CN105800562A - Extraction method for hydrogen peroxide preparation by anthraquinone process and preparation method of hydrogen peroxide - Google Patents

Extraction method for hydrogen peroxide preparation by anthraquinone process and preparation method of hydrogen peroxide Download PDF

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Publication number
CN105800562A
CN105800562A CN201410852648.1A CN201410852648A CN105800562A CN 105800562 A CN105800562 A CN 105800562A CN 201410852648 A CN201410852648 A CN 201410852648A CN 105800562 A CN105800562 A CN 105800562A
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China
Prior art keywords
hydrogen peroxide
solution
anthraquinone
membrane tube
passage
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CN201410852648.1A
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Inventor
佘喜春
向明林
易娇
汪永军
敖博
李庆华
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Hunan Changling Petrochemical Technology Development Co Ltd
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Hunan Changling Petrochemical Technology Development Co Ltd
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Abstract

The invention discloses an extraction method for hydrogen peroxide preparation by an anthraquinone process and a preparation method of hydrogen peroxide. The extraction method comprises the steps: (1) injecting an oxidation liquid containing hydrogen peroxide and alkyl anthraquinone into a phosphoric acid aqueous solution through pores with the average pore size of nanometer size, and pre-extracting, to obtain a mixed solution; and (2) sending the mixed solution into a fibrous membrane contactor, extracting, and carrying out oil-water separation of the extracted product, to obtain hydrogen peroxide. The method can effectively improve the extraction efficiency of hydrogen peroxide, reduces the content of hydrogen peroxide in extraction raffinate, and improves the stability of hydrogen peroxide.

Description

The extracting process of anthraquinone legal system hydrogen peroxide and the preparation method of hydrogen peroxide
Technical field
The preparation method that the present invention relates to the hydrogen peroxide of the extracting process of a kind of anthraquinone legal system hydrogen peroxide and this extracting process of use.
Background technology
Hydrogen peroxide is as a kind of important green chemical, it is widely used in the every field such as chemosynthesis, food, weaving, metallurgy, electronics, agricultural, medicine, papermaking, national defence and environmental protection, particularly emerging green chemical industry technique, such as the oximate etc. of the epoxidation of propylene and Ketohexamethylene, open up the application that hydrogen peroxide is new.
At present, the main production process of hydrogen peroxide is anthraquinone, in purification by liquid extraction process, dispersion phase is bigger with the flow ratio of continuous phase, in traditional extraction equipment (turntable extracting tower, perforated-plate extraction tower etc.), dispersion phase is shorter in the time of staying of device interior, and mass-transfer efficiency is relatively low；Simultaneously because the interfacial tension of oxidation solution-aqueous systems is bigger, dispersion phase cannot be broken for less drop by traditional extraction equipment effectively, cause mass transfer area less, extraction efficiency is poor, in raffinate, concentration of hydrogen peroxide is up to 0.4g/L, have impact on device hydrogen peroxide total recovery, and add the load of aftertreatment device and there is potential safety hazard.It addition, when traditional extraction equipment is for hydrogen peroxide manufacture, there is comparatively significantly feed liquid air-teturning mixed phenomenon, cause that extraction efficiency reduces.
In view of current in the extraction process process of anthraquinone legal system hydrogen peroxide, the problems that traditional extraction equipment exists, it is badly in need of a kind of hydrogen peroxide extracting process in hgher efficiency.
Summary of the invention
The invention aims to solve how to improve the problem of the extraction efficiency of extraction process in anthraquinone legal system hydrogen peroxide, it is provided that the extracting process of anthraquinone legal system hydrogen peroxide and the preparation method of hydrogen peroxide.
To achieve these goals, the present invention provides the extracting process of a kind of anthraquinone legal system hydrogen peroxide, the method includes: the oxidation solution containing hydrogen peroxide and alkyl-anthraquinone is injected in phosphate aqueous solution by the hole that average pore size is nano-scale and carries out pre-extracted by (1), obtains mixed liquor；(2) described mixed liquor is sent into fiber-film contact to extract, and the product of described extraction is carried out oil-water separation, obtain hydrogen peroxide.
The preparation method that present invention also offers a kind of hydrogen peroxide, the method includes: when hydrogenation, the working solution containing raw material, hydrogen and the catalyst with catalytic hydrogenation is contacted, obtains the hydride containing alkyl hydrogen anthraquinone；Described hydride is contacted with oxygen under oxidation reaction condition, obtains the oxidation solution containing hydrogen peroxide and alkyl-anthraquinone；Adopt extracting process provided by the invention, from described oxidation solution, isolate hydrogen peroxide；Described raw material is alkyl-anthraquinone.
Extract with fiber-film contact by extracting process provided by the invention using membrane tube carry out mixing, and use extractant phosphoric acid to realize pre-extracted in membrane tube mixed process simultaneously, the extraction efficiency of hydrogen peroxide can be effectively improved, reduce the content of hydrogen peroxide in raffinate oil phase, and use extractant can improve the stability of hydrogen peroxide.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.In the accompanying drawings:
Fig. 1 is for schematically illustrating a kind of preferred implementation of the membrane tube of connection first passage and second channel in the mixing arrangement that the present invention uses；
Fig. 2 is a kind of cross sectional representation of the membrane tube shown in Fig. 1；
Fig. 3 is the another kind of cross sectional representation of the membrane tube shown in Fig. 1；
Fig. 4 is the structural representation of the mixing arrangement that the present invention uses；
Fig. 5 is a kind of embodiment of the extracting process with fiber-film contact provided by the invention；
Fig. 6 is a kind of embodiment of method provided by the invention.
Description of reference numerals
1: passage 2: tube wall
3: perforated membrane 4: membrane tube
5: housing 6: the first entrance
7: the second entrances 8: outlet
9: extract mixing arrangement 10: containing the oxidation solution of hydrogen peroxide and alkyl-anthraquinone
11: phosphate aqueous solution 12: fiber-film contact
13: the first mixing arrangements 14: hydrogen
15: the working solution 16 containing raw material: tubular fixed-bed reactor
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The present invention provides the extracting process of a kind of anthraquinone legal system hydrogen peroxide, the method includes: the oxidation solution containing hydrogen peroxide and alkyl-anthraquinone is injected in phosphate aqueous solution by the hole that average pore size is nano-scale and carries out pre-extracted by (1), obtains mixed liquor；(2) described mixed liquor is sent into fiber-film contact to extract, and the product of described extraction is carried out oil-water separation, obtain hydrogen peroxide.
In the step (1) of extracting process provided by the invention, use extract phosphate aqueous solution to carry out pre-extracted and can improve the efficiency of extraction of hydrogen peroxide, and take to inject in phosphate aqueous solution by the oxidation solution containing hydrogen peroxide and alkyl-anthraquinone by the hole that average pore size is nano-scale simultaneously, the hydrogen peroxide in oxidation solution can be made to mix better with extract, be favorably improved the effect of pre-extracted.
In the present invention, described average pore size is the average pore size in the hole of nano-scale can be generally 1nm to 1000nm, it is preferred to 30nm to 1000nm, more preferably 30nm to 800nm, more preferably 30nm to 500nm.Described average pore size adopts scanning electron microscope method to measure.
Various method can be adopted to be injected in phosphate aqueous solution by the hole that average pore size is nano-scale by oxidation solution.
In the preferred embodiment of the present invention, described oxidation solution is injected in phosphate aqueous solution by extracting mixing arrangement；Described extraction mixing arrangement includes at least one first passage and at least one second channel, connected by membrane tube between described first passage and described second channel, described membrane tube at least partially have porose area, described have porose area to have hole that described average pore size is nano-scale, described first passage is used for holding described oxidation solution, described second channel is used for holding described phosphate aqueous solution, and described oxidation solution is injected in described phosphate aqueous solution by the hole that described average pore size is nano-scale.
Described membrane tube at least partially have porose area, described in have porose area to extend along the length direction of described membrane tube.Preferably, porose area is had to cover whole membrane tube (that is, by having the membrane tube connection in the hole that described average pore size is nano-scale between described first passage and described second channel, described oxidation solution is injected in phosphate aqueous solution) by described hole described in.Described have porose area to have hole that described average pore size is nano-scale so that described oxidation solution pass through described in there is the hole that average pore size is nano-scale be injected in phosphate aqueous solution.
Described membrane tube can enter the membrane tube in the phosphate aqueous solution being contained in second channel for the various described oxidation solutions that can make to be contained in described first passage by hole that described average pore size is nano-scale.In an example, described membrane tube is formed by porous material, and the average pore size in hole therein is nano-scale.In another example, described membrane tube includes matrix and attachment perforated membrane on the matrix, described matrix has through hole, described perforated membrane may be located on the surface contacted with the phosphate aqueous solution being contained in described second channel of described matrix and/or be positioned at described matrix the surface contacted with the described oxidation solution being contained in described first passage on.Preferably, described perforated membrane is positioned on the surface contacted with the phosphate aqueous solution being contained in described second channel of described matrix.Hole in described perforated membrane is previously described average pore size is the hole of nano-scale.The average pore size of the through hole on described matrix is not particularly limited, as long as described oxidation solution can be passed through.Preferably, the average pore size of the through hole on described matrix is 1nm to 1000nm (such as 50-200nm).
The shape of described membrane tube can select according to the position relationship of first passage and second channel, is connected by this membrane tube and is as the criterion enabling to described first passage and described second channel.
In one embodiment of the invention, described membrane tube is have the pipeline of at least one passage, and the tube wall of described membrane tube has through hole, and described through hole is average pore size is the hole of nano-scale.
In another embodiment of the invention, described membrane tube is have the pipeline of at least one passage, being attached with perforated membrane on the outer wall of described membrane tube and/or the inwall of passage, the tube wall of described membrane tube has through hole, the hole on described perforated membrane is average pore size is the hole of nano-scale.
Specifically, as Figure 1-3, membrane tube 4 has at least one passage 1.Membrane tube 4 has the pipeline of through hole as matrix on tube wall 2, the inwall of the passage 1 of membrane tube 4 and/or be attached with perforated membrane 3 on the outer wall of membrane tube 4.The average pore size of the through hole on tube wall 2 is not particularly limited, as long as oxidation solution can be made to pass through, can be generally 1nm to 1000nm (such as 50-200nm)；Hole on described perforated membrane is previously described average pore size is the hole of nano-scale.
In above two embodiment, the quantity of the passage in described membrane tube is preferably at least two, such as 4-40 bar.
In actual mechanical process, as shown in Figure 4, membrane tube 4 can with housing 5 with the use of.That is, described extraction mixing arrangement also includes housing 5, and it is internal that at least one membrane tube 4 is arranged on housing 5, Existential Space between outer wall and the inwall of housing 5 of membrane tube 4.Passage in membrane tube 4 is as being used for holding the described second channel of phosphate aqueous solution, and the space that the inwall of the outer wall of membrane tube 4 and housing 5 is formed is as the described first passage for holding described oxidation solution；Or, the passage in membrane tube 4 is as being used for holding the described first passage of oxidation solution, and the space that the inwall of the outer wall of membrane tube 4 and housing 5 is formed is as the described second channel for holding phosphate aqueous solution.Preferably, the passage in membrane tube 4 is as being used for holding the described second channel of phosphate aqueous solution, and the space that the inwall of the outer wall of membrane tube 4 and housing 5 is formed is as the described first passage for holding oxidation solution.
As shown in Figure 4, housing 5 can have the first entrance 6, second entrance 7 and outlet 8, the space that the inwall of the outer wall of membrane tube 4 and housing 5 is formed is as described first passage, passage in membrane tube 4 is as described second channel, described first passage connects with described first entrance 6, the two ends of described second channel connect with described second entrance 7 and described outlet 8 respectively, described first entrance 6 is for importing in described first passage by described oxidation solution, described second entrance is for importing in described second channel by described phosphate aqueous solution, under the effect of pressure differential, oxidation solution enters in described phosphate aqueous solution by the hole on tube wall, carry out pre-extracted and obtain mixed liquor, described mixed liquor leaves described extraction mixing arrangement by described outlet 8.
The material forming described membrane tube can be inorganic material (such as inorganic ceramic), it is also possible to for organic material, if formed the material of this membrane tube not with oxidation solution and phosphate aqueous solution generation chemical interaction.
Described membrane tube filling rate in described housing can be generally 20-50%.Described filling rate refers to the percent value in space that membrane tube occupies and the total measurement (volume) of housing.
According to the present invention, the amount sending into the oxidation solution in phosphate aqueous solution can select according to concrete reaction condition.Oxidation solution can once or gradation send in phosphate aqueous solution, it is ensured that phosphate aqueous solution can effectively extract the hydrogen peroxide component in oxidation solution.Preferably, oxidation solution is 10-100:1 with the volume ratio of phosphate aqueous solution.
In the present invention, the temperature of pre-extracted can be 30-70 DEG C, and the pressure of pre-extracted can for 0.1-0.7MPa with gauge pressure meter.
In the present invention, alkyl-anthraquinone can be 2-alkyl-anthraquinone and/or tetrahydrochysene 2-alkyl-anthraquinone, for instance 2-ethyl-anthraquinone and/or tetrahydrochysene 2-ethyl-anthraquinone；Preferred alkyl-anthraquinone is 2-ethyl-anthraquinone.
In the present invention, possibly together with solvent in described oxidation solution, specifically solvent is the first solvent and the mixture of the second solvent, and described first solvent is C9-C11Aromatic hydrocarbons and/or alkylnaphthalene, described second solvent is phosphate ester and/or alkyl carboxylates.Described first solvent can be such as one or more in methyl naphthalene, hemimellitol, a trimethylbenzene and pseudocumene.Described second solvent can be such as trioctyl phosphate and/or methyl cyclohexanol acetate.Ratio between described first solvent and described second solvent can be conventional selection, and usually, the volume ratio of described first solvent and described second solvent can be 0.5-4:1.
In the present invention, in described oxidation solution, the content of hydrogen peroxide can be 7-18g/L.
In the present invention, in described phosphate aqueous solution, the content of phosphoric acid can be 0.2-0.8g/L.
According to the invention it is preferred in situation, described extraction mixing arrangement is arranged on the feed end of described fiber-film contact.
In the present invention, described fiber-film contact can be conventional various fiber-film contacts, it is possible to for the cylinder of both ends open, two ends are feed end and discharge end.The feed end of fiber-film contact connects with described extraction mixing arrangement, and the discharge end of fiber-film contact connects with the extraction settlement separator for oil-water separation.In described fiber-film contact, fluid distributor and mass transfer space cylinder can be set gradually from feed end to discharge end direction, in the cylinder of mass transfer space, set gradually fluid redistributor and cellosilk from feed end to discharge end direction.Fluid distributor and fluid redistributor can optional holes be board-like, one in overflow-type and board-like fluid distributor, fluid redistributor can have a set of more than.Fluid distributor and fluid redistributor enable the fluid of entrance fiber-film contact to have good distribution on filametntary cross section, thus improving the mass transfer effect of fluid in fiber-film contact.Cellosilk is arranged in the mass transfer space cylinder of fiber-film contact, the fluid being evenly distributed through distributor flows through cellosilk, utilize capillarity different with aqueous phase, the oil phase surface tension on cellosilk, the aqueous phase in addition fiber-film contact and oil phase is made to form liquid film at filament surface, thus increasing two surface areas contacted, make mass-transfer efficiency be greatly enhanced, reach the effect extracted.
In the present invention, described mixed liquor by fiber-film contact mode can there is no particular limitation, the setting of preferred described extraction mixing arrangement mixed liquor described in step (2) can be made in the way of upper entering and lower leaving by fiber-film contact, namely enter from the top of fiber-film contact.So described mixed liquor can be distributed in filament surface better, forms liquid film and improves effect of extracting.
According to the present invention, described fiber-film contact uses the cellosilk of great cluster.Flow through filametntary oxidation solution and phosphate aqueous solution forms liquid film, it is preferable that in situation, the cellosilk used in described fiber-film contact is lipophilic fiber silk or composite fibre silk；Described lipophilic fiber silk at least one in polyester fiber silk, nylon fiber silk, polyurethane fiber silk, polypropylene filaments, polyacrylonitrile fibre silk and polyvinyl chloride fibre silk；Described composite fibre silk is the composite filament of described lipophilic fiber silk and stainless steel silk, and the volume ratio of described lipophilic fiber silk and stainless steel silk is 0.1-10:1.Specifically, polyester fiber silk is the polyester fiber silk purchased from Changzhou Zhu Wei construction material company limited, and composite fibre silk is by the polyester fiber silk purchased from Changzhou Zhu Wei construction material company limited and obtains purchased from the stainless steel silk compound of 316 series of the sensible company in Loudi, Hunan Province.
According to the invention it is preferred in situation, described filametntary average diameter is 10-500 μm.Better fluid mass-transfer effect can be provided when filametntary average diameter is in scope.
According to the present invention, the mass transfer space cylinder that described fiber-film contact includes has provides described oxidation solution to carry out extracting required size, makes oxidation solution and phosphate aqueous solution have suitable liquid film contact area.Under preferable case, the draw ratio of the mass transfer space cylinder of described fiber-film contact is 5-100:1, it is preferred to 10-50:1.
According to the invention it is preferred in situation, in the mass transfer space cylinder of described fiber-film contact, described filametntary filling voidage is 10-90%.Voidage refers in the lateral cross section of mass transfer space cylinder, the percentage ratio of the area of the lateral cross section of the area in the space not occupied by cellosilk and mass transfer space cylinder.Voidage is excessive or too small is not provided that the effect of extracting that the extracting process of anthraquinone hydrogen peroxide obtains, and affects the yield of hydrogen peroxide.
According to the present invention, when carrying out the extraction in step (2), there is no particular limitation for the condition of extraction, but for the effect of extracting obtained, under preferable case, with the filametntary weight in described fiber-film contact for benchmark, the charging weight (hourly) space velocity (WHSV) of described oxidation solution is 2-80h-1, the temperature of described extraction is 30-70 DEG C, with the pressure of the described extraction of gauge pressure meter for 0.1-0.7MPa.
In the present invention, the method also includes in advance oxidation solution and phosphate aqueous solution are preheated to 40-70 DEG C respectively, then adds fiber-film contact contact, extracts.Oxidation solution after preheating can be identical with the temperature of phosphate aqueous solution, it is also possible to differs, it is preferred to identical.The mode wherein preheated can be the preheating method of any routine in this area.
According to the present invention, the profit that described oil-water separation in the method can be conventional is settlement separate, the operating condition of routine can be used, as the mixture after fiber-film contact processes is stood in gun barrel, time of repose can be 1-40 minute, obtaining the raffinate oil phase and the aqueous phase extracted that separate after settlement separate end, wherein aqueous phase extracted is the aqueous solution (being also called aqueous hydrogen peroxide solution) containing hydrogen peroxide；Raffinate oil phase includes solvent, alkyl-anthraquinone etc..Can passing through the discharge outlet below gun barrel and discharge aqueous phase extracted, this aqueous phase extracted can enter follow-up purifying column；And raffinate oil phase can enter follow-up raffinate separator.
The present invention one preferred embodiment in, described extraction mixing arrangement and fiber-film contact can be multiple, and described extraction mixing arrangement is consistent with the quantity of fiber-film contact, the feed end at each fiber-film contact arranges a described extraction mixing arrangement.Preferably, multiple fiber-film contacts adopt the mode of series connection.
Shown in Fig. 5 be the one of the method according to the invention preferred embodiment.In this embodiment, in extracting mixing arrangement 9, the oxidation solution 10 containing hydrogen peroxide and alkyl-anthraquinone is injected and phosphate aqueous solution 11 carries out pre-extracted, obtain mixed liquor；Mixed liquor enters in fiber-film contact 12 and contacts with cellosilk, thus extracting, and the product being extracted.
The preparation method that present invention also offers a kind of hydrogen peroxide, the method includes: when hydrogenation, the working solution containing raw material, hydrogen and the catalyst with catalytic hydrogenation is contacted, obtains the hydride containing alkyl hydrogen anthraquinone；Described hydride is contacted with oxygen under oxidation reaction condition, obtains the oxidation solution containing hydrogen peroxide and alkyl-anthraquinone；Adopt extracting process provided by the invention, from described oxidation solution, isolate hydrogen peroxide；Described raw material is alkyl-anthraquinone.
In the present invention, it is preferable that described raw material is 2-ethyl-anthraquinone and/or tetrahydrochysene 2-ethyl-anthraquinone, more preferably 2-ethyl-anthraquinone.
In the present invention, it is preferable that described alkyl hydrogen anthraquinone is 2-ethyl hydrogen anthraquinone and/or tetrahydrochysene 2-ethyl hydrogen anthraquinone, more preferably 2-ethyl hydrogen anthraquinone.
According to the invention it is preferred in situation, the method that the working solution containing raw material, hydrogen and the catalyst with catalytic hydrogenation contact is included: hydrogen is injected in the working solution containing raw material by the hole that average pore size is nano-scale, obtains containing hydrogen solution；By described containing hydrogen solution to send in tubular fixed-bed reactor in the way of flowing up, contact described with the catalyst with catalytic hydrogenation containing hydrogen solution when hydrogenation.
In the present invention, described average pore size is the average pore size in the hole of nano-scale can be generally 30nm to 800nm, more preferably 30nm to 500nm.Described average pore size adopts scanning electron microscope method to measure.
In the present invention, it is possible to adopt various method to be injected in the working solution containing raw material by the hole that average pore size is nano-scale by hydrogen.
In the preferred embodiment of the present invention, hydrogen is injected in the described working solution containing raw material by the first mixing arrangement, thus obtaining described containing hydrogen solution, described first mixing arrangement can the mixing arrangement shown in Fig. 4 foregoing, this is no longer going to repeat them.Membrane tube therein membrane tube also as described above, repeats no more.
The amount sending into the hydrogen in the working solution containing raw material can select according to concrete reaction condition.Hydrogen is sent in the working solution containing raw material by the method for the present invention by the hole that average pore size is nano-scale, it is possible to makes hydrogen high degree of dispersion and is dissolved in the working solution containing raw material, thus providing enough hydrogen sources for hydrogenation.Therefore, even if the method for the present invention does not send into hydrogen in a large number in the working solution containing raw material, simultaneously without maintaining certain hydrogen dividing potential drop in the reactor, also can obtain high hydrogenation ratio, and reduce the trend of catalyst green coke.According to the inventive method, described hydrogen can once or gradation send in the working solution containing raw material, the mol ratio of total feeding amount of hydrogen and the raw material in the described working solution containing raw material is 0.5-1:1.
It is in the working solution containing raw material under hydrogenation temperature and hydrogenation pressure with the method for the invention it is preferred to hydrogen to be sent into temperature and pressure, so can reduce hydrogen further from containing the trend of effusion hydrogen solution.Specifically, it is possible to hydrogen is sent in the working solution containing raw material that temperature is 40-70 DEG C and pressure is 0.1-0.5MPa (in gauge pressure).
Described tubular fixed-bed reactor refers to the reactor with relatively larger ratio of height to diameter being wherein filled with beds.Specifically, the height of described tubular fixed-bed reactor can be 10-200:1 (such as 10-50:1) with the ratio (that is, ratio of height to diameter) of internal diameter.The internal diameter of described tubular fixed-bed reactor can be conventional selection, for instance can be 20-2000mm.Adopt tubular fixed-bed reactor can reduce the volume of reactor on the one hand, on the other hand when by previously described first mixing arrangement, directly described first mixing arrangement is arranged on the material inlet pipeline of described tubular fixed-bed reactor, flexible operation and convenient.
The method according to the invention, described containing hydrogen solution to be admitted in the way of flowing up in described tubular fixed-bed reactor.Can pass through to send into described from the bottom of described tubular fixed-bed reactor containing hydrogen solution, contact with the catalyst with catalytic hydrogenation in the beds being seated in described tubular fixed-bed reactor, and the post-hydrogenation stream that contact obtains is exported from the top of described tubular fixed-bed reactor.
The present invention can be conventional selection for the concentration of the described working solution Raw containing raw material.Usually, the concentration of the raw material in the described working solution containing raw material can be 10-30 weight %, such as 12-24 weight %.
Heretofore described working solution is possibly together with solvent.Described solvent is not particularly limited, it is possible to select for routine.Specifically, solvent can be the mixture of the first solvent and the second solvent, and described first solvent is C9-C11Aromatic hydrocarbons and/or alkylnaphthalene, described second solvent is phosphate ester and/or alkyl carboxylates.Described first solvent can be such as one or more in methyl naphthalene, hemimellitol, a trimethylbenzene and pseudocumene.Described second solvent can be such as trioctyl phosphate and/or methyl cyclohexanol acetate.Ratio between described first solvent and described second solvent can be conventional selection, and usually, the volume ratio of described first solvent and described second solvent can be 0.5-4:1.
According to the present invention, described can carry out under conventional hydrotreating temperatures and pressure with contacting of catalyst containing hydrogen solution, it does not have be particularly limited to.Under preferable case, described hydrogenation condition includes: temperature is 40-70 DEG C；In gauge pressure, the pressure in tubular fixed-bed reactor is 0.1-0.7MPa；The described volume space velocity containing hydrogen solution is 10-100h-1。
In the present invention, when will send into tubular fixed-bed reactor containing hydrogen solution, the internal diameter described first mixing arrangement being used for export the outlet containing hydrogen solution is r1, the internal diameter described tubular fixed-bed reactor being used for input the entrance containing hydrogen solution is r2, r1/r2=0.6-1 (such as 0.85-1).The internal diameter connecting the pipe of described outlet and described entrance is r3, r1/r3=0.85-1.5 (such as 0.85-1).So containing hydrogen solution in transport process more stable such that it is able to obtain better hydrogenation effect.
Shown in Fig. 6 be the one of the method according to the invention preferred embodiment.In this embodiment, in the first mixing arrangement 13, hydrogen 14 is injected in the solution 15 containing raw material, obtain containing hydrogen solution；Entering in tubular fixed-bed reactor 16 containing hydrogen solution and contact with catalyst, thus carrying out hydrogenation, obtaining the hydride containing alkyl hydrogen anthraquinone.
The method of the present invention is not particularly limited for the kind with the catalyst of catalytic hydrogenation, it is possible to for common various can the hydrogenation of catalysis alkyl-anthraquinone and/or alkyl hydrides anthraquinone to generate the material of alkyl hydrogen anthraquinone.Preferably, described catalyst includes carrier and load active component on the carrier, and described active component is palladium.In described catalyst, the content of the active component counted with element can for 0.25-1 weight %.Described carrier can be conventional selection, it does not have be particularly limited to.Usually, described carrier can be one or more in aluminium oxide, silicon oxide, activated carbon and titanium oxide.
The present invention is for being not particularly limited described hydride and oxygen catalytic concrete grammar under oxidation reaction condition, it is possible to select for routine.For example, it is possible to oxygen is mixed with described hydride, and the mixture obtained is reacted under oxidation reaction condition.Can adopt common various blenders (such as static mixer or dynamic mixer) by oxygen with as described in hydride mix.Described static mixer realizes gas uniform with liquid mixing by changing the flow regime of fluid, be specifically as follows but be not limited in SV type static mixer, SK type static mixer, SX type static mixer, SH type static mixer and SL type static mixer one or more.Described dynamic mixer can be that the various motion by moving component realizes gas and the uniform mixing apparatus of liquid mixing, and described moving component can be such as the common various parts with agitating function.
The present invention one preferred embodiment in, oxygen is injected in described hydride by identical with previously described first mixing arrangement the second mixing arrangement, obtains described oxygen-containing solution；Under oxidation reaction condition, make oxygen-containing solution by the inner space of tubular reactor in the way of flowing up.Namely from solution oxygen-containing described in the bottom feed of stock market's reactor, the oxidation solution obtained after exporting oxidation reaction from the top of tubular reactor.
The mixing arrangement being used for injecting hydrogen working solution for purposes of clarity, is called the first mixing arrangement by the present invention, and the mixing arrangement being used for injecting oxygen hydride is called the second mixing arrangement.
The structure of described second mixing arrangement and the method being connected with tubular reactor, identical with previously described first mixing arrangement, no longer describe in detail herein.
Preferably, in described second mixing arrangement, described first entrance is used for introducing oxygen in described first passage, and described second entrance is for importing in described second channel by hydride, and described oxygen-containing solution leaves described second mixing arrangement by described outlet.
The specification of described tubular reactor and identical with tubular fixed-bed reactor described previously with the connected mode of described second mixing arrangement, can loading catalyst bed in the tubular reactor simply used in oxidation reaction, can not also loading catalyst bed, filler can also be loaded as the case may be.
Oxygen as oxidant.Purity oxygen can be used, it is possible to use the gaseous mixture of oxygen and non-active gas, described non-active gas is group 0 element gas (such as argon), nitrogen such as.In described gaseous mixture, the content of oxygen can be generally 10-50 volume %.The instantiation of described gaseous mixture can be air.
The present invention is not particularly limited for the consumption of oxygen, it is possible to select according to the embodiment of the kind of oxygen and oxidation reaction.When adopting previously described optimal way that oxygen is injected hydride, though the oxidation effectiveness that also can realize under relatively low flow of oxygen.Usually, when adopting previously described method that oxygen is injected hydride, the mol ratio of the alkyl hydrogen anthraquinone in total feeding amount of oxygen and hydride can be 1-3:1.
The specification of described tubular reactor is identical with previously described tubular fixed-bed reactor, and namely the ratio of height to diameter of tubular reactor can be 10-200:1.
Described oxidation reaction condition is not particularly limited, it is possible to select for routine.Usually, described oxidation reaction condition includes: temperature is 40-70 DEG C；In gauge pressure, the pressure in tubular reactor is 0.1-0.7MPa；Described oxygen-containing solution time of staying in described tubular reactor can be 10-500 second (such as the 20-300 second).
It should be noted that, what the present invention used in pretreatment extracts mixing arrangement, the first mixing arrangement used when obtaining containing hydrogen solution, and when obtaining oxygen-containing solution use the second mixing arrangement, all there is the structure of mixing arrangement as shown in Figure 4, the parameter of the membrane tube simply wherein used is variant according to the purpose of mixing, and the material that first passage on device, second channel, outlet and entrance hold according to the purpose of mixing is had any different, described in concrete difference sees above.
In the present invention, being extracted by the oxidation solution that described oxidation reaction obtains, the product of the extraction obtained carries out oil-water separation again, and aqueous phase extracted therein obtains hydrogen peroxide.The method of described extraction is as it has been described above, repeat no more.
Hereinafter will be described the present invention by embodiment.
In following example, pressure is all in gauge pressure.
Scanning electron microscope method is adopted to measure average pore size；
Adopting permanganate titration method to measure the content of hydrogen peroxide, it should be noted that, for meeting the custom of the industry, in aqueous phase extracted, the concentration of hydrogen peroxide is in %, and in raffinate oil phase, the content of hydrogen peroxide is in g/L.
In following example and comparative example, hydrogen peroxide extracts yield and calculates according to following formula:
Embodiment 1
The present embodiment preparation method for the hydrogen peroxide of the present invention is described.
The mixing arrangement used in the present embodiment is as shown in Figure 4, mixing arrangement is used for the membrane tube connecting first passage and second channel as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is evenly distributed with 19 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 100nm, and the average pore size in the hole on perforated membrane is 30nm).With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, passage in membrane tube is as second channel, in the present embodiment, in step (1) and step (2), first passage is used for holding gas, second channel is used for holding liquid, and membrane tube filling rate in the housing is 40%.
In the present embodiment, step (1) and step (2) are respectively adopted the mode shown in Fig. 6 and carry out.
(1) by the working solution containing raw material, (raw material is 2-ethyl-anthraquinone, solvent is volume ratio is the hemimellitol of 3:1:1, the mixed liquor of trioctyl phosphate and methyl cyclohexanol acetate, material concentration is 18 weight %) mix in table 1 is listed when in the first mixing arrangement with hydrogen, then by obtain containing hydrogen solution send into tubular fixed-bed reactor (internal diameter of tubular fixed-bed reactor is 50mm, tubular reactor is provided with 1 beds, the ratio of height to diameter of Catalyst packing is 15:1) in, (active component Pd for 0.3 weight % is counted with element under the conditions shown in Table 1 with the catalyst with catalytic hydrogenation, carrier is aluminium oxide) contact.Wherein, 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 0.9, and the internal diameter of the material outlet of mixing arrangement is 0.9 with the ratio of the material outlet being connected mixing arrangement and the internal diameter of the pipeline of the material inlet of tubular fixed-bed reactor.
(2) effluent (being the hydride containing 2-ethyl hydrogen anthraquinone) of tubular fixed-bed reactor in step (1) is sent in the second mixing arrangement with oxygen mix, and by the oxygen-containing solution obtained to send into tubular reactor (non-loading catalyst and filler inside tubular reactor in the way of flowing up, internal diameter is 50mm, ratio of height to diameter is 15:1) in, oxidation reaction is carried out, the effluent (being the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone) in tubular reactor when table 1 is listed.Wherein, the ratio of the internal diameter of the internal diameter of the material outlet of mixing arrangement and the material inlet of tubular reactor is 0.9, and the internal diameter of the material outlet of mixing arrangement is 0.9 with the ratio of the material outlet being connected mixing arrangement and the internal diameter of the pipeline of the material inlet of tubular reactor.Measuring content of hydrogen peroxide in the oxidation solution prepared containing hydrogen peroxide and 2-ethyl-anthraquinone is 8.6g/L.
(3) mode shown in Fig. 5 is adopted to carry out pre-extracted and extraction the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone prepared in step (2).
Oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is preheated to 40 DEG C, phosphate aqueous solution (phosphorus acid content is 0.8g/L) is preheated to 40 DEG C, then the extraction mixing arrangement 9 that structure is same as shown in Figure 4 is adopted, oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is injected phosphate aqueous solution, carry out pre-extracted, obtain mixed liquor.Wherein, extract the membrane tube in mixing arrangement 9 as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is uniformly distributed 32 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 400nm, the average pore size in the hole on perforated membrane is 30nm), membrane tube filling rate in the housing is 40%；With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, and the passage in membrane tube is as second channel.Extracting the oxidation solution that first passage in mixing arrangement 9 is used for holding containing hydrogen peroxide and 2-ethyl-anthraquinone, second channel is used for holding phosphate aqueous solution；First entrance of housing is for introducing in first passage by the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone, and the second entrance of housing is for importing in second channel by phosphate aqueous solution, and mixed liquor leaves extraction mixing arrangement 9 by outlet.
The temperature of the pre-extracted extracting mixing arrangement 9 is 50 DEG C, and the pressure of pre-extracted is 0.7MPa；The volume ratio of the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone and phosphate aqueous solution is 50:1.
The mixed liquor obtained through above-mentioned pre-extracted is fed in fiber-film contact as shown in Figure 5 and extracts.
The mass transfer space cylinder of fiber-film contact is installed polypropylene filaments (Changzhou Zhu Wei construction material company limited, filametntary average diameter is 200 μm), the draw ratio of mass transfer space cylinder is 20:1, the filametntary weight installed is 1.5kg, and filametntary filling voidage is 70%.The temperature extracted is 45 DEG C, and the pressure of extraction is 0.1MPa, and the charging weight (hourly) space velocity (WHSV) containing hydrogen peroxide and the oxidation solution of 2-ethyl-anthraquinone is 6h-1。
(4) product of extraction step (3) obtained enters to extract in settling tank and stands 5 minutes.The aqueous phase extracted containing hydrogen peroxide is discharged from the lower exit port extracting settling tank.The concentration measuring hydrogen peroxide therein is 42.4%, and the extraction yield calculating hydrogen peroxide is 98.5%.
In raffinate oil phase in analytical extraction settling tank, the content of hydrogen peroxide is 0.05g/L.
Embodiment 2
The present embodiment preparation method for the hydrogen peroxide of the present invention is described.
The mixing arrangement used in the present embodiment is as shown in Figure 4, mixing arrangement is used for the membrane tube connecting first passage and second channel as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is evenly distributed with 4 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 5000nm, and the average pore size in the hole on perforated membrane is 200nm).With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, passage in membrane tube is as second channel, in the present embodiment, in step (1) and step (2), first passage is used for holding gas, second channel is used for holding liquid, and membrane tube filling rate in the housing is 20%.
In the present embodiment, step (1) and step (2) are respectively adopted the mode shown in Fig. 6 and carry out.
(1) by the working solution containing raw material, (raw material is 2-ethyl-anthraquinone, solvent is volume ratio is the hemimellitol of 3:1:1, the mixed liquor of trioctyl phosphate and methyl cyclohexanol acetate, material concentration is 12 weight %) mix in table 1 is listed when in the first mixing arrangement with hydrogen, then by obtain containing hydrogen solution send into tubular fixed-bed reactor (internal diameter of tubular fixed-bed reactor is 1000mm, tubular reactor is provided with 1 beds, the ratio of height to diameter of Catalyst packing is 15:1) in, (active component Pd for 0.5 weight % is counted with element under the conditions shown in Table 1 with the catalyst with catalytic hydrogenation, carrier is aluminium oxide) contact.Wherein, 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 0.9, and the internal diameter of the material outlet of mixing arrangement is 0.9 with the ratio of the material outlet being connected mixing arrangement and the internal diameter of the pipeline of the material inlet of tubular fixed-bed reactor.
(2) effluent (being the hydride containing 2-ethyl hydrogen anthraquinone) of tubular fixed-bed reactor in step (1) is sent in the second mixing arrangement with oxygen mix, and by the oxygen-containing solution obtained to send into tubular reactor (non-loading catalyst and filler inside tubular reactor in the way of flowing up, internal diameter is 50mm, ratio of height to diameter is 15:1) in, oxidation reaction is carried out, the effluent (being the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone) in tubular reactor when table 1 is listed.Wherein, the ratio of the internal diameter of the internal diameter of the material outlet of mixing arrangement and the material inlet of tubular reactor is 0.9, and the internal diameter of the material outlet of mixing arrangement is 0.9 with the ratio of the material outlet being connected mixing arrangement and the internal diameter of the pipeline of the material inlet of tubular reactor.Measuring content of hydrogen peroxide in the oxidation solution prepared containing hydrogen peroxide and 2-ethyl-anthraquinone is 7.8g/L.
(3) mode shown in Fig. 5 is adopted to carry out pre-extracted and extraction the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone prepared in step (2).
Oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is preheated to 45 DEG C, phosphate aqueous solution (phosphorus acid content is 0.6g/L) is preheated to 45 DEG C, then the extraction mixing arrangement 9 that structure is same as shown in Figure 4 is adopted, oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is injected phosphate aqueous solution, carry out pre-extracted, obtain mixed liquor.Wherein, extract the membrane tube in mixing arrangement 9 as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is uniformly distributed 32 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 600nm, the average pore size in the hole on perforated membrane is 200nm), membrane tube filling rate in the housing is 40%；With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, and the passage in membrane tube is as second channel.Extracting the oxidation solution that first passage in mixing arrangement 9 is used for holding containing hydrogen peroxide and 2-ethyl-anthraquinone, second channel is used for holding phosphate aqueous solution；First entrance of housing is for introducing in first passage by the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone, and the second entrance of housing is for importing in second channel by phosphate aqueous solution, and mixed liquor leaves extraction mixing arrangement 9 by outlet.
The temperature of the pre-extracted extracting mixing arrangement 9 is 55 DEG C, and the pressure of pre-extracted is 0.5MPa；The volume ratio of the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone and phosphate aqueous solution is 40:1.
The mixed liquor obtained through above-mentioned pre-extracted is fed in fiber-film contact as shown in Figure 5 and extracts.
The mass transfer space cylinder of fiber-film contact is installed polypropylene filaments (Changzhou Zhu Wei construction material company limited, filametntary average diameter is 500 μm), the draw ratio of mass transfer space cylinder is 10:1, the filametntary weight installed is 1.5kg, and filametntary filling voidage is 70%.The temperature extracted is 50 DEG C, and the pressure of extraction is 0.3MPa, and the charging weight (hourly) space velocity (WHSV) containing hydrogen peroxide and the oxidation solution of 2-ethyl-anthraquinone is 4h-1。
(4) product of extraction step (3) obtained enters to extract in settling tank and stands 10 minutes.The aqueous phase extracted containing hydrogen peroxide is discharged from the lower exit port extracting settling tank.The concentration measuring hydrogen peroxide therein is 30.9%, and the extraction yield calculating hydrogen peroxide is 99.0%.
In raffinate oil phase in analytical extraction settling tank, the content of hydrogen peroxide is 0.08g/L.
Embodiment 3
The present embodiment preparation method for the hydrogen peroxide of the present invention is described.
The mixing arrangement used in the present embodiment is as shown in Figure 4, mixing arrangement is used for the membrane tube connecting first passage and second channel as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is evenly distributed with 10 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 200nm, and the average pore size in the hole on perforated membrane is 500nm).With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, passage in membrane tube is as second channel, in the present embodiment, in step (1) and step (2), first passage is used for holding gas, second channel is used for holding liquid, and membrane tube filling rate in the housing is 50%.
In the present embodiment, step (1) and step (2) are respectively adopted the mode shown in Fig. 6 and carry out.
(1) by the working solution containing raw material, (raw material is 2-ethyl-anthraquinone, solvent is volume ratio is the hemimellitol of 3:1:1, the mixed liquor of trioctyl phosphate and methyl cyclohexanol acetate, material concentration is 24 weight %) mix in table 1 is listed when in the first mixing arrangement with hydrogen, then by obtain containing hydrogen solution send into tubular fixed-bed reactor (internal diameter of tubular fixed-bed reactor is 2000mm, tubular reactor is provided with 1 beds, the ratio of height to diameter of Catalyst packing is 15:1) in, (active component Pd for 1 weight % is counted with element under the conditions shown in Table 1 with the catalyst with catalytic hydrogenation, carrier is aluminium oxide) contact.Wherein, 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 0.9, and the internal diameter of the material outlet of mixing arrangement is 0.9 with the ratio of the material outlet being connected mixing arrangement and the internal diameter of the pipeline of the material inlet of tubular fixed-bed reactor.
(2) effluent (being the hydride containing 2-ethyl hydrogen anthraquinone) of tubular fixed-bed reactor in step (1) is sent in the second mixing arrangement with oxygen mix, and by the oxygen-containing solution obtained to send into tubular reactor (non-loading catalyst and filler inside tubular reactor in the way of flowing up, internal diameter is 50mm, ratio of height to diameter is 15:1) in, oxidation reaction is carried out, the effluent (being the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone) in tubular reactor when table 1 is listed.Wherein, the ratio of the internal diameter of the internal diameter of the material outlet of mixing arrangement and the material inlet of tubular reactor is 0.9, and the internal diameter of the material outlet of mixing arrangement is 0.9 with the ratio of the material outlet being connected mixing arrangement and the internal diameter of the pipeline of the material inlet of tubular reactor.Measuring content of hydrogen peroxide in the oxidation solution prepared containing hydrogen peroxide and 2-ethyl-anthraquinone is 10.7g/L.
(3) mode shown in Fig. 5 is adopted to carry out pre-extracted and extraction the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone prepared in step (2).
Oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is preheated to 50 DEG C, phosphate aqueous solution (phosphorus acid content is 0.2g/L) is preheated to 50 DEG C, then the extraction mixing arrangement 9 that structure is same as shown in Figure 4 is adopted, oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is injected phosphate aqueous solution, carry out pre-extracted, obtain mixed liquor.Wherein, extract the membrane tube in mixing arrangement 9 as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is uniformly distributed 19 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 750nm, the average pore size in the hole on perforated membrane is 500nm), membrane tube filling rate in the housing is 50%；With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, and the passage in membrane tube is as second channel.Extracting the oxidation solution that first passage in mixing arrangement 9 is used for holding containing hydrogen peroxide and 2-ethyl-anthraquinone, second channel is used for holding phosphate aqueous solution；First entrance of housing is for introducing in first passage by the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone, and the second entrance of housing is for importing in second channel by phosphate aqueous solution, and mixed liquor leaves extraction mixing arrangement 9 by outlet.
The temperature of the pre-extracted extracting mixing arrangement 9 is 60 DEG C, and the pressure of pre-extracted is 0.1MPa；The volume ratio of the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone and phosphate aqueous solution is 20:1.
The mixed liquor obtained through above-mentioned pre-extracted is fed in fiber-film contact as shown in Figure 5 and extracts.
The mass transfer space cylinder of fiber-film contact is installed polyurethane fiber silk (Changzhou Zhu Wei construction material company limited, filametntary average diameter is 10 μm), the draw ratio of mass transfer space cylinder is 20:1, the filametntary weight installed is 1.5kg, and filametntary filling voidage is 70%.The temperature extracted is 60 DEG C, and the pressure of extraction is 0.7MPa, and the charging weight (hourly) space velocity (WHSV) containing hydrogen peroxide and the oxidation solution of 2-ethyl-anthraquinone is 12h-1。
(4) product of extraction step (3) obtained enters to extract in settling tank and stands 8 minutes.The aqueous phase extracted containing hydrogen peroxide is discharged from the lower exit port extracting settling tank.The concentration measuring hydrogen peroxide therein is 21.3%, and the extraction yield calculating hydrogen peroxide is 99.5%.
In raffinate oil phase in analytical extraction settling tank, the content of hydrogen peroxide is 0.05g/L.
Table 1
Embodiment 4
The present embodiment preparation method for the hydrogen peroxide of the present invention is described.
Step (1) and (2) in the present embodiment carry out according to the step (1) in embodiment 3 and (2), and measuring content of hydrogen peroxide in the oxidation solution prepared containing hydrogen peroxide and 2-ethyl-anthraquinone is 10.7g/L.
(3) mode shown in Fig. 5 is adopted to carry out pre-extracted and extraction the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone prepared in step (2).
Oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is preheated to 30 DEG C, phosphate aqueous solution (phosphorus acid content is 0.2g/L) is preheated to 30 DEG C, then the extraction mixing arrangement 9 that structure is same as shown in Figure 4 is adopted, oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is injected phosphate aqueous solution, carry out pre-extracted, obtain mixed liquor.Wherein, extract the membrane tube in mixing arrangement 9 as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is uniformly distributed 19 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 700nm, the average pore size in the hole on perforated membrane is 500nm), membrane tube filling rate in the housing is 50%；With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, and the passage in membrane tube is as second channel.Extracting the oxidation solution that first passage in mixing arrangement 9 is used for holding containing hydrogen peroxide and 2-ethyl-anthraquinone, second channel is used for holding phosphate aqueous solution；First entrance of housing is for introducing in first passage by the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone, and the second entrance of housing is for importing in second channel by phosphate aqueous solution, and mixed liquor leaves extraction mixing arrangement 9 by outlet.
The temperature of the pre-extracted extracting mixing arrangement 9 is 40 DEG C, and the pressure of pre-extracted is 0.5MPa；The volume ratio of the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone and phosphate aqueous solution is 40:1.
The mixed liquor obtained through above-mentioned pre-extracted is fed in fiber-film contact as shown in Figure 5 and extracts.
The mass transfer space cylinder of fiber-film contact is installed polyester fiber silk (Changzhou Zhu Wei construction material company limited, filametntary average diameter is 10 μm), the draw ratio of mass transfer space cylinder is 5:1, and the filametntary weight of installation is 1.5kg, and filametntary filling voidage is 70%.The temperature extracted is 40 DEG C, and the pressure of extraction is 0.7MPa, and the charging weight (hourly) space velocity (WHSV) containing hydrogen peroxide and the oxidation solution of 2-ethyl-anthraquinone is 2h-1。
(4) product of extraction step (3) obtained enters to extract in settling tank and stands 10 minutes.The aqueous phase extracted containing hydrogen peroxide is discharged from the lower exit port extracting settling tank.The concentration measuring hydrogen peroxide therein is 42.3%, and the extraction yield calculating hydrogen peroxide is 98.9%.
In raffinate oil phase in analytical extraction settling tank, the content of hydrogen peroxide is 0.10g/L.
Embodiment 5
The present embodiment preparation method for the hydrogen peroxide of the present invention is described.
Step (1) and (2) in the present embodiment carry out according to the step (1) in embodiment 3 and (2), and measuring content of hydrogen peroxide in the oxidation solution prepared containing hydrogen peroxide and 2-ethyl-anthraquinone is 10.2g/L.
(3) mode shown in Fig. 5 is adopted to carry out pre-extracted and extraction the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone prepared in step (2).
Oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is preheated to 30 DEG C, phosphate aqueous solution (phosphorus acid content is 0.2g/L) is preheated to 30 DEG C, then the extraction mixing arrangement 9 that structure is same as shown in Figure 4 is adopted, oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is injected phosphate aqueous solution, carry out pre-extracted, obtain mixed liquor.Wherein, extract the membrane tube in mixing arrangement 9 as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is uniformly distributed 19 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 800nm, the average pore size in the hole on perforated membrane is 500nm), membrane tube filling rate in the housing is 50%；With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, and the passage in membrane tube is as second channel.Extracting the oxidation solution that first passage in mixing arrangement 9 is used for holding containing hydrogen peroxide and 2-ethyl-anthraquinone, second channel is used for holding phosphate aqueous solution；First entrance of housing is for introducing in first passage by the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone, and the second entrance of housing is for importing in second channel by phosphate aqueous solution, and mixed liquor leaves extraction mixing arrangement 9 by outlet.
The temperature of the pre-extracted extracting mixing arrangement 9 is 50 DEG C, and the pressure of pre-extracted is 0.5MPa；The volume ratio of the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone and phosphate aqueous solution is 40:1.
The mixed liquor obtained through above-mentioned pre-extracted is fed in fiber-film contact as shown in Figure 5 and extracts.
The mass transfer space cylinder of fiber-film contact is installed polyvinyl chloride fibre silk (Changzhou Zhu Wei construction material company limited, filametntary average diameter is 10 μm), the draw ratio of mass transfer space cylinder is 5:1, the filametntary weight installed is 1.5kg, and filametntary filling voidage is 70%.The temperature extracted is 50 DEG C, and the pressure of extraction is 0.7MPa, and the charging weight (hourly) space velocity (WHSV) containing hydrogen peroxide and the oxidation solution of 2-ethyl-anthraquinone is 2h-1。
(4) product of extraction step (3) obtained enters to extract in settling tank and stands 1 minute.The aqueous phase extracted containing hydrogen peroxide is discharged from the lower exit port extracting settling tank.The concentration measuring hydrogen peroxide therein is 40.2%, and the extraction yield calculating hydrogen peroxide is 98.7%.
In raffinate oil phase in analytical extraction settling tank, the content of hydrogen peroxide is 0.09g/L.
Embodiment 6
The present embodiment preparation method for the hydrogen peroxide of the present invention is described.
Step (1) and (2) in the present embodiment carry out according to the step (1) in embodiment 3 and (2), and measuring content of hydrogen peroxide in the oxidation solution prepared containing hydrogen peroxide and 2-ethyl-anthraquinone is 12.0g/L.
(3) mode shown in Fig. 5 is adopted to carry out pre-extracted and extraction the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone prepared in step (2).
Oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is preheated to 55 DEG C, phosphate aqueous solution (phosphorus acid content is 0.2g/L) is preheated to 55 DEG C, then the extraction mixing arrangement 9 that structure is same as shown in Figure 4 is adopted, oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone is injected phosphate aqueous solution, carry out pre-extracted, obtain mixed liquor.Wherein, extract the membrane tube in mixing arrangement 9 as shown in Figure 2 (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, membrane tube is uniformly distributed 32 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on matrix is 900nm, the average pore size in the hole on perforated membrane is 500nm), membrane tube filling rate in the housing is 50%；With this membrane tube with the use of a housing, the space that the outer wall of membrane tube and the inwall of housing are formed is as first passage, and the passage in membrane tube is as second channel.Extracting the oxidation solution that first passage in mixing arrangement 9 is used for holding containing hydrogen peroxide and 2-ethyl-anthraquinone, second channel is used for holding phosphate aqueous solution；First entrance of housing is for introducing in first passage by the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone, and the second entrance of housing is for importing in second channel by phosphate aqueous solution, and mixed liquor leaves extraction mixing arrangement 9 by outlet.
The temperature of the pre-extracted extracting mixing arrangement 9 is 60 DEG C, and the pressure of pre-extracted is 0.5MPa；The volume ratio of the oxidation solution containing hydrogen peroxide and 2-ethyl-anthraquinone and phosphate aqueous solution is 30:1.
The mixed liquor obtained through above-mentioned pre-extracted is fed in fiber-film contact as shown in Figure 5 and extracts.
(composite fibre silk is by the polyester fiber silk purchased from Changzhou Zhu Wei construction material company limited and obtains purchased from the stainless steel silk compound of 316 series of the sensible company in Loudi, Hunan Province to install composite fibre silk in the mass transfer space cylinder of fiber-film contact, the volume ratio of polyester fiber silk and stainless steel silk is 0.5:1, filametntary average diameter is 10 μm), the draw ratio of mass transfer space cylinder is 100:1, the filametntary weight installed is 1.5kg, and filametntary filling voidage is 70%.The temperature extracted is 55 DEG C, and the pressure of extraction is 0.7MPa, and the charging weight (hourly) space velocity (WHSV) containing hydrogen peroxide and the oxidation solution of 2-ethyl-anthraquinone is 40h-1。
(4) product of extraction step (3) obtained enters to extract in settling tank and stands 40 minutes.The aqueous phase extracted containing hydrogen peroxide is discharged from the lower exit port extracting settling tank.The concentration measuring hydrogen peroxide therein is 35.4%, and the extraction yield calculating hydrogen peroxide is 98.4%.
In raffinate oil phase in analytical extraction settling tank, the content of hydrogen peroxide is 0.07g/L.
Comparative example 1
According to the method for embodiment 1, the difference is that, step does not have pre-extracted in (3).
Namely specifically, the oxidation solution (content of hydrogen peroxide is 8.6g/L) containing hydrogen peroxide and 2-ethyl-anthraquinone is preheated to 40 DEG C laggard expect in fiber-film contact extract.
The concentration measuring hydrogen peroxide therein is 40.8%, and the extraction yield calculating hydrogen peroxide is 95.0%.
In raffinate oil phase in analytical extraction settling tank, the content of hydrogen peroxide is 0.23g/L.
By embodiment and comparative example result it can be seen that adopt the extracting process of anthraquinone legal system hydrogen peroxide provided by the invention can improve the efficiency that hydrogen peroxide extracts, the extraction yield of hydrogen peroxide reaches more than 98.0%；Also illustrating to improve the stability of hydrogen peroxide, in raffinate phase, the content of hydrogen peroxide is lower than 0.10g/L.

Claims (18)

1. an extracting process for anthraquinone legal system hydrogen peroxide, the method includes:
(1) oxidation solution containing hydrogen peroxide and alkyl-anthraquinone is injected in phosphate aqueous solution by hole that average pore size is nano-scale carry out pre-extracted, obtain mixed liquor；
(2) described mixed liquor is sent into fiber-film contact to extract, and the product of described extraction is carried out oil-water separation, obtain hydrogen peroxide.
2. extracting process according to claim 1, wherein, injects described oxidation solution in phosphate aqueous solution by extracting mixing arrangement；Described extraction mixing arrangement includes at least one first passage and at least one second channel, connected by membrane tube between described first passage and described second channel, described membrane tube at least partially have porose area, described have porose area to have hole that described average pore size is nano-scale, described first passage is used for holding described oxidation solution, described second channel is used for holding described phosphate aqueous solution, and described oxidation solution is injected in described phosphate aqueous solution by the hole that described average pore size is nano-scale.
3. extracting process according to claim 2, wherein, described membrane tube is have the pipeline of at least one passage, and the tube wall of described membrane tube has through hole, and described through hole is average pore size is the hole of nano-scale；Or being attached with perforated membrane on the inwall of the outer wall of described membrane tube and/or passage, the tube wall of described membrane tube has through hole, the hole on described perforated membrane is average pore size is the hole of nano-scale.
4. extracting process according to claim 3, wherein, described extraction mixing arrangement also includes housing, at least one described membrane tube is arranged on described enclosure interior, Existential Space between outer wall and the inwall of described housing of described membrane tube, described housing has the first entrance, second entrance and exit, the space that the inwall of the outer wall of described membrane tube and described housing is formed is as described first passage, passage in described membrane tube is as described second channel, described first passage connects with described first entrance, the two ends of described second channel respectively with described second entrance and described outlet, described first entrance is for importing in described first passage by described oxidation solution, described second entrance is for importing in described second channel by described phosphate aqueous solution, described mixed liquor leaves described extraction mixing arrangement by described outlet.
5. the extracting process according to any one in claim 1-4, wherein, average pore size is the average pore size in the hole of nano-scale is 1-1000nm.
6. the extracting process according to any one in claim 2-4, wherein, described extraction mixing arrangement is arranged on the feed end of described fiber-film contact.
7. the extracting process according to claim 1 or 6, wherein, the cellosilk used in described fiber-film contact is lipophilic fiber silk or composite fibre silk；Described lipophilic fiber silk at least one in polyester fiber silk, nylon fiber silk, polyurethane fiber silk, polypropylene filaments, polyacrylonitrile fibre silk and polyvinyl chloride fibre silk；Described composite fibre silk is the composite filament of described lipophilic fiber silk and stainless steel silk, and the volume ratio of described lipophilic fiber silk and stainless steel silk is 0.1-10:1.
8. extracting process according to claim 7, wherein, described filametntary average diameter is 10-500 μm.
9. the extracting process according to any one in claim 1-8, wherein, the draw ratio of the mass transfer space cylinder of described fiber-film contact is 5-100:1, it is preferred to 10-50:1.
10. the extracting process according to any one in claim 1-9, wherein, in step (1), the volume ratio of described oxidation solution and phosphate aqueous solution is 10-100:1；In described oxidation solution, the content of hydrogen peroxide is 7-18g/L, and in phosphate aqueous solution, the content of phosphoric acid is 0.2-0.8g/L；The temperature of described pre-extracted is 30-70 DEG C, with the pressure of the described pre-extracted of gauge pressure meter for 0.1-0.7MPa；In step (2), with the filametntary weight in described fiber-film contact for benchmark, the charging weight (hourly) space velocity (WHSV) of described oxidation solution is 2-80h-1, the temperature of described extraction is 30-70 DEG C, with the pressure of the described extraction of gauge pressure meter for 0.1-0.7MPa.
11. a preparation method for hydrogen peroxide, the method includes: when hydrogenation, the working solution containing raw material, hydrogen and the catalyst with catalytic hydrogenation is contacted, obtains the hydride containing alkyl hydrogen anthraquinone；Described hydride is contacted with oxygen under oxidation reaction condition, obtains the oxidation solution containing hydrogen peroxide and alkyl-anthraquinone；Adopt the extracting process described in any one in claim 1-10, from described oxidation solution, isolate hydrogen peroxide；Described raw material is alkyl-anthraquinone.
12. method according to claim 11, wherein, the method that working solution containing raw material, hydrogen and the catalyst with catalytic hydrogenation contact is included: hydrogen is injected in the working solution containing raw material by the hole that average pore size is nano-scale, obtains containing hydrogen solution；By described containing hydrogen solution to send in tubular fixed-bed reactor in the way of flowing up, contact described with the catalyst with catalytic hydrogenation containing hydrogen solution when hydrogenation.
13. the method according to claim 11 or 12, wherein, the mol ratio of the raw material in total feeding amount of hydrogen and the described working solution containing raw material is 0.5-1:1.
14. the method according to claim 11 or 12, wherein, described hydrogenation condition includes: temperature is 40-70 DEG C；In gauge pressure, the pressure in tubular fixed-bed reactor is 0.1-0.7MPa；The described volume space velocity containing hydrogen solution is 10-100h-1。
15. the method according to claim 11 or 12, wherein, the solvent of the working solution containing raw material is the first solvent and the mixture of the second solvent, and described first solvent is C9-C11Aromatic hydrocarbons and/or alkylnaphthalene, described second solvent is phosphate ester and/or alkyl carboxylates, and the volume ratio of described first solvent and described second solvent is 0.5-4:1.
16. method according to claim 11, wherein, the method that described hydride contacts under oxidation reaction condition with oxygen is included: oxygen is injected in described hydride by the hole that average pore size is nano-scale, obtains oxygen-containing solution；Under oxidation reaction condition, make oxygen-containing solution by the inner space of tubular reactor in the way of flowing up.
17. the method according to claim 11 or 16, wherein, the mol ratio of the alkyl hydrogen anthraquinone in total feeding amount of oxygen and hydride is 1-3:1.
18. the method according to claim 11 or 16, wherein, described oxidation reaction condition includes: temperature is 40-70 DEG C；In gauge pressure, the pressure in tubular reactor is 0.1-0.7MPa；The described oxygen-containing solution time of staying in described tubular reactor is the 10-500 second.
CN201410852648.1A 2014-12-31 2014-12-31 Extraction method for hydrogen peroxide preparation by anthraquinone process and preparation method of hydrogen peroxide Pending CN105800562A (en)

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