthrahydroquinone, the raw material are alkyl-anthraquinone and/or alkyl hydrides anthraquinone；Using the first party according to the present invention
The method that face provides aoxidizes the alkyl anthrahydroquinone in the mixture containing alkyl anthrahydroquinone；Divide in the mixture obtained from oxidation
Separate out hydrogen peroxide.
The oxidation effectiveness that the method for oxidation of the present invention can also obtain under relatively low oxidizer, raw material conversion
Rate is high and the selectivity of hydrogen peroxide is good.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is used for the component of adjacent first passage and second channel in the mixing arrangement that schematically the explanation present invention uses
A kind of preferred embodiment.
Fig. 2 is a kind of cross-sectional view of the component shown in Fig. 1.
Fig. 3 is another cross-sectional view of the component shown in Fig. 1.
Fig. 4 is the structural representation for the mixing arrangement that the present invention uses.
Fig. 5 is a kind of embodiment of method provided by the invention.
Fig. 6 is the another embodiment of method provided by the invention.
Fig. 7 is another embodiment of method provided by the invention.
Fig. 8 is used to illustrate the annexation between mixing arrangement and tubular reactor or tubular fixed-bed reactor.
Description of reference numerals
1：Passage 2：Tube wall
3：Perforated membrane 4：For abutting the component of first passage and second channel
5：Housing 6：First entrance
7：Second entrance 8：Outlet
9：First mixing arrangement 10：Oxygen
11：The solution 12 of the anthrahydroquinone containing alkyl：Tubular fixed-bed reactor
13：Ring flange 14：Ring flange
15：Ring flange 16：Ring flange
Embodiment
The invention provides a kind of method for oxidation of alkyl anthrahydroquinone, it is to receive by average pore size that this method, which is included oxygen,
In the solution of hole injection anthrahydroquinone containing alkyl of meter ruler cun, oxygen-containing solution is obtained；Under oxidation reaction condition, make described oxygen-containing molten
Liquid passes through the inner space of tubular reactor in a manner of flowing up.
In the present invention, the average pore size is that the average pore size in the hole of nano-scale typically can be 1nm to 1000nm, excellent
Elect 30nm to 1000nm, more preferably 30-500nm as.The average pore size is determined using ESEM method.
It can use various methods that oxygen is injected into the molten of the anthrahydroquinone containing alkyl for the hole of nano-scale by average pore size
In liquid.
In the preferred embodiment of the present invention, oxygen is injected into the hydrogen of anthracene containing alkyl by the first mixing arrangement
In the solution of quinone, so as to obtain the oxygen-containing solution, first mixing arrangement includes at least one first passage and at least one
Individual second channel, abutted between the first passage and the second channel by a component, the component is at least partially
There are porose area, the hole for having porose area that there is the average pore size to be nano-scale, the first passage is used to accommodate the oxygen,
The second channel is used for the solution for accommodating the anthrahydroquinone containing alkyl, and the oxygen is nano-scale by the average pore size
Hole be injected into the solution of the anthrahydroquinone containing alkyl.
The component at least partially has porose area, the length direction extension for having porose area along the component.Preferably,
It is described to there is porose area to cover whole component（That is, by with the average pore size between described first passage and the second channel
For the component adjoining in the hole of nano-scale, oxygen is injected into the solution of the anthrahydroquinone containing alkyl by the hole）.It is described to have hole
Area has the hole that the average pore size is nano-scale, so that oxygen passes through the hole quilt with average pore size for nano-scale
Inject in the solution of the anthrahydroquinone containing alkyl.
The component can be that the various oxygen that can make to be contained in the first passage are by the average pore size
The hole of nano-scale and enter the component being contained in the solution of the anthrahydroquinone containing alkyl in second channel.In an example,
The component is formed by porous material, and the average pore size in hole therein is nano-scale.In another example, the component bag
The perforated membrane of matrix and attachment on the matrix is included, described matrix has through hole, and the perforated membrane can be located at the base
On the surface contacted with the solution for the anthrahydroquinone containing alkyl being contained in the second channel of body and/or positioned at described matrix
On the surface contacted with the oxygen being contained in the first passage.Preferably, the perforated membrane be located at described matrix with appearance
On the surface of the solution contact for the anthrahydroquinone containing alkyl being contained in the second channel.Hole in the perforated membrane is described previously
Average pore size be nano-scale hole.The average pore size of through hole in described matrix is not particularly limited, as long as can pass through
Gas.Preferably, the average pore size of the through hole in described matrix is 1nm to 1000 μm（Such as 50-200 μm）.
The shape of the component can be selected according to the position relationship of first passage and second channel, to enable to
The first passage and the second channel are defined by component adjoining.
In one embodiment of the invention, the component is the pipeline with least one passage.The pipeline
There is through hole, and the average pore size of the through hole is previously described nano-scale on tube wall.
In another embodiment of the invention, the component is the pipeline with least one passage, the pipeline
Outer wall and/or passage inwall on be attached with perforated membrane, the tube wall has a through hole, and the hole on the perforated membrane is average hole
Footpath is the hole of nano-scale, and this component is referred to as into membrane tube below.Specifically, as Figure 1-3, the component is with least
The membrane tube of one passage.For the pipeline with through hole as matrix, the pipeline has at least one to lead to the membrane tube using on tube wall 2
Road 1, perforated membrane 3 is attached with the inwall of passage 1 and/or the outer wall of pipeline of the pipeline.The average hole of through hole on tube wall
Footpath is not particularly limited, as long as can make oxygen by that typically can be 1nm to 1000 μm（Such as 50-200 μm）；It is described more
Hole on pore membrane is the hole that previously described average pore size is nano-scale.
In above two embodiment, the quantity of the pipeline or the passage in the membrane tube is preferably at least two,
Such as 4-20 bars.
In actual mechanical process, when the component is pipeline or membrane tube, as shown in figure 4, component 4 can be with housing 5
It is used cooperatively.That is, described first mixing arrangement can also include housing 5, at least one component 4 is placed in housing 5, and make structure
Existential Space between the outer wall of part 4 and the inwall of housing 5.Passage on the component is as accommodating the anthrahydroquinone containing alkyl
The space that the inwall of the second channel of solution, the outer wall of the component and the housing is formed is as accommodating oxygen
The first passage；Or the passage on the component is as accommodating the first passage of oxygen, the component it is outer
The second channel of the space that the inwall of wall and the housing is formed as the solution for accommodating the anthrahydroquinone containing alkyl.It is preferred that
Ground, the second channel of the passage as the solution for accommodating the anthrahydroquinone containing alkyl on the component, the component it is outer
The space that the inwall of wall and the housing is formed is as the first passage for accommodating oxygen.
As shown in figure 4, housing 5 has first entrance 6, second entrance 7 and outlet 8, first passage connects with first entrance 6
Logical, the both ends of second channel connect with second entrance 7 and outlet 8 respectively.First entrance 6 is used to introduce oxygen into first passage
In, second entrance 7 is used to import the solution of the anthrahydroquinone containing alkyl in second channel, and in the presence of pressure differential, oxygen passes through
Hole on tube wall enters in the solution of the anthrahydroquinone containing alkyl, and so as to obtain oxygen-containing solution, oxygen-containing solution is left by outlet 8
First mixing arrangement.
The material for forming the component can be inorganic material（Such as inorganic ceramic）, or organic material, as long as shape
With the solution of oxygen and the anthrahydroquinone containing alkyl chemical interaction does not occur for the material into the component.
Filling rate of the component in the housing typically can be 20-50%（Such as 35-45%）.The filling rate refers to
The space and the percent value of the total measurement (volume) of housing that component occupies.
The amount for the oxygen being sent into the solution of the anthrahydroquinone containing alkyl can be selected according to specific reaction condition.This hair
Oxygen is sent into the solution of the anthrahydroquinone containing alkyl by bright method by average pore size for the hole of nano-scale, can make oxygen height
Degree is dispersed and dissolved in the solution of the anthrahydroquinone containing alkyl, so as to provide enough oxygen sources for oxidation reaction.Therefore, it is of the invention
Even if method is largely sent into oxygen, the oxidation effectiveness that can have also obtained not into the solution of the anthrahydroquinone containing alkyl.According to the present invention
Method, the oxygen can be sent into the solution of the anthrahydroquinone containing alkyl once or by several times, and total feeding amount of oxygen contains alkyl with this
The mol ratio of alkyl anthrahydroquinone in the solution of anthrahydroquinone can be 1-3：1.
With the method for the invention it is preferred to oxygen feeding temperature and pressure is in containing under oxidizing temperature and oxidative pressure
In the solution of alkyl anthrahydroquinone, the trend that oxygen escapes from oxygen-containing solution so can be further reduced.Specifically, can incite somebody to action
Oxygen feeding temperature is 30-70 DEG C and pressure is 0.1-0.7MPa（In terms of gauge pressure）The anthrahydroquinone containing alkyl solution in.
The tubular reactor refers to the reactor with compared with larger ratio of height to diameter.Specifically, the height of the tubular reactor
With the ratio of internal diameter（That is, ratio of height to diameter）Can be 10-200：1（Such as 10-50：1）.The internal diameter of the tubular reactor can be normal
Rule selection, such as can be 20-2000mm（Such as 30-100mm）.The body of reactor on the one hand can be reduced using tubular reactor
Product, is on the other hand passing through previously described first mixing arrangement（It is pipeline or membrane tube particularly in the component）When, directly
First mixing arrangement is arranged on the material inlet pipeline of the tubular reactor, operation is flexibly and conveniently.Institute
Tubular reactor is stated according to specific method for oxidation, can with loading catalyst, can not also loading catalyst, according to specific feelings
Condition, various fillers can also be loaded in the tubular reactor.
The method according to the invention, the oxygen-containing solution are admitted in a manner of flowing up in the tubular reactor.
Can be by the way that the oxygen-containing solution be sent into from the bottom of the tubular reactor, and logistics will be contacted after obtained oxidation from institute
State the top output of tubular reactor.
The method according to the invention, the quantity of the tubular reactor can be 1, or more than 2.Described
When the quantity of tubular reactor is more than 2, the tubular reactor can be to be connected in series, or be connected in parallel, also
Can be series connection and combination in parallel.Described be connected in series refers to that the effluent of previous tubular reactor is anti-for next tubular type
Answer the charging of device；Described be connected in parallel refers to do not have material exchange between tubular reactor.
The method of the present invention can be to various alkyl anthrahydroquinones（Including alkyl hydrides anthrahydroquinone）Aoxidized.Preferably,
The raw material is 2- ethyl anthrahydroquinones and/or tetrahydrochysene 2- ethyl anthrahydroquinones.
According to the method for oxidation of the present invention, the concentration of the alkyl anthrahydroquinone in the solution of the anthrahydroquinone containing alkyl can be conventional
Selection, can be typically 10-30 weight %, such as 10-24 weight %.It is that the two or more tubular type that is connected in series is anti-in tubular reactor
When answering device, the concentration of raw material refers to enter the alkyl anthrahydroquinone in the solution of the anthrahydroquinone containing alkyl of first tubular reactor
Concentration.
The present invention is not particularly limited for the solvent of the solution containing raw material, can be conventional selection.Specifically, institute
The solvent for stating the solution containing raw material is phosphate and/or alkyl carboxylates, such as trioctyl phosphate and/or methyl cyclohexanol acetate.
The oxidation reaction condition is not particularly limited, and can be conventional selection.Usually, the oxidation reaction condition bag
Include：Temperature is 40-70 DEG C；In terms of gauge pressure, the pressure in tubular reactor is 0.1-0.7MPa；Oxygen-containing solution is anti-in the tubular type
It can be the 10-500 seconds to answer the residence time in device（Such as the 20-300 seconds）.
Oxygen is injected to the solution of the anthrahydroquinone containing alkyl using previously described first mixing arrangement, it is oxygen-containing molten to obtain
Liquid, and when oxygen-containing solution is sent into tubular reactor, the outlet for being used on first mixing arrangement exporting oxygen-containing solution it is interior
Footpath is r1, the internal diameter for the entrance for being used on the tubular reactor input oxygen-containing solution is r2, r1/r2=0.6-1（Such as 0.85-1）.
The internal diameter for connecting the pipe of the outlet and the entrance is r3, r1/r3=0.85-1.5（Such as 0.85-1）.So oxygen-containing solution is defeated
It is more stable during fortune, so as to obtain more preferable oxidation effectiveness.
It is a kind of preferred embodiment of the method according to the invention shown in Fig. 5.In this embodiment, it is mixed first
Attach together to put in 9 and inject oxygen 10 in the solution 11 of the anthrahydroquinone containing alkyl, obtain oxygen-containing solution.Oxygen-containing solution enters pipe reaction
Oxidation reaction is carried out in device 12, obtains the reactant mixture containing hydrogen peroxide.
According to the embodiment, multiple tubular reactors can be set（Such as two or more tubular reactor）, multiple tubular types
Can be to be connected in series between reactor, or be connected in parallel, can also be series connection and combination in parallel.In multiple tubular types
When reactor is connected in series, along the flow direction of material, the first mixing arrangement can be arranged on to first tubular reactor
Arrival end；Can also be as shown in fig. 6, the arrival end in each tubular reactor 12 sets the first mixing arrangement 9 respectively.Multiple
When tubular reactor is connected in parallel, first mixing arrangement can be only set, solution and the oxygen of the anthrahydroquinone containing alkyl are mixed
Close, be then respectively fed to obtained oxygen-containing solution in multiple tubular reactors for being connected in parallel；Can also be as shown in Figure 7 every
The arrival end of individual tubular reactor 12 sets the first mixing arrangement 9 respectively.
It can adopt and the first mixing arrangement is connected on the entrance pipe of tubular reactor in various manners, such as：Can be with
At the both ends of mixing arrangement, one ring flange is respectively set（Fig. 8 is shown in which a ring flange 13）, each with corresponding entrance
Flangeseal connection on pipeline（As shown in figure 8, the ring flange 13 of mixing arrangement one end and the ring flange 14 on entrance pipe
It is tightly connected）；The other end of entrance pipe is connected by ring flange 15 with the ring flange 16 of the arrival end of tubular reactor 12.
According to the method for oxidation of the present invention, can use purity oxygen as oxidant, can also using oxygen with it is nonactive
The gaseous mixture of gas is as oxidant, the non-active gas such as group 0 element gas（Such as argon gas）, nitrogen.The gaseous mixture
The content of middle oxygen typically can be 10-50 volumes %.The instantiation of the gaseous mixture can be air.
Present invention also offers a kind of method for producing hydrogen peroxide, this method includes：Under the conditions of hydrogenation, it will contain
The solution and hydrogen of raw material contact with the catalyst with catalytic hydrogenation, obtain the mixture containing alkyl anthrahydroquinone, institute
It is alkyl-anthraquinone and/or alkyl hydrides anthraquinone to state raw material；Using method provided by the invention by the mixing containing alkyl anthrahydroquinone
Alkyl anthrahydroquinone oxidation in thing；Hydrogen peroxide is isolated in the mixture obtained from oxidation
Detailed description has been carried out above for the method that alkyl anthrahydroquinone is aoxidized, and here is omitted.
Method according to the invention it is possible to using conventional various methods by the solution containing raw material and hydrogen with having catalysis
The catalyst of hydrogenation contacts under the conditions of hydrogenation, obtains the mixture containing alkyl anthrahydroquinone.Such as：Can be by hydrogen
Gas is with the solution containing raw material in conventional various blenders（Such as static mixer or dynamic mixer）Middle mixing, it will be mixed
Thing is sent into and is filled with the fixed bed reactors with catalytic hydrogenation, carries out hydrogenation.The static mixer passes through
Change the flow regime of fluid and realize and be well mixed gas with liquid, be specifically as follows but be not limited to SV type static mixings
One kind or more in device, SK types static mixer, SX types static mixer, SH types static mixer and SL type static mixers
Kind.The dynamic mixer can be realized for the various motions by moving component and set the mixing that gas is well mixed with liquid
Standby, the moving component for example can be the common various parts with agitating function.
In a kind of preferred embodiment of the present invention, hydrogen is passed through identical with previously described first mixing arrangement
The second mixing arrangement injection solution containing raw material in, will obtain containing hydrogen solution be sent into tubular fixed-bed reactor with
Catalyst contact with catalytic hydrogenation.
For purposes of clarity, the mixing arrangement of the solution for oxygen to be injected to the anthrahydroquinone containing alkyl is referred to as by the present invention
First mixing arrangement, by for the mixing arrangement of solution of the hydrogen injection containing raw material to be referred to as into the second mixing arrangement.
The structure of second mixing arrangement and mixed with the connected mode of tubular fixed-bed reactor and previously described first
Attach together and put identical, be no longer described in detail herein.Preferably, in second mixing arrangement, the first entrance is used to import hydrogen
In the first passage, the second entrance is used to import the solution containing raw material in the second channel, described hydrogeneous
Solution leaves second mixing arrangement by the outlet.
The specification of the tubular fixed-bed reactor is identical with previously described tubular reactor.
The amount for the hydrogen being sent into the solution containing raw material can be selected according to specific reaction condition.The side of the present invention
Hydrogen is sent into the solution containing raw material by method by average pore size for the hole of nano-scale, can be made hydrogen high degree of dispersion and be dissolved
In the solution containing raw material, so as to provide enough hydrogen sources for hydrogenation.Therefore, even if method of the invention is not to containing raw material
Solution in it is a large amount of be sent into hydrogen, while without maintain certain hydrogen dividing potential drop in the reactor, can also obtain high hydrogenation ratio, and
Reduce the trend of catalyst coking.According to the inventive method, the hydrogen can be sent into the solution containing raw material once or by several times,
The mol ratio that total feeding amount of hydrogen contains the raw material in the solution of raw material with this can be 0.5-1：1.
With the method for the invention it is preferred to hydrogen feeding temperature and pressure is in containing under hydrogenation temperature and hydrogenation pressure
In the solution of raw material, the trend that hydrogen escapes from containing hydrogen solution so can be further reduced.Specifically, hydrogen can be sent
Enter that temperature is 40-70 DEG C and pressure is 0.1-0.5MPa（In terms of gauge pressure）The solution containing raw material in.
The method according to the invention, it is described that tubular fixed-bed reactor can be sent into a manner of flowing up containing hydrogen solution
In, it can also be admitted in a manner of flowing downward in the tubular fixed-bed reactor.It is preferred that the quilt in a manner of flowing up
It is sent into the tubular fixed-bed reactor, accordingly even when under lower hydrogen usage, the hydrogenation that can have also obtained is imitated
Fruit, while catalyst still shows long service life.
It is described to be carried out containing contact of the hydrogen solution with catalyst under the hydrotreating temperatures of routine and pressure, without spy
Do not limit.Usually, include described in making containing hydrogen solution with the condition that the catalyst with catalytic hydrogenation contacts：Temperature can be with
For 40-70 DEG C；In terms of gauge pressure, the pressure in tubular fixed-bed reactor can be 0.1-0.5MPa；The volume of liquid material is empty
Speed can be 10-100h-1。
Raw material in the solution containing raw material can be 2- EAQs and/or tetrahydrochysene 2- EAQs.
The present invention can be conventional selection for the concentration of raw material in the solution containing raw material.Usually, it is described containing original
The concentration of raw material in the solution of material can be 10-30 weight %, such as 10-24 weight %.It is series connection in tubular fixed-bed reactor
During the two or more tubular fixed-bed reactor of connection, the concentration of raw material refers to enter containing for first tubular fixed-bed reactor
The concentration of raw material in the solution of raw material.
The present invention is not particularly limited for the solvent of the solution containing raw material, can be conventional selection.Specifically, institute
The solvent for stating the solution containing raw material is the first solvent and the mixture of the second solvent, and first solvent is C9-C11Aromatic hydrocarbons and/
Or alkylnaphthalene, second solvent are phosphate and/or alkyl carboxylates.First solvent for example can be methyl naphthalene, neighbour
It is more than one or both of trimethylbenzene, a trimethylbenzene and pseudocumene.Second solvent for example can be trioctyl phosphate
And/or methyl cyclohexanol acetate.Ratio between first solvent and second solvent can be conventional selection, typically
Ground, the volume ratio of first solvent and second solvent can be 0.5-4：1.
The method of the present invention is not particularly limited for the species of the catalyst with catalytic hydrogenation, can be common
The various hydrogenations that can be catalyzed alkyl-anthraquinone and/or alkyl hydrides anthraquinone to generate the material of alkyl anthrahydroquinone.It is preferred that
Ground, the catalyst include the active component of carrier and load on the carrier, and the active component is palladium.The catalysis
In agent, the content of the active component in terms of element can be 0.25-1 weight %.The carrier can be conventional selection, without spy
Do not limit.Usually, the carrier can be more than one or both of aluminum oxide, silica, activated carbon and titanium oxide.
The present invention is not particularly limited for isolating the method for hydrogen peroxide from the obtained mixture of oxidation, Ke Yiwei
Conventional selection.Preferably, hydrogen peroxide is isolated in the mixture obtained using the method for extraction from oxidation.Extract the extraction used
It can be extractant commonly used in the art, preferably water to take agent, can so directly obtain hydrogen peroxide.Obtaining hydrogen peroxide can adopt
Post-processed with conventional various methods.
The method according to the invention, the surplus solution of hydrogen peroxide is isolated（Such as raffinate phase）Can be as hydrogenation extremely
Solution of the small part containing raw material recycles.
The present invention is described in detail with comparative example with reference to embodiments, but and be not so limited the present invention model
Enclose.
In following examples and comparative example, average pore size is determined using ESEM method, pressure is in terms of gauge pressure.
In following examples and comparative example, using high performance liquid chromatography to as the tubular fixed-bed anti-of hydrogenation reactor
Answer the composition of the effluent of device to be analyzed, on this basis, hydrogenation ratio is calculated using below equation.
Hydrogenation ratio=[molal quantity of alkyl-anthraquinone in the molal quantity of alkyl anthrahydroquinone/solution containing raw material in effluent] ×
100%。
In following examples and comparative example, using high performance liquid chromatography to the tubular reactor as oxidation reactor
The composition of effluent is analyzed, and on this basis, the conversion ratio and hydrogen peroxide of alkyl anthrahydroquinone is calculated using below equation
Selectivity.
The conversion ratio of alkyl anthrahydroquinone=[（Alkane in molal quantity-effluent of alkyl anthrahydroquinone in the mixture that hydrogenation obtains
The molal quantity of base anthrahydroquinone）The molal quantity of alkyl anthrahydroquinone in the mixture that/hydrogenation obtains] × 100%；
The selectivity of hydrogen peroxide=[molal quantity of hydrogen peroxide in effluent/（Hydrogenate alkyl anthracene in obtained mixture
The molal quantity of alkyl anthrahydroquinone in molal quantity-effluent of quinhydrones）]×100%.
Embodiment 1-8 is used for the method for the alkyl anthrahydroquinone method for oxidation for illustrating the present invention and production hydrogen peroxide.
Embodiment 1
The mixing arrangement used in the present embodiment in mixing arrangement for abutting first passage and second as shown in figure 4, lead to
The component in road is membrane tube as shown in Figure 2（Commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, it is uniformly distributed on pipeline
Have 19 passages, the internal diameter of each passage is 3.3mm, and the average pore size in the hole on matrix is 100 μm, the hole on perforated membrane it is flat
Equal aperture is 30nm）With the housing used with the tube fit, the space that the outer wall of pipeline and the inwall of housing are formed is made
For first passage, the passage on pipeline is as second channel, and first passage is used to accommodate gas, and second channel is used to accommodate liquid
Body, the filling rate of membrane tube in the housing are 40%.
In the present embodiment, step（1）And step（2）The mode shown in Fig. 5 is respectively adopted to carry out.
（1）By the solution containing raw material（Raw material is 2- EAQs, and solvent is that volume ratio is 3：1：1 hemimellitol, phosphoric acid
The mixed liquor of three monooctyl esters and methyl cyclohexanol acetate, material concentration are 12 weight %）With hydrogen in the second mixing arrangement in table 1
Mixed under conditions of listing, then will obtain being sent into tubular fixed-bed reactor containing hydrogen solution（Tubular fixed-bed reaction
The internal diameter of device is 50mm, 1 beds is provided with tubular reactor, the ratio of height to diameter of Catalyst packing is 15：1）In,
With having the catalyst of catalytic hydrogenation under conditions of shown in table 1（Active component is counted as 0.3wt%Pd using element, carrier is oxygen
Change aluminium）Contact.The effluent of tubular fixed-bed reactor is analyzed and calculates hydrogenation ratio, is as a result listed in table 1.
Wherein, the ratio of the internal diameter of the material inlet of the internal diameter of the material outlet of mixing arrangement and tubular fixed-bed reactor
For 0.9, the internal diameter of the material outlet of mixing arrangement is with being connected the material outlet of mixing arrangement and the thing of tubular fixed-bed reactor
The ratio for expecting the internal diameter of the pipeline of entrance is 0.9.
（2）By step（1）The effluent of middle tubular fixed-bed reactor be sent into the first mixing arrangement with oxygen mix, and
Obtained oxygen-containing mixture is sent into tubular reactor in a manner of flowing up（Inside tubular reactor non-loading catalyst with
And filler, internal diameter 50mm, ratio of height to diameter 15：1）In, carry out oxidation reaction under conditions of table 4 is listed.To tubular reactor
Effluent analyzed and calculate the conversion ratio of alkyl anthrahydroquinone and the conversion ratio of hydrogen peroxide, as a result listed in table 1.
Wherein, the ratio of the internal diameter of the material inlet of the internal diameter of the material outlet of mixing arrangement and tubular reactor is 0.9,
The internal diameter of the material outlet of mixing arrangement and the pipeline for being connected the material outlet of mixing arrangement and the material inlet of tubular reactor
Internal diameter ratio be 0.9.
Comparative example 1
Hydrogen peroxide is produced using method same as Example 1, unlike, step（2）The middle mixing arrangement used
In, in the component for abutting first passage and second channel, the average pore size on perforated membrane is 5 μm（Commercially available from day in Beijing
First environment engineering finite responsible company）.
Experimental result is listed in table 1.
Embodiment 2
Hydrogen peroxide is produced using method same as Example 1, unlike, step（1）The middle mixing arrangement used
In, in the component for abutting first passage and second channel, the average pore size on perforated membrane is 5 μm（Commercially available from day in Beijing
First environment engineering finite responsible company）.
Experimental result is listed in table 1.
Comparative example 2
Hydrogen peroxide is produced using method same as Example 1, unlike, step（2）In, mixing arrangement is static
Blender（SV type static mixers purchased from Qidong person of outstanding talent along more petrochemical equipment Co., Ltds）Instead of.
Experimental result is listed in table 1.
Embodiment 3
Hydrogen peroxide is produced using method same as Example 1, unlike, step（1）In, mixing arrangement is static
Blender（SV type static mixers purchased from Qidong person of outstanding talent along more petrochemical equipment Co., Ltds）Instead of.
Experimental result is listed in table 1.
Comparative example 3
Alkyl anthrahydroquinone is produced using method same as Example 1, unlike, step（2）In, liquid material is in pipe
Flow direction in formula reactor is to flow downward.
Experimental result is listed in table 1.
Table 1
Table 1 as a result, it was confirmed that using the present invention method alkyl anthrahydroquinone is aoxidized, even in relatively low oxidizer
Under the oxidation effectiveness that can also obtain, feed stock conversion is high and the selectivity of hydrogen peroxide is good；Meanwhile according to the side of the present invention
Method, the residence time of material in the reactor is short, can obtain higher production efficiency.
Embodiment 4
The difference for the mixing arrangement that the mixing arrangement used in the present embodiment uses with embodiment 1 is：
The average pore size in the hole on the perforated membrane of membrane tube used in mixing arrangement is 500nm；Membrane tube filling out in the housing
Rate is filled for 35%；The internal diameter of the material outlet of mixing arrangement is with the tubular fixed-bed reactor as hydrogenation reactor and as oxygen
The ratio for changing the internal diameter of the material inlet of the tubular reactor of reactor is respectively 0.85, the internal diameter of the material outlet of mixing arrangement
With the internal diameter of the pipeline that is connected the material outlet of mixing arrangement and the material inlet of tubular fixed-bed reactor/tubular reactor
Ratio is respectively 1.
（1）Using with the step of embodiment 1（1）Identical method carries out hydrogenation, produces containing the molten of alkyl anthrahydroquinone
Liquid.
（2）Using the method shown in Fig. 6, by the solution containing alkyl anthrahydroquinone and oxygen in first Liqiud-gas mixing device
In mixed under conditions of table 2 is listed, then by obtained oxygen-containing solution be sent into first tubular reactor（Specification is the same as real
Apply example 1）In, carry out oxidation reaction under conditions of table 2 is listed.
Under conditions of table 2 is listed, by second Liqiud-gas mixing device into the effluent of first tubular reactor
After injecting oxygen, obtained oxygen-containing mixture is sent into second tubular fixed-bed reactor（Specification is the same as first pipe reaction
Device）In, carry out oxidation reaction under conditions of table 2 is listed.
The effluent of second tubular fixed-bed reactor is analyzed and calculates the conversion ratio and mistake of alkyl anthrahydroquinone
The conversion ratio of hydrogen oxide, as a result listed in table 2.
Table 2
Embodiment 5
Hydrogen peroxide is produced using method same as Example 1, unlike：
（1）Raw material in solution containing raw material is tetrahydrochysene 2- alkyl-anthraquinones, and solvent is that volume ratio is 4：Between 1 trimethylbenzene and
The mixed liquor of trioctyl phosphate, material concentration are 15 weight %；
（2）It is the pipeline formed by porous material to be used to abut first passage and the component of second channel in mixing arrangement
（Commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd；19 passages, the internal diameter of each passage are evenly distributed with pipeline
For 3.3mm, the average pore size in the hole on tube wall is 500nm）；Using the passage on pipeline as second channel, by the outer wall of pipeline
With the space that the inwall of housing is formed as first passage, the filling rate of pipeline in the housing is 45%；
The ratio of the internal diameter of the internal diameter of the material outlet of mixing arrangement and the material inlet of tubular fixed-bed reactor is 1,
The internal diameter of the material outlet of mixing arrangement is with being connected the material outlet of mixing arrangement and the material inlet of tubular fixed-bed reactor
Pipeline internal diameter ratio be 1；
（3）Oxidation reaction is carried out under conditions of table 3 is listed respectively.
Experimental result is listed in table 3.
Table 3
Embodiment 6
The mixing arrangement used in the present embodiment is same as Example 1.
（1）Using the method shown in Fig. 6, by the solution containing raw material（Raw material is 2- EAQs, and solvent is that volume ratio is 1：
1 pseudocumene and the mixed liquor of methyl cyclohexanol acetate）The bar listed with hydrogen in first Liqiud-gas mixing device in table 4
Mixed under part, then will obtain being sent into first tubular fixed-bed reactor containing hydrogen solution（Tubular fixed-bed reactor
Internal diameter be 50mm, be provided with 1 beds in tubular reactor, the ratio of height to diameter of Catalyst packing is 15：1）In, in table
With having the catalyst of catalytic hydrogenation under conditions of shown in 4（Active component is 0.4wt%Pd, and carrier is silica）Connect
Touch.
Under conditions of table 4 is listed, the stream by second Liqiud-gas mixing device to first tubular fixed-bed reactor
Go out in thing after injecting hydrogen, will obtain being sent into second tubular fixed-bed reactor containing hydrogen mixture（Tubular fixed-bed reaction
The internal diameter of device is 50mm, 1 beds is provided with tubular reactor, the ratio of height to diameter of Catalyst packing is 10：1）In,
With having the catalyst of catalytic hydrogenation under conditions of shown in table 4（It is identical with first tubular fixed-bed reactor）Contact.
The effluent of second tubular fixed-bed reactor is analyzed and calculates hydrogenation ratio, is as a result listed in table 4.
（2）Using method same as Example 1, oxygen is injected into the anthrahydroquinone containing alkyl under conditions of table 4 is listed
In solution, and obtained oxygen-containing solution is subjected to oxidation reaction under conditions of table 4 is listed, experimental result is listed in table 4.
Embodiment 7
Hydrogen peroxide is produced using method same as Example 6, unlike,
（1）Step（1）In, the operating condition of mixing arrangement and the condition of hydrogenation are as shown in table 4；
（2）Step（2）In, the operating condition of mixing arrangement and the condition of hydrogenation are as shown in table 4.
Experimental result is listed in table 4.
Embodiment 8
Alkyl anthrahydroquinone is prepared using method same as Example 6, unlike,
（1）Step（1）In, the operating condition of mixing arrangement and the condition of hydrogenation are as shown in table 4；
（2）Step（2）In, the operating condition of mixing arrangement and the condition of hydrogenation are as shown in table 4.
Experimental result is listed in table 4.
Table 4
The confirmation of embodiment 1-8 result, method of the invention can be given birth to high feed stock conversion and selectivity of product
Produce hydrogen peroxide.
Claims (15)
1. a kind of method for producing hydrogen peroxide, this method include：
By hydrogen by average pore size be 30-500nm hole injection be in hydrogenation temperature and hydrogenation pressure under containing the molten of raw material
In liquid, obtain containing hydrogen solution, the total feeding amount and the mol ratio of the raw material in the solution containing raw material of hydrogen are 0.5-1：1；
Be sent into described containing hydrogen solution in tubular fixed-bed reactor in a manner of flowing up, under the conditions of the hydrogenation will described in contain
Hydrogen solution contacts with the catalyst with catalytic hydrogenation, obtains the mixture containing alkyl anthrahydroquinone, the raw material is alkane
Base anthraquinone and/or alkyl hydrides anthraquinone, the hydrogenation condition include：Temperature is 40-70 DEG C；In terms of gauge pressure, tubular type is fixed
Pressure in bed reactor is 0.1-0.7MPa；The volume space velocity of liquid material is 10-100h-1；
Oxygen is injected in the mixture containing alkyl anthrahydroquinone by average pore size for the hole of nano-scale, obtained oxygen-containing molten
Liquid；Under oxidation reaction condition, make the oxygen-containing solution in a manner of flowing up by the inner space of tubular reactor, will
Alkyl anthrahydroquinone oxidation in oxygen-containing solution；
Hydrogen peroxide is isolated in the mixture obtained from oxidation.
2. according to the method for claim 1, wherein, hydrogen is injected into the solution containing raw material by the second mixing arrangement
In, so as to obtain it is described contain hydrogen solution, second mixing arrangement includes at least one first passage and at least one second and led to
Road, is abutted between the first passage and the second channel by a component, and the component at least partially has porose area, institute
The hole that there is porose area the average pore size to be 30-500nm is stated, the first passage is used to accommodate the hydrogen, and described second
Passage is used to accommodate the solution containing raw material, and the hydrogen is injected into described by the hole that the average pore size is 30-500nm
In solution containing raw material.
3. according to the method for claim 2, wherein, in second mixing arrangement, the component is with least one
The pipeline of passage, there is through hole on the tube wall of the pipeline, the through hole is the hole that average pore size is 30-500nm；It is or described
Perforated membrane is attached with the outer wall of pipeline and/or the inwall of passage, there is through hole on the tube wall of the pipeline, on the perforated membrane
Hole be hole that average pore size is 30-500nm.
4. according to the method for claim 3, wherein, second mixing arrangement also includes housing, at least one structure
Part is arranged on the enclosure interior, Existential Space between the outer wall of the component and the inwall of the housing, and the housing has
The space that the inwall of first entrance, second entrance and outlet, the outer wall of the pipeline and the housing is formed is as described first
Passage, the passage on the pipeline connect as the second channel, the first passage with the first entrance, and described second
The both ends of passage are used to hydrogen importing described first with the second entrance and the outlet, the first entrance respectively
In passage, the second entrance is used to import the solution containing raw material in the second channel, described to pass through containing hydrogen solution
Leave second mixing arrangement in the outlet.
5. according to the method described in any one in claim 1-4, wherein, second mixing arrangement is arranged on the tubular type
The arrival end of fixed bed reactors.
6. according to any one methods described in claim 1-4, wherein, the solvent of the solution containing raw material is the first solvent and the
The mixture of two solvents, first solvent are C9-C11Aromatic hydrocarbons and/or alkylnaphthalene, second solvent be phosphate and/or
Alkyl carboxylates, the volume ratio of first solvent and second solvent is 0.5-4：1.
7. according to the method for claim 1, wherein, the method bag of hydrogen peroxide is isolated from the obtained mixture of oxidation
Include：The mixture obtained with water to oxidation extracts, and collects the extraction phase containing hydrogen peroxide.
8. according to the method for claim 1, wherein, oxygen is injected into the anthrahydroquinone containing alkyl by the first mixing arrangement
Solution in, so as to obtain the oxygen-containing solution, first mixing arrangement includes at least one first passage and at least one
Second channel, is abutted between the first passage and the second channel by a component, and the component at least partially has
Porose area, the hole for having porose area that there is the average pore size to be nano-scale, the first passage are used to accommodate the oxygen, institute
The solution that second channel is used to accommodate the anthrahydroquinone containing alkyl is stated, the oxygen is nano-scale by the average pore size
Hole is injected into the solution of the anthrahydroquinone containing alkyl.
9. according to the method for claim 8, wherein, in first mixing arrangement, the component is with least one
The pipeline of passage, there is through hole on the tube wall of the pipeline, the through hole is the hole that average pore size is nano-scale；It is or described
Perforated membrane is attached with the outer wall of pipeline and/or the inwall of passage, there is through hole on the tube wall of the pipeline, on the perforated membrane
Hole be hole that average pore size is nano-scale.
10. according to the method for claim 9, wherein, first mixing arrangement also includes housing, at least one structure
Part is arranged on the enclosure interior, Existential Space between the outer wall of the component and the inwall of the housing, and the housing has
The space that the inwall of first entrance, second entrance and outlet, the outer wall of the pipeline and the housing is formed is as described first
Passage, the passage on the pipeline connect as the second channel, the first passage with the first entrance, and described second
The both ends of passage are used to introduce oxygen into described first with the second entrance and the outlet, the first entrance respectively
In passage, the second entrance is used to import the solution of the anthrahydroquinone containing alkyl in the second channel, described oxygen-containing molten
Liquid leaves first mixing arrangement by the outlet.
11. according to the method described in any one in claim 8-10, wherein, first mixing arrangement is arranged on the pipe
The arrival end of formula reactor.
12. according to the method described in any one in claim 1 and 8-10, wherein, in first mixing arrangement, average hole
Footpath is that the average pore size in the hole of nano-scale is 30-1000nm.
13. according to the method described in any one in claim 1 and 8-10, wherein, total feeding amount of oxygen contains alkane with described
The mol ratio of alkyl anthrahydroquinone is 1-3 in the solution of base anthrahydroquinone：1.
14. according to the method for claim 1, wherein, the oxidation reaction condition includes：Temperature is 40-70 DEG C；With gauge pressure
Count, the pressure in tubular reactor is 0.1-0.7MPa；Residence time of the oxygen-containing solution in the tubular reactor is 10-
500 seconds.
15. the method according to claim 1 or 14, wherein, the ratio of height to diameter of the tubular reactor is 10-200：1.
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