CN104926630A - Alkyl anthrahydroquinone oxidation method and hydrogen peroxide production method - Google Patents
Alkyl anthrahydroquinone oxidation method and hydrogen peroxide production method Download PDFInfo
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- CN104926630A CN104926630A CN201410108219.3A CN201410108219A CN104926630A CN 104926630 A CN104926630 A CN 104926630A CN 201410108219 A CN201410108219 A CN 201410108219A CN 104926630 A CN104926630 A CN 104926630A
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- 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
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- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
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Abstract
The present invention provides an alkyl anthrahydroquinone oxidation method which is as follows: oxygen is injected into an alkyl anthrahydroquinone-containing solution by pores with the average pore size in nano-size to obtain an oxygen-containing solution; under the oxidation reaction conditions, the oxygen-containing solution passes through the interior space of a tubular reactor in the upflowing manner. The present invention also provides a hydrogen peroxide production method comprising the following steps: under hydrogenation reaction conditions, a raw-material-containing solution and hydrogen are in contact with a catalyst having a catalytic hydrogenation effect to obtain an alkyl anthrahydroquinone-containing mixture, and the raw material is alkyl anthraquinone and / or hydrogenated alkyl anthraquinone; alkyl anthrahydroquinone in the alkyl anthrahydroquinone-containing mixture is oxidized by the method; and hydrogen peroxide is separated from the mixture obtained by oxidation. The oxidation process can achieve good oxidation effects even the dosage of the oxidant is low, the raw material conversion rate is high, and the hydrogen peroxide selectivity is good.
Description
Technical field
The present invention relates to a kind of method for oxidation of alkyl anthrahydroquinone, the invention still further relates to a kind of method of producing hydrogen peroxide.
Background technology
Hydrogen peroxide is one of main basic chemical in the world, as oxygenant, SYNTHETIC OPTICAL WHITNER, sterilizing agent, polymerization starter and linking agent, the numerous areas such as papermaking, weaving, chemical synthesis, electronics, military project, food-processing, medicine, makeup and metallurgy can be widely used in.Only produce water and oxygen after peroxide decomposition, to environment non-secondary pollution, belong to green chemical.Along with the development of social demand, especially ecological environmental protection is paid attention to day by day, and the application for hydrogen peroxide opens more wide market.
Anthraquinone is the prevailing technology producing hydrogen peroxide in the world, it comprises the processes such as hydrogenation, oxidation, extraction and aftertreatment, wherein oxidizing reaction is reaction automatically, it is the important step in anthraquinone producing hydrogen peroxide, this process, to raising oxidation efficiency, keeps the stability of this reaction and security to have great effect.
At present, the oxidising process of domestic hydrogen peroxide manufacture device adopts tower equipment to realize usually, and in the oxidizing reaction of carrying out in tower equipment, oxidising process is slow, and residence time of material is long, and then causes oxidation efficiency low, and equipment volume is large; There is the phenomenons such as wall stream and axial backmixing in tower simultaneously, reduce mass-transfer efficiency.
Therefore, the deficiency that the efficient method for oxidation of development solves the existence of existing anthraquinone legal system hydrogen peroxide process is badly in need of.
Summary of the invention
The object of the invention is to the method for oxidation above shortcomings overcoming existing anthraquinone legal system hydrogen peroxide process, provide a kind of alkyl anthrahydroquinone method for oxidation and a kind of method of producing hydrogen peroxide, the method can obtain high oxidation efficiency.
According to a first aspect of the invention, the invention provides a kind of method for oxidation of alkyl anthrahydroquinone, the method comprises injects by the hole that mean pore size is nano-scale the solution containing alkyl anthrahydroquinone by oxygen, obtains containing oxygen solution; Under oxidation reaction condition, make the described oxygen solution that contains with the internal space of the mode upwards flowed by tubular reactor.
According to a second aspect of the invention, the invention provides a kind of method of producing hydrogen peroxide, the method comprises: under hydrogenation condition, by containing the solution of raw material and hydrogen and the catalyst exposure with catalytic hydrogenation, obtain the mixture containing alkyl anthrahydroquinone, described raw material is alkyl-anthraquinone and/or alkyl hydrides anthraquinone; Adopt the method provided according to a first aspect of the invention by the alkyl anthrahydroquinone oxidation in the mixture containing alkyl anthrahydroquinone; Hydrogen peroxide is isolated from the mixture that oxidation obtains.
Even if the oxidation effectiveness that method for oxidation of the present invention also can obtain under lower oxygenant consumption, feed stock conversion is high and the selectivity of hydrogen peroxide is good.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.
Fig. 1 is used for schematically illustrating a kind of preferred implementation of the component of adjacent first channel and second passage in the mixing device that the present invention uses.
Fig. 2 is a kind of cross sectional representation of the component shown in Fig. 1.
Fig. 3 is the another kind of cross sectional representation of the component shown in Fig. 1.
Fig. 4 is the structural representation of the mixing device that the present invention uses.
Fig. 5 is a kind of embodiment of method provided by the invention.
Fig. 6 is the another kind of embodiment of method provided by the invention.
Fig. 7 is another embodiment of method provided by the invention.
Fig. 8 is for illustration of the annexation between mixing device and tubular reactor or tubular fixed-bed reactor.
Description of reference numerals
1: passage 2: tube wall
3: porous-film 4: for the component of adjacent first channel and second passage
5: housing 6: the first entrance
7: the second entrances 8: outlet
9: the first mixing devices 10: oxygen
11: the solution 12 containing alkyl anthrahydroquinone: 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, the method comprises injects by the hole that mean pore size is nano-scale the solution containing alkyl anthrahydroquinone by oxygen, obtains containing oxygen solution; Under oxidation reaction condition, make the described oxygen solution that contains with the internal space of the mode upwards flowed by tubular reactor.
In the present invention, described mean pore size is the mean pore size in the hole of nano-scale can be generally 1nm to 1000nm, is preferably 30nm to 1000nm, is more preferably 30-500nm.Described mean pore size adopts scanning electron microscope method to measure.
Can adopt various method that oxygen is injected by the hole that mean pore size is nano-scale the solution containing alkyl anthrahydroquinone.
In the preferred embodiment of the present invention, oxygen is injected the described solution containing alkyl anthrahydroquinone by the first mixing device, thus obtain described containing oxygen solution, described first mixing device comprises at least one first channel and at least one second passage, adjoined by a component between described first channel and described second passage, described component at least part of for there being porose area, described have porose area to have hole that described mean pore size is nano-scale, described first channel is for holding described oxygen, described second passage is for holding the described solution containing alkyl anthrahydroquinone, described oxygen is injected into described containing in the solution of alkyl anthrahydroquinone by the hole that described mean pore size is nano-scale.
Described component at least part of for there being porose area, described in have porose area to extend along the length direction of described component.Preferably, porose area is had to cover whole component (that is, be that the component in the hole of nano-scale adjoins by having described mean pore size between described first channel and described second passage, oxygen is injected in the solution containing alkyl anthrahydroquinone by described hole) described in.Described have porose area to have hole that described mean pore size is nano-scale, with make oxygen pass through described in there is the hole that mean pore size is nano-scale be injected in the solution containing alkyl anthrahydroquinone.
Described component can for various can make to be contained in oxygen in described first channel by the hole and entering that described mean pore size is nano-scale be contained in second passage containing the component in the solution of alkyl anthrahydroquinone.In an example, described component is formed by porous material, and the mean pore size in hole is wherein nano-scale.In another example, described component comprises matrix and attachment porous-film on the matrix, described matrix has through hole, described porous-film can be positioned at described matrix with on the surface contacted containing the solution of alkyl anthrahydroquinone being contained in described second passage and/or be positioned on the surface contacted with the oxygen being contained in described first channel of described matrix.Preferably, described porous-film is positioned on the surface contacted with the solution containing alkyl anthrahydroquinone being contained in described second passage of described matrix.The hole of to be previously described mean pore size be the hole in described porous-film nano-scale.The mean pore size of the through hole on described matrix is not particularly limited, as long as can by gas.Preferably, the mean pore size of the through hole on described matrix is 1nm to 1000 μm (as 50-200 μm).
The shape of described component can be selected according to the position relationship of first channel and second passage, is as the criterion by this component is adjacent can make described first channel and described second passage.
In one embodiment of the invention, described component is the pipeline with at least one passage.The tube wall of described pipeline has through hole, and the mean pore size of described through hole is previously described nano-scale.
In another embodiment of the invention, described component is the pipeline with at least one passage, the outer wall of described pipeline and/or the inwall of passage are attached with porous-film, described tube wall has through hole, the hole of to be mean pore size be the hole on described porous-film nano-scale, is called film pipe by this component below.Particularly, as Figure 1-3, described component is the film pipe with at least one passage.Described film pipe has the pipeline of through hole as matrix on tube wall 2, and described pipeline has at least one passage 1, and the inwall of passage 1 of described pipeline and/or the outer wall of pipeline are attached with porous-film 3.The mean pore size of the through hole on tube wall is not particularly limited, as long as oxygen can be made to pass through, can be generally 1nm to 1000 μm (as 50-200 μm); The hole of to be previously described mean pore size be the hole on described porous-film nano-scale.
In above-mentioned two kinds of embodiments, the quantity of the passage on described pipeline or described film pipe is preferably at least two, as 4-20 bar.
In actual mechanical process, described component be pipeline or film pipe time, as shown in Figure 4, component 4 can with housing 5 with the use of.That is, described first mixing device can also comprise housing 5, at least one component 4 is placed in housing 5, and makes Existential Space between the outer wall of component 4 and the inwall of housing 5.Passage on described component is as the described second passage for holding the solution containing alkyl anthrahydroquinone, and the space that the outer wall of described component and the inwall of described housing are formed is as the described first channel for holding oxygen; Or the passage on described component is as the described first channel for holding oxygen, and the space that the outer wall of described component and the inwall of described housing are formed is as the described second passage for holding the solution containing alkyl anthrahydroquinone.Preferably, the passage on described component is as the described second passage for holding the solution containing alkyl anthrahydroquinone, and the space that the outer wall of described component and the inwall of described housing are formed is as the described first channel for holding oxygen.
As shown in Figure 4, housing 5 has the first entrance 6, second entrance 7 and outlet 8, and first channel is communicated with the first entrance 6, the two ends of second passage respectively with the second entrance 7 with export 8 and be communicated with.First entrance 6 is for importing in first channel by oxygen, second entrance 7 is for importing in second passage by the solution containing alkyl anthrahydroquinone, under the effect of pressure difference, oxygen enters described containing in the solution of alkyl anthrahydroquinone by the hole on tube wall, thus obtain, containing oxygen solution, leaving the first mixing device containing oxygen solution by outlet 8.
The material forming described component can for inorganic materials (as inorganic ceramic), also can be organic materials, if the material forming this component not with oxygen and the solution generation chemical interaction containing alkyl anthrahydroquinone.
The filling ratio of described component in described housing can be generally that 20-50%(is as 35-45%).Described filling ratio refers to the percent value of the cubic capacity of the space that component occupies and housing.
The amount sent into containing the oxygen in the solution of alkyl anthrahydroquinone can be selected according to concrete reaction conditions.Oxygen is sent in the solution containing alkyl anthrahydroquinone by the hole that mean pore size is nano-scale by method of the present invention, can make oxygen high dispersing and be dissolved in the solution containing alkyl anthrahydroquinone, thus provides enough oxygen sources for oxidizing reaction.Therefore, even if method of the present invention does not send into oxygen, the oxidation effectiveness that also can obtain in a large number to containing in the solution of alkyl anthrahydroquinone.According to the inventive method, described oxygen can once or gradation send in the solution containing alkyl anthrahydroquinone, total feeding amount of oxygen with can should be 1-3:1 containing the mol ratio of the alkyl anthrahydroquinone in the solution of alkyl anthrahydroquinone.
According to method of the present invention, preferably oxygen is sent into temperature and pressure be under oxidizing temperature and oxidative pressure containing in the solution of alkyl anthrahydroquinone, oxygen can be reduced so further from containing the trend of overflowing oxygen solution.Particularly, oxygen can be sent into temperature and be 30-70 DEG C and pressure is that 0.1-0.7MPa(is in gauge pressure) containing in the solution of alkyl anthrahydroquinone.
Described tubular reactor refers to the reactor had compared with larger ratio of height to diameter.Particularly, the height of described tubular reactor and the ratio (that is, aspect ratio) of internal diameter can be that 10-200:1(is as 10-50:1).The internal diameter of described tubular reactor can be conventional selection, such as, can be that 20-2000mm(is as 30-100mm).Adopt tubular reactor can reduce the volume of reactor on the one hand, on the other hand when by previously described first mixing device (be particularly pipeline or film pipe at described component), directly described first mixing device is arranged on the material inlet pipeline of described tubular reactor, flexible operation and convenient.Described tubular reactor, can loading catalyst according to concrete method for oxidation, also can not loading catalyst, as the case may be, can also load various filler in described tubular reactor.
According to method of the present invention, the described oxygen solution that contains is admitted in described tubular reactor in the mode upwards flowed.Can pass through to send into described from the bottom of described tubular reactor containing oxygen solution, and after oxidation contact obtained, logistics exports from the top of described tubular reactor.
According to method of the present invention, the quantity of described tubular reactor can be 1, also can be more than 2.When the quantity of described tubular reactor is more than 2, described tubular reactor can, for being connected in series, can, for being connected in parallel, can also be also series connection and combination in parallel.Described being connected in series refers to that the effluent of previous tubular reactor is the charging of next tubular reactor; Described being connected in parallel refers to do not have material to exchange between tubular reactor.
Method of the present invention can be oxidized various alkyl anthrahydroquinone (comprising alkyl hydrides anthrahydroquinone).Preferably, described raw material is 2-ethyl anthracene quinhydrones and/or tetrahydrochysene 2-ethyl anthracene quinhydrones.
According to method for oxidation of the present invention, the concentration containing the alkyl anthrahydroquinone in the solution of alkyl anthrahydroquinone can be conventional selection, can be generally 10-30 % by weight, as 10-24 % by weight.When tubular reactor is the two or more tubular reactor be connected in series, the concentration of raw material refers to the concentration containing the alkyl anthrahydroquinone in the solution of alkyl anthrahydroquinone entering first tubular reactor.
The present invention is not particularly limited for the solvent of the described solution containing raw material, can be conventional selection.Particularly, the solvent of the described solution containing raw material is phosphoric acid ester and/or alkyl carboxylates, as trioctyl phosphate and/or methyl cyclohexanol acetate.
Described oxidation reaction condition is not particularly limited, and can be conventional selection.Usually, described oxidation reaction condition comprises: temperature is 40-70 DEG C; In gauge pressure, the pressure in tubular reactor is 0.1-0.7MPa; It can be 10-500 second (as 20-300 second) containing the residence time of oxygen solution in described tubular reactor.
Adopt previously described first mixing device to inject containing the solution of alkyl anthrahydroquinone by oxygen, to obtain containing oxygen solution, and will containing oxygen solution feeding tubular reactor time, described first mixing device is r for the internal diameter exported containing the outlet of oxygen solution
1, described tubular reactor is r for the internal diameter inputted containing the entrance of oxygen solution
2, r
1/ r
2=0.6-1(is as 0.85-1).The internal diameter connecting the pipe of described outlet and described entrance is r
3, r
1/ r
3=0.85-1.5(is as 0.85-1).More stable in transport process containing oxygen solution like this, thus better oxidation effectiveness can be obtained.
According to the one of method of the present invention preferred embodiment shown in Fig. 5.In this embodiment, oxygen 10 is injected the solution 11 containing alkyl anthrahydroquinone in the first mixing device 9, obtain containing oxygen solution.Enter in tubular reactor 12 containing oxygen solution and carry out oxidizing reaction, obtain the reaction mixture containing hydrogen peroxide.
According to this embodiment, can arrange multiple tubular reactor (as two or more tubular reactor), can, for being connected in series, can, for being connected in parallel, can also be also series connection and combination in parallel between multiple tubular reactor.When multiple tubular reactor is connected in series, along the flow direction of material, the first mixing device can be arranged on the inlet end of first tubular reactor; Also as shown in Figure 6, the first mixing device 9 can be set respectively at the inlet end of each tubular reactor 12.When multiple tubular reactor is connected in parallel, first mixing device only can be set, will solution and the oxygen mix of alkyl anthrahydroquinone be contained, then send in the multiple tubular reactors be connected in parallel by what obtain respectively containing oxygen solution; Also as shown in Figure 7 the first mixing device 9 can be set respectively at the inlet end of each tubular reactor 12.
Can adopt and in various manners the first mixing device is connected on the entrance pipe of tubular reactor, such as: a ring flange (Fig. 8 shows one of them ring flange 13) respectively can be set at the two ends of mixing device, be connected with the flangeseal on corresponding entrance pipe separately (as shown in Figure 8, the ring flange 13 of mixing device one end is tightly connected with the ring flange 14 on entrance pipe); The other end of entrance pipe is connected with the ring flange 16 of the inlet end of tubular reactor 12 by ring flange 15.
According to method for oxidation of the present invention, purity oxygen can be used as oxygenant, the gas mixture of oxygen and non-active gas also can be used as oxygenant, described non-active gas is neutral element gas (as argon gas), nitrogen such as.In described gas mixture, the content of oxygen can be generally 10-50 volume %.The specific examples of described gas mixture can be air.
Present invention also offers a kind of method of producing hydrogen peroxide, the method comprises: under hydrogenation condition, by containing the solution of raw material and hydrogen and the catalyst exposure with catalytic hydrogenation, obtain the mixture containing alkyl anthrahydroquinone, described raw material is alkyl-anthraquinone and/or alkyl hydrides anthraquinone; Adopt method provided by the invention by the alkyl anthrahydroquinone oxidation in the mixture containing alkyl anthrahydroquinone; Hydrogen peroxide is isolated from the mixture that oxidation obtains
The method that alkyl anthrahydroquinone is oxidized is described in detail above, repeats no more herein.
According to method of the present invention, conventional various methods can be adopted to be contacted under hydrogenation condition with the catalyzer with catalytic hydrogenation with hydrogen by the solution containing raw material, obtain the mixture containing alkyl anthrahydroquinone.Such as: hydrogen can mix in conventional various mixing tanks (as static mixer or dynamic mixer) with the solution containing raw material, be filled with have in the fixed-bed reactor of catalytic hydrogenation by obtaining mixture feeding, carry out hydrogenation.Described static mixer realizes gas and liquid mixing even by the flow state of alter, 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 parts realizes gas and the uniform mixing equipment of liquid mixing, and described moving parts such as can for the common various parts with agitating function.
One of the present invention preferred embodiment in, hydrogen is injected the described solution containing raw material by the second mixing device identical with previously described first mixing device, sends in tubular fixed-bed reactor containing hydrogen solution by what obtain and there is the catalyst exposure of catalytic hydrogenation.
The mixing device be used for oxygen injects containing the solution of alkyl anthrahydroquinone, for clearly object, is called the first mixing device by the present invention, and the mixing device be used for hydrogen injects containing the solution of raw material is called the second mixing device.
The structure of the second mixing device and identical with previously described first mixing device with the mode of connection of tubular fixed-bed reactor, no longer describes in detail herein.Preferably, in described second mixing device, described first entrance is used for hydrogen to import in described first channel, and described second entrance is used for the described solution containing raw material to import in described second passage, and the described hydrogen solution that contains leaves described second mixing device by described outlet.
The specification of described tubular fixed-bed reactor is identical with previously described tubular reactor.
The amount sent into containing the hydrogen in the solution of raw material can be selected according to concrete reaction conditions.Hydrogen is sent in the solution containing raw material by the hole that mean pore size is nano-scale by method of the present invention, can make hydrogen high dispersing and be dissolved in the solution containing raw material, thus provides enough hydrogen sources for hydrogenation.Therefore, even if method of the present invention does not send into hydrogen in a large number to containing in the solution of raw material, simultaneously without the need to maintaining certain hydrogen dividing potential drop in the reactor, also can obtain high hydrogenation ratio, and reducing the trend of catalyzer coking.According to the inventive method, described hydrogen can once or gradation send in the solution containing raw material, total feeding amount of hydrogen with can should be 0.5-1:1 containing the mol ratio of the raw material in the solution of raw material.
According to method of the present invention, preferably hydrogen is sent into temperature and pressure be under hydrogenation temperature and hydrogenation pressure containing in the solution of raw material, hydrogen can be reduced so further from containing the trend of overflowing hydrogen solution.Particularly, hydrogen can be sent into temperature and be 40-70 DEG C and pressure is that 0.1-0.5MPa(is in gauge pressure) containing in the solution of raw material.
According to method of the present invention, the described hydrogen solution that contains can be sent in tubular fixed-bed reactor in the mode upwards flowed, and also can be admitted in described tubular fixed-bed reactor in the mode flowed downward.Preferably be admitted in described tubular fixed-bed reactor in the mode upwards flowed, even if like this under lower hydrogen usage, the hydrogenation effect that also can obtain, catalyzer still demonstrates long work-ing life simultaneously.
The described contact containing hydrogen solution and catalyzer can be carried out under the hydrotreating temperatures of routine and pressure, is not particularly limited.Usually, the described hydrogen solution that contains is comprised with the condition of the catalyst exposure with catalytic hydrogenation: temperature can be 40-70 DEG C; In gauge pressure, the pressure in tubular fixed-bed reactor can be 0.1-0.5MPa; The volume space velocity of liquid material can be 10-100h
-1.
Described can be 2-ethyl-anthraquinone and/or tetrahydrochysene 2-ethyl-anthraquinone containing the raw material in the solution of raw material.
The present invention can be conventional selection for the concentration of the described solution Raw containing raw material.Usually, the described concentration containing the raw material in the solution of raw material can be 10-30 % by weight, as 10-24 % by weight.When tubular fixed-bed reactor is the two or more tubular fixed-bed reactor be connected in series, the concentration of raw material refers to the concentration containing the raw material in the solution of raw material entering first tubular fixed-bed reactor.
The present invention is not particularly limited for the solvent of the described solution containing raw material, can be conventional selection.Particularly, the solvent of the described solution containing raw material is the mixture of the first solvent and the second solvent, and described first solvent is C
9-C
11aromatic hydrocarbons and/or alkylnaphthalene, described second solvent is phosphoric acid ester and/or alkyl carboxylates.Described first solvent can be such as one or more in methylnaphthalene, hemimellitol, a trimethylbenzene and unsym-trimethyl benzene.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.
Method of the present invention is not particularly limited for the kind of the catalyzer with catalytic hydrogenation, can be common various can the hydrogenation of catalysis alkyl-anthraquinone and/or alkyl hydrides anthraquinone to generate the material of alkyl anthrahydroquinone.Preferably, described catalyzer comprises carrier and load activeconstituents on the carrier, and described activeconstituents is palladium.In described catalyzer, can be 0.25-1 % by weight in the content of the activeconstituents of element.Described carrier can be conventional selection, is not particularly limited.Usually, described carrier can be one or more in aluminum oxide, silicon oxide, gac and titanium oxide.
The present invention is not particularly limited for the method isolating hydrogen peroxide in the mixture obtained from oxidation, can be conventional selection.Preferably, the method for extraction is adopted to isolate hydrogen peroxide from the mixture that oxidation obtains.The extraction agent that the extraction agent that extraction uses can be commonly used for this area, is preferably water, directly can obtains hydrogen peroxide like this.Obtaining hydrogen peroxide can adopt conventional various methods to carry out aftertreatment.
According to method of the present invention, the surplus solution (as extracting phase) having isolated hydrogen peroxide can using containing the solution circulated of raw material as hydrogenation at least partly.
Below in conjunction with embodiment and comparative example, the present invention is described in detail, but therefore do not limit the scope of the invention.
In following examples and comparative example, adopt scanning electron microscope method to measure mean pore size, pressure is all in gauge pressure.
In following examples and comparative example, adopt the composition of high performance liquid chromatography to the effluent of the tubular fixed-bed reactor as hydrogenation reactor to analyze, on this basis, adopt following formulae discovery hydrogenation ratio.
Hydrogenation ratio=the mole number/containing the mole number of alkyl-anthraquinone in the solution of raw material of alkyl anthrahydroquinone [in the effluent] × 100%.
In following examples and comparative example, adopt the composition of high performance liquid chromatography to the effluent of the tubular reactor as oxidation reactor to analyze, on this basis, adopt the following transformation efficiency of formulae discovery alkyl anthrahydroquinone and the selectivity of hydrogen peroxide.
The transformation efficiency of alkyl anthrahydroquinone=[(in the mixture that hydrogenation obtains alkyl anthrahydroquinone mole number-effluent in the mole number of alkyl anthrahydroquinone) mole number of alkyl anthrahydroquinone in the mixture that obtains of/hydrogenation] × 100%;
The selectivity of hydrogen peroxide=[in effluent hydrogen peroxide mole number/(in the mixture that hydrogenation obtains alkyl anthrahydroquinone mole number-effluent in the mole number of alkyl anthrahydroquinone)] × 100%.
Embodiment 1-8 is for illustration of alkyl anthrahydroquinone method for oxidation of the present invention and the method for producing hydrogen peroxide.
Embodiment 1
The mixing device used in the present embodiment as shown in Figure 4, be that film pipe as shown in Figure 2 (is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd for the component of adjacent first channel and second passage in mixing device, pipeline is evenly distributed with 19 passages, the internal diameter of each passage is 3.3mm, the mean pore size in the hole on matrix is 100 μm, the mean pore size in the hole on porous-film is 30nm) and a housing using with this tube fit, the space that the outer wall of pipeline and the inwall of housing are formed is as first channel, passage on pipeline is as second passage, first channel is for holding gas, second passage is used for receiving fluids, film pipe filling ratio is in the housing 40%.
In the present embodiment, step (1) and step (2) adopt the mode shown in Fig. 5 to carry out respectively.
(1) by the solution containing raw material, (raw material is 2-ethyl-anthraquinone, the hemimellitol of solvent to be volume ratio be 3:1:1, the mixed solution of trioctyl phosphate and methyl cyclohexanol acetate, material concentration is 12 % by weight) mix under the condition listed in table 1 in the second mixing device with hydrogen, then by obtain containing hydrogen solution send into tubular fixed-bed reactor (internal diameter of tubular fixed-bed reactor is 50mm, 1 beds is provided with in tubular reactor, the aspect ratio of catalyst loading is 15:1) in, under the conditions shown in Table 1 with there is the catalyzer of catalytic hydrogenation (in element active ingredient for 0.3wt%Pd, carrier is aluminum oxide) contact.Analyze the effluent of tubular fixed-bed reactor and calculate hydrogenation ratio, result is listed in Table 1.
Wherein, the ratio of the internal diameter of the internal diameter of the material outlet of mixing device and the material inlet of tubular fixed-bed reactor is 0.9, and the internal diameter of the material outlet of mixing device is 0.9 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular fixed-bed reactor that are connected mixing device.
(2) effluent of tubular fixed-bed reactor in step (1) is sent in the first mixing device with oxygen mix, and the oxygen-containing mixture obtained is sent into tubular reactor (the non-loading catalyst in tubular reactor inside and filler in the mode upwards flowed, internal diameter is 50mm, aspect ratio is 15:1) in, under the condition that table 4 is listed, carry out oxidizing reaction.Analyze the effluent of tubular reactor and calculate the transformation efficiency of alkyl anthrahydroquinone and the transformation efficiency of hydrogen peroxide, result is listed in Table 1.
Wherein, the ratio of the internal diameter of the internal diameter of the material outlet of mixing device and the material inlet of tubular reactor is 0.9, and the internal diameter of the material outlet of mixing device is 0.9 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular reactor that are connected mixing device.
Comparative example 1
The method identical with embodiment 1 is adopted to produce hydrogen peroxide, unlike, in the mixing device used in step (2), in the component of adjacent first channel and second passage, the mean pore size on porous-film is 5 μm (being purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd).
Experimental result is listed in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to produce hydrogen peroxide, unlike, in the mixing device used in step (1), in the component of adjacent first channel and second passage, the mean pore size on porous-film is 5 μm (being purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd).
Experimental result is listed in Table 1.
Comparative example 2
The method identical with embodiment 1 is adopted to produce hydrogen peroxide, unlike, in step (2), mixing device static mixer (purchased from the SV type static mixer of Qidong person of outstanding talent along many petrochemical equipments company limited) replaces.
Experimental result is listed in Table 1.
Embodiment 3
The method identical with embodiment 1 is adopted to produce hydrogen peroxide, unlike, in step (1), mixing device static mixer (purchased from the SV type static mixer of Qidong person of outstanding talent along many petrochemical equipments company limited) replaces.
Experimental result is listed in Table 1.
Comparative example 3
The method identical with embodiment 1 is adopted to produce alkyl anthrahydroquinone, unlike, in step (2), the flow direction of liquid material in tubular reactor is for flowing downward.
Experimental result is listed in Table 1.
Table 1
The result of table 1 confirms, adopt method of the present invention to be oxidized by alkyl anthrahydroquinone, even if the oxidation effectiveness that also can obtain under lower oxygenant consumption, feed stock conversion is high and the selectivity of hydrogen peroxide is good; Meanwhile, according to method of the present invention, the material residence time is in the reactor short, can obtain higher production efficiency.
Embodiment 4
The difference of the mixing device that the mixing device used in the present embodiment and embodiment 1 use is:
The mean pore size in the hole on the porous-film of mixing device film pipe used is 500nm; The filling ratio of film pipe in described housing is 35%; The ratio of the internal diameter of the material inlet of the internal diameter of the material outlet of mixing device and the tubular fixed-bed reactor as hydrogenation reactor and the tubular reactor as oxidation reactor is 0.85 separately, and the internal diameter of the material outlet of mixing device is 1 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular fixed-bed reactor/tubular reactor that are connected mixing device separately.
(1) adopt the method identical with embodiment 1 step (1) to carry out hydrogenation, produce the solution containing alkyl anthrahydroquinone.
(2) method shown in Fig. 6 is adopted, is mixed under the condition that solution containing alkyl anthrahydroquinone and oxygen are listed in table 2 in first Liqiud-gas mixing device, then by sending in first tubular reactor (specification is with embodiment 1) containing oxygen solution of obtaining, under the condition listed by table 2, oxidizing reaction is carried out.
Under the condition that table 2 is listed, after injecting oxygen by second Liqiud-gas mixing device in the effluent of first tubular reactor, the oxygen-containing mixture obtained is sent in second tubular fixed-bed reactor (specification is with first tubular reactor), under the condition listed by table 2, carry out oxidizing reaction.
Analyze the effluent of second tubular fixed-bed reactor and calculate the transformation efficiency of alkyl anthrahydroquinone and the transformation efficiency of hydrogen peroxide, result is listed in table 2.
Table 2
Embodiment 5
The method identical with embodiment 1 is adopted to produce hydrogen peroxide, unlike:
(1) be tetrahydrochysene 2-alkyl-anthraquinone containing the raw material in the solution of raw material, the mixed solution of solvent to be volume ratio be trimethylbenzene and trioctyl phosphate between 4:1, material concentration is 15 % by weight;
(2) be that the pipeline formed by porous material (is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd for the component of adjacent first channel and second passage in mixing device; Pipeline is evenly distributed with 19 passages, the internal diameter of each passage is 3.3mm, and the mean pore size in the hole on tube wall is 500nm); Using the passage on pipeline as second passage, the space formed by the inwall of the outer wall of pipeline and housing is as first channel, and pipeline filling ratio is in the housing 45%;
The ratio of the internal diameter of the internal diameter of the material outlet of mixing device and the material inlet of tubular fixed-bed reactor is 1, and the internal diameter of the material outlet of mixing device is 1 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular fixed-bed reactor that are connected mixing device;
(3) carry out under the condition that oxidizing reaction is listed at table 3 respectively.
Experimental result is listed in table 3.
Table 3
Embodiment 6
The mixing device used in the present embodiment is identical with embodiment 1.
(1) method shown in Fig. 6 is adopted, by the solution containing raw material, (raw material is 2-ethyl-anthraquinone, solvent is volume ratio is the unsym-trimethyl benzene of 1:1 and the mixed solution of methyl cyclohexanol acetate) mix under the condition listed in table 4 in first Liqiud-gas mixing device with hydrogen, then send into first tubular fixed-bed reactor by what obtain containing hydrogen solution (internal diameter of tubular fixed-bed reactor is 50mm, 1 beds is provided with in tubular reactor, the aspect ratio of catalyst loading is 15:1) in, (active ingredient is 0.4wt%Pd with the catalyzer with catalytic hydrogenation under the conditions shown in Table 4, carrier is silicon-dioxide) contact.
Under the condition that table 4 is listed, after injecting hydrogen by second Liqiud-gas mixing device in the effluent of first tubular fixed-bed reactor, send into second tubular fixed-bed reactor by what obtain containing hydrogen mixture (internal diameter of tubular fixed-bed reactor is 50mm, 1 beds is provided with in tubular reactor, the aspect ratio of catalyst loading is 10:1) in, contact with the catalyzer (identical with first tubular fixed-bed reactor) with catalytic hydrogenation under the conditions shown in Table 4.
Analyze the effluent of second tubular fixed-bed reactor and calculate hydrogenation ratio, result is listed in table 4.
(2) adopt the method identical with embodiment 1, under the condition that table 4 is listed, oxygen injected the solution containing alkyl anthrahydroquinone, and by obtain contain the condition that oxygen solution lists at table 4 under carry out oxidizing reaction, experimental result is listed in table 4.
Embodiment 7
The method identical with embodiment 6 is adopted to produce hydrogen peroxide, unlike,
(1) in step (1), the operational condition of mixing device and the condition of hydrogenation as shown in table 4;
(2) in step (2), the operational condition of mixing device and the condition of hydrogenation as shown in table 4.
Experimental result is listed in table 4.
Embodiment 8
The method identical with embodiment 6 is adopted to prepare alkyl anthrahydroquinone, unlike,
(1) in step (1), the operational condition of mixing device and the condition of hydrogenation as shown in table 4;
(2) in step (2), the operational condition of mixing device and the condition of hydrogenation as shown in table 4.
Experimental result is listed in table 4.
Table 4
The confirmation of the result of embodiment 1-8, method of the present invention can produce hydrogen peroxide with high feed stock conversion and selectivity of product.
Claims (22)
1. a method for oxidation for alkyl anthrahydroquinone, the method comprises injects by the hole that mean pore size is nano-scale the solution containing alkyl anthrahydroquinone by oxygen, obtains containing oxygen solution; Under oxidation reaction condition, make the described oxygen solution that contains with the internal space of the mode upwards flowed by tubular reactor.
2. method according to claim 1, wherein, oxygen is injected the described solution containing alkyl anthrahydroquinone by the first mixing device, thus obtain described containing oxygen solution, described first mixing device comprises at least one first channel and at least one second passage, adjoined by a component between described first channel and described second passage, described component at least part of for there being porose area, described have porose area to have hole that described mean pore size is nano-scale, described first channel is for holding described oxygen, described second passage is for holding the described solution containing alkyl anthrahydroquinone, described oxygen is injected into described containing in the solution of alkyl anthrahydroquinone by the hole that described mean pore size is nano-scale.
3. method according to claim 2, wherein, described component is the pipeline with at least one passage, and the tube wall of described pipeline has through hole, the hole of described through hole to be mean pore size be nano-scale; Or the outer wall of described pipeline and/or the inwall of passage are attached with porous-film, the tube wall of described pipeline has through hole, the hole of to be mean pore size be the hole on described porous-film nano-scale.
4. method according to claim 3, wherein, described first mixing device also comprises housing, component described at least one is arranged on described enclosure interior, Existential Space between the outer wall of described component and the inwall of described housing, described housing has the first entrance, second entrance and exit, the space that the outer wall of described pipeline and the inwall of described housing are formed is as described first channel, passage on described pipeline is as described second passage, described first channel is communicated with described first entrance, the two ends of described second passage respectively with described second entrance and described outlet, described first entrance is used for oxygen to import in described first channel, described second entrance is used for the described solution containing alkyl anthrahydroquinone to import in described second passage, the described oxygen solution that contains leaves described first mixing device by described outlet.
5. according to the method in claim 2-4 described in any one, wherein, described first mixing device is arranged on the inlet end of described tubular reactor.
6. according to the method in claim 1-4 described in any one, wherein, mean pore size is the mean pore size in the hole of nano-scale is 30-1000nm.
7. according to the method in claim 1-4 described in any one, wherein, in total feeding amount of oxygen and the described solution containing alkyl anthrahydroquinone, the mol ratio of alkyl anthrahydroquinone is 1-3:1.
8. method according to claim 1, wherein, described oxidation reaction condition comprises: temperature is 40-70 DEG C; In gauge pressure, the pressure in tubular reactor is 0.1-0.7MPa; It is 10-500 second containing the residence time of oxygen solution in described tubular reactor.
9. the method according to claim 1 or 8, wherein, the aspect ratio of described tubular reactor is 10-200:1.
10. according to the method in claim 1-4 and 8 described in any one, wherein, the solvent of the described solution containing alkyl anthrahydroquinone is phosphoric acid ester and/or alkyl carboxylates.
11. according to the method in claim 1-4 and 8 described in any one, and wherein, described alkyl anthrahydroquinone is 2-ethyl anthracene quinhydrones and/or tetrahydrochysene 2-ethyl anthracene quinhydrones.
12. 1 kinds of methods of producing hydrogen peroxide, the method comprises: under hydrogenation condition, by containing the solution of raw material and hydrogen and the catalyst exposure with catalytic hydrogenation, obtain the mixture containing alkyl anthrahydroquinone, described raw material is alkyl-anthraquinone and/or alkyl hydrides anthraquinone; The method in claim 1-11 described in any one is adopted to be oxidized by the alkyl anthrahydroquinone in the mixture containing alkyl anthrahydroquinone; Hydrogen peroxide is isolated from the mixture that oxidation obtains.
13. methods according to claim 12, wherein, comprise containing the solution of raw material and hydrogen with the method for the catalyst exposure with catalytic hydrogenation: hydrogen is injected the solution containing raw material by the hole that mean pore size is nano-scale, obtain containing hydrogen solution; Send in tubular fixed-bed reactor containing hydrogen solution in the mode upwards flowed by described, under hydrogenation condition, contain hydrogen solution and the catalyst exposure with catalytic hydrogenation by described.
14. methods according to claim 13, wherein, hydrogen is injected the described solution containing raw material by the second mixing device, thus obtain described containing hydrogen solution, described second mixing device comprises at least one first channel and at least one second passage, adjoined by a component between described first channel and described second passage, described component at least part of for there being porose area, described have porose area to have hole that described mean pore size is nano-scale, described first channel is for holding described hydrogen, described second passage is for holding the described solution containing raw material, described hydrogen is injected into described containing in the solution of raw material by the hole that described mean pore size is nano-scale.
15. methods according to claim 14, wherein, described component is the pipeline with at least one passage, and the tube wall of described pipeline has through hole, the hole of described through hole to be mean pore size be nano-scale; Or the outer wall of described pipeline and/or the inwall of passage are attached with porous-film, the tube wall of described pipeline has through hole, the hole of to be mean pore size be the hole on described porous-film nano-scale.
16. methods according to claim 15, wherein, described second mixing device also comprises housing, component described at least one is arranged on described enclosure interior, Existential Space between the outer wall of described component and the inwall of described housing, described housing has the first entrance, second entrance and exit, the space that the outer wall of described pipeline and the inwall of described housing are formed is as described first channel, passage on described pipeline is as described second passage, described first channel is communicated with described first entrance, the two ends of described second passage respectively with described second entrance and described outlet, described first entrance is used for hydrogen to import in described first channel, described second entrance is used for the described solution containing raw material to import in described second passage, the described hydrogen solution that contains leaves described second mixing device by described outlet.
17. according to the method in claim 14-16 described in any one, and wherein, described second mixing device is arranged on the inlet end of described tubular fixed-bed reactor.
18. according to the method in claim 13-16 described in any one, and wherein, mean pore size is the mean pore size in the hole of nano-scale is 30-1000nm.
19. according to the method in claim 12-16 described in any one, and wherein, total feeding amount and the described mol ratio containing the raw material in the solution of raw material of hydrogen are 0.5-1:1.
20. methods according to claim 12 or 13, wherein, described hydrogenation condition comprises: temperature is 40-70 DEG C; In gauge pressure, the pressure in tubular fixed-bed reactor is 0.1-0.7MPa; The volume space velocity of liquid material is 10-100h
-1.
21. according to method described in any one in claim 12-16, and wherein, the solvent containing the solution of raw material is the mixture of the first solvent and the second solvent, and described first solvent is C
9-C
11aromatic hydrocarbons and/or alkylnaphthalene, described second solvent is phosphoric acid ester and/or alkyl carboxylates, and the volume ratio of described first solvent and described second solvent is 0.5-4:1.
22. methods according to claim 12, wherein, the method isolating hydrogen peroxide from the mixture that oxidation obtains comprises: extract being oxidized the mixture obtained with water, and collect the extraction phase containing hydrogen peroxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892408A (en) * | 2015-12-18 | 2017-06-27 | 中国石油化工股份有限公司 | A kind of method for oxidation of hydrogen peroxide production process |
| CN114436804A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Alkylanthraquinone compositions and methods of making the same |
| CN114436797A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Process for preparing 2-alkyl anthraquinone |
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2014
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892408A (en) * | 2015-12-18 | 2017-06-27 | 中国石油化工股份有限公司 | A kind of method for oxidation of hydrogen peroxide production process |
| CN106892408B (en) * | 2015-12-18 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of method for oxidation of hydrogen peroxide production process |
| CN114436804A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Alkylanthraquinone compositions and methods of making the same |
| CN114436797A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Process for preparing 2-alkyl anthraquinone |
| CN114436797B (en) * | 2020-10-19 | 2024-05-17 | 中国石油化工股份有限公司 | Preparation method of 2-alkylanthraquinone |
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