CN108455536A - Peroxidating method for preparing hydrogen - Google Patents
Peroxidating method for preparing hydrogen Download PDFInfo
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- CN108455536A CN108455536A CN201810122076.XA CN201810122076A CN108455536A CN 108455536 A CN108455536 A CN 108455536A CN 201810122076 A CN201810122076 A CN 201810122076A CN 108455536 A CN108455536 A CN 108455536A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
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Abstract
The present invention relates to a kind of peroxidating method for preparing hydrogen comprising：(A) process for supplying the working solution containing Anthraquinones and solvent and hydrogenation catalyst to hydrogenation reactor；(B) in hydrogenation reactor, hydrogen-rich gas is supplied, the Anthraquinones that reduction working solution is included generate the hydrogenation process of oxanthranol class；(C) process that the working solution containing oxanthranol class and solvent and hydrogen depleted gas is discharged from hydrogenation reactor；(D) it converts the oxanthranol class in the working solution being discharged in process (C) to Anthraquinones, generates the oxidation operation of hydrogen peroxide；(E) abstraction process of hydrogen peroxide is detached from working solution；And at least part for the working solution for being extracted hydrogen peroxide in process (E) is back to the circulating process of process (B) by (F), which, which further includes (G) by the concentration of the water in the working solution in process (B), maintains process at 20%~160% relative to saturation capacity.
Description
Technical field
The present invention relates to the peroxidating method for preparing hydrogen for having used Anthraquinones.
Background technology
Hydrogen peroxide is with oxidizing force and with powerful bleaching, bactericidal effect, therefore, is used as paper, paper pulp, fiber etc.
Bleaching agent, fungicide etc..The decomposition product of hydrogen peroxide is therefore water and oxygen from the viewpoint of Green Chemistry, also occupy
Very important position is concerned especially as chlorine system bleaching agent instead of material.In addition, in the table of semiconductor substrate etc.
In the semiconductor industry of the cleaning in face, the etching of chemical grinding, electronic circuit of copper, tin and other copper alloy surfaces etc., peroxide
The usage amount for changing hydrogen also constantly increases.In addition, being widely used in the oxidation reaction for turning to representative with epoxidation and hydroxyl, peroxidating
Hydrogen is very important industrial products.
Currently, it has been known that there is anthraquinone for industrial peroxidating method for preparing hydrogen.In this method, Anthraquinones have been dissolved in
Solvent obtains working solution, restores Anthraquinones using hydrogen in the presence of a hydrogenation catalyst in hydrogenation process, raw
At oxanthranol class.Then, oxanthranol class is again converted to Anthraquinones in oxidation operation, while generates hydrogen peroxide.Work
Hydrogen peroxide in solution is detached by the method for water extraction etc. from working solution.It is extracted the working solution of hydrogen peroxide again
It is back in hydrogenation process, forms circulation technology.
In the hydrogenation process of above-mentioned circulation technology, the anthraquinone of the reacting dose i.e. productivity of technique per unit time is indicated
The hydrogenation speed of class is affected by multiple factors, and especially reaction temperature, hydrogen partial pressure, the admixture of gas-liquid-solid, work is molten
Liquid composition, the moisture concentration in working solution, hydrogenation catalyst type, hydrogenating catalytic dosage.Here, in maintaining practical factory
Productivity, the aspect of stability, be estimated to be by the hydrogenation catalyst caused by water activity reduce often become problem.
As one of solution, a kind of method is disclosed in patent document 1：To being extracted peroxidating in abstraction process
Water is added in the working solution of hydrogen or aqueous hydrogen peroxide solution is mixed, and dispersed phase is detached using coalescer, it as a result, will be adjoint
The water tariff collection of working solution is certain.
As another solution, it is known to a kind of method, that is, between abstraction process and the technique of hydrogenation process, make
Working solution is contacted with solution of potassium carbonate, removes the water in working solution as a result,.It may be residual in working solution after abstraction process
There are inexpungible hydrogen peroxide in abstraction process.Hydrogen peroxide is unstable under alkaline condition, it may occur that abnormal point
Solution, therefore, which leads to the problem of for security.In addition, in order not to bring potassium carbonate into hydrogenation process, need after drying
Working solution removes potassium carbonate, but as a result, just form complicated technique as a result, for processes such as sedimentation, separation, filterings.Separately
Outside, according to patent document 2, solution of potassium carbonate is reduced by absorbing the water in working solution, proportion repeatedly, and water separation capability reduces,
Therefore, it needs to concentrate solution of potassium carbonate after use, there are the increases of thermal energy and the increase of the labour of operator etc. to lack for the process
Point.
In addition, as another solution, being disclosed in patent document 3 a kind of being extracted hydrogen peroxide in abstraction process
Working solution in the method that is removed by being dried in vacuo of water, if described using the invention, after vacuum drying
Water in working solution becomes 15ppm.Saturation of the amount of water in the working solution relative to the water in common working solution
Amount is that extremely low value considers hydrogenating catalytic although the inactivation in hydrogenation catalyst prevents having a degree of effect
When the activity of agent, it is difficult to say that the water in the working solution in hydrogenation container is controlled so as to range appropriate.
Above-mentioned is by reducing the water being extracted in abstraction process in the working solution of hydrogen peroxide, preventing hydrogen indirectly
Change the method that the activity of catalyst reduces, there is its effect to a certain extent, but be not achieved and utilize hydrogenation catalyst to greatest extent
Intrinsic activity.
In existing hydrogen peroxide manufacturing process, carry out reducing as far as possible in the working solution in hydrogenation container mostly
Water moisture method of adjustment.But accurate and easy process management is required of in the operation of practical factory.Therefore, it needs
It reasonably to set for the concentration model of the water in the working solution that should be managed using the activity of hydrogenation catalyst to greatest extent
It encloses, and the method for the method or both combinations using method, addition water by reducing water, by the work in hydrogenation container
Make the water management in solution above range moisture adjusting method.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 63-100002 bulletins
Patent document 2：CN101353158A
Patent document 3：CN103641073A
Invention content
Problems to be solved by the invention
It is an object of the present invention to solve the above subject in the prior art, one kind is provided and is urged to greatest extent using hydrogenation
The activity of agent is come the method that manufactures hydrogen peroxide.
Solution for solving the problem
The present inventor has made intensive studies in order to solve the above problems, as a result, it has been found that, by by hydrogenation
The relative concentration relative to saturation capacity of the water in working solution in device is set in a specific range, can be utilized to greatest extent
The intrinsic activity of hydrogenation catalyst, so as to complete the present invention.That is, the present invention relates to a kind of peroxidating method for preparing hydrogen, lead to
Anthraquinone manufacture hydrogen peroxide is crossed, which is characterized in that, by the water phase pair in the working solution in hydrogenation reactor
The concentration at 20%~160% is maintained in saturation capacity.
The present invention includes the following contents.
[1] a kind of peroxidating method for preparing hydrogen, which is characterized in that including：
(A) process for supplying the working solution containing Anthraquinones and solvent and hydrogenation catalyst to hydrogenation reactor；
(B) in hydrogenation reactor, hydrogen-rich gas is supplied, the Anthraquinones that reduction working solution is included generate oxanthranol
The hydrogenation process of class；
(C) process that the working solution containing oxanthranol class and solvent and hydrogen depleted gas is discharged from hydrogenation reactor；
(D) it converts the oxanthranol class in the working solution being discharged in process (C) to Anthraquinones, generates the oxygen of hydrogen peroxide
Chemical industry sequence；
(E) abstraction process of hydrogen peroxide is detached from working solution；And
(F) at least part for the working solution for being extracted hydrogen peroxide in process (E) is back to the cycle of process (B)
Process,
Above-mentioned peroxidating method for preparing hydrogen further includes (G) concentration of the water in the working solution in process (B) is opposite
The process at 20%~160% is maintained in saturation capacity.
[2] the peroxidating method for preparing hydrogen as recorded in [1], wherein
Process (G) be the concentration of the water in the working solution in process (B) is maintained at 70% relative to saturation capacity~
130% process.
[3] the peroxidating method for preparing hydrogen as recorded in [1], wherein
Process (G) be the concentration of the water in the working solution in process (B) is maintained at 100% relative to saturation capacity~
160% process.
[4] the peroxidating method for preparing hydrogen as recorded in any one of [1]~[3], wherein
Process (G) is carried out by following at least one means,
(G1) with the means of the moisture of the working solution supplied to hydrogenation reactor in adjustment process (A)；
(G2) with the means of the moisture for the working solution being discharged from hydrogenation reactor in adjustment process (C)；
(G3) with the means of the moisture of the hydrogen-rich gas supplied to hydrogenation reactor in adjustment process (B)；
(G4) with the means of the moisture for the hydrogen depleted gas being discharged from hydrogenation reactor in adjustment process (C)；
(G5) means of water are introduced directly into hydrogenation reactor in process (A)；
(G6) with the means of the moisture for the working solution for being back to process (B) in adjustment process (F).
[5] the peroxidating method for preparing hydrogen as recorded in [4], wherein
At least one process of process (G1), process (G2) and process (G6) is implemented by following process：
A) displacement of the tank lower part separation of adjustment working solution of setting before and after hydrogenation, oxidation or abstraction process
Process；
B) the heat exchanger adjustment moisture of the working solution of setting before and after hydrogenation, oxidation or abstraction process is utilized
Process；
C) using the filter of working solution, the process that moisture is adjusted by Liquid liquid Separation；
D) process for utilizing coalescer adjustment moisture；
E) by making working solution and solution of potassium carbonate contact the process to adjust water；
F) process that moisture is adjusted by evaporation；Or
G) process that moisture is adjusted by distillation.
[6] the peroxidating method for preparing hydrogen as recorded in [4], wherein
At least one process of process (G1), process (G2) and process (G6) is implemented by following process：
A) draining of adjustment tank lower part separation of the working solution of setting before and after hydrogenation, oxidation or extraction each process
The process of amount；Or
B) the heat exchanger tune of the working solution of setting before and after hydrogenation process, oxidation operation or abstraction process is utilized
The process of whole moisture.
[7] the peroxidating method for preparing hydrogen as recorded in [4], wherein
Process (G3) and/or process (G4) utilize device, gas-liquid separation device or the activated carbon for adjusting hydrogenated gas flow
Adsorption-desorption device is implemented.
[8] the peroxidating method for preparing hydrogen as recorded in [4], wherein
Process (G5), which utilizes, makes the microdispersed device of water implement.
[9] the peroxidating method for preparing hydrogen as recorded in any one of [1]~[3], wherein
Anthraquinones are 2-methylanthraquinone, 1,3- dimethyl anthraquinone, 2,3- dimethyl anthraquinone, 1,4- dimethyl anthraquinone or 2,7-
Dimethyl anthraquinone, 2- ethyl hydrazine, 2- n-propyls anthraquinone, 2- isopropyls anthraquinone, 2- sec-butyls anthraquinone or 2- tertiary butyls anthraquinone or
Person 2- amylanthraquinones or 2- tertiary pentyl anthraquinones.
[10] the peroxidating method for preparing hydrogen as recorded in any one of [1]~[3], wherein
Solvent is the mixed solution of the nonpolar solvent for dissolving Anthraquinones and the polar solvent of dissolving oxanthranol class.
[11] the peroxidating method for preparing hydrogen as recorded in any one of [1]~[3], wherein
Hydrogenation catalyst contains is used as active metallic element selected from one or more of nickel, rhenium, ruthenium, rhodium, palladium and platinum.
[12] a kind of manufacture system of hydrogen peroxide, which is characterized in that including：
(A) conduit of the working solution containing Anthraquinones and solvent and hydrogenation catalyst is supplied to hydrogenation reactor；
(B) conduit and hydrogenation reactor of hydrogen-rich gas, the anthracene which is included by working solution are supplied
Quinones is restored, and oxanthranol class is generated；
(C) conduit of the working solution containing oxanthranol class and solvent and hydrogen depleted gas is discharged from hydrogenation reactor；
(D) oxidation unit converts the oxanthranol class in the working solution of discharge to Anthraquinones, generates hydrogen peroxide；
(E) extraction element detaches hydrogen peroxide from working solution；And
(F) at least part for the working solution for being extracted hydrogen peroxide is back to hydrogenation by cycle conduit
Device,
The manufacture system of above-mentioned hydrogen peroxide further includes (G) by the concentration phase of the water in the working solution in hydrogenation reactor
Device at 20%~160% is maintained for saturation capacity.
[13] manufacture system of the hydrogen peroxide as recorded in [12], wherein
Device (G) be by the concentration of the water in the working solution in hydrogenation reactor (B) relative to saturation capacity maintain at
70%~130% device.
[14] manufacture system of the hydrogen peroxide as recorded in [12], wherein
Device (G) be by the concentration of the water in the working solution in hydrogenation reactor (B) relative to saturation capacity maintain at
100%~160% device.
[15] manufacture system of the hydrogen peroxide as recorded in any one of [12]~[14], wherein
Device (G) includes at least one of following device device,
(G1) with the device of the moisture of the working solution supplied to hydrogenation reactor in adjustment conduit (A)；
(G2) with the device of the moisture for the working solution being discharged from hydrogenation reactor in adjustment conduit (C)；
(G3) with the device of the moisture of the hydrogen-rich gas supplied to hydrogenation reactor in adjustment hydrogenation reactor (B)；
(G4) with the device of the moisture for the hydrogen depleted gas being discharged from hydrogenation reactor in adjustment conduit (C)；
(G5) device of water is introduced directly into hydrogenation reactor in conduit (A)；
(G6) with the device of the moisture for the working solution for being back to hydrogenation reactor (B) in adjustment conduit (F).
[16] manufacture system of the hydrogen peroxide as recorded in [15], wherein
At least one device of device (G1), device (G2) and device (G6) includes：
A) before and after hydrogenation, oxidation or extraction element the working solution of setting tank；
B) before and after hydrogenation, oxidation or extraction element the working solution of setting heat exchanger；
C) filter of working solution；
D) coalescer；
E) device of water is adjusted by so that working solution and solution of potassium carbonate is contacted；
F) device of moisture is adjusted by evaporation；Or
G) device of moisture is adjusted by distillation.
[17] manufacture system of the hydrogen peroxide as recorded in [15], wherein
At least one device of device (G1), device (G2) and device (G6) includes：
A) displacement of the tank lower part separation of adjustment working solution of setting before and after hydrogenation, oxidation or extraction element
Device；Or
B) the heat exchanger adjustment moisture of the working solution of setting before and after hydrogenation, oxidation or extraction element is utilized
Device.
[18] manufacture system of the hydrogen peroxide as recorded in [15], wherein
Device (G3) and/or device (G4) include device, gas-liquid separation device or the activated carbon for adjusting hydrogenated gas flow
Adsorption-desorption device.
[19] manufacture system of the hydrogen peroxide as recorded in [15], wherein
Device (G5) includes making the microdispersed device of water.
[20] manufacture system of the hydrogen peroxide as recorded in any one of [12]~[14], wherein
Anthraquinones are 2-methylanthraquinone, 1,3- dimethyl anthraquinone, 2,3- dimethyl anthraquinone, 1,4- dimethyl anthraquinone or 2,7-
Dimethyl anthraquinone, 2- ethyl hydrazine, 2- n-propyls anthraquinone, 2- isopropyls anthraquinone, 2- sec-butyls anthraquinone or 2- tertiary butyls anthraquinone or
Person 2- amylanthraquinones or 2- tertiary pentyl anthraquinones.
[21] manufacture system of the hydrogen peroxide as recorded in any one of [12]~[14], wherein
Solvent is the mixed solution of the nonpolar solvent for dissolving Anthraquinones and the polar solvent of dissolving oxanthranol class.
[22] manufacture system of the hydrogen peroxide as recorded in any one of [12]~[14], wherein
Hydrogenation catalyst contains is used as active metallic element selected from one or more of nickel, rhenium, ruthenium, rhodium, palladium and platinum.
Invention effect
According to the method for the present invention, the activity that hydrogenation catalyst has can be utilized to greatest extent, and reaches production efficiency
Raising, significantly the simplifying of equipment, the rationalization of process management.
Description of the drawings
Fig. 1 is relative concentration relative to saturation capacity and the hydrogenation of the water in the working solution indicated in hydrogenation container
The chart of the relationship of the activity value of catalyst；
Fig. 2 is the skeleton diagram of the manufacture system of the hydrogen peroxide of the present invention.
Specific implementation mode
It suitably refers to Fig. 2 and illustrates the present invention.The meaning of symbol in Fig. 2 is as described below.
1 hydrogenation reactor
2 oxidation units
3 extraction elements
4 moisture adjusting apparatus (working solution use before hydrogenation process)
5 moisture adjusting apparatus (hydrogen-rich gas use)
6 moisture adjusting apparatus (hydrogenation catalyst use)
7 moisture adjusting apparatus (working solution use after abstraction process)
8 control devices
9 moisture transducers (working solution use before hydrogenation process)
10 moisture transducers (working solution use in hydrogenation reactor)
11 heat exchangers (working solution use before hydrogenation process)
12 heat exchangers (working solution use after hydrogenation process)
13 heat exchangers (working solution use after oxidation operation)
14 heat exchangers (working solution use after abstraction process)
15 heat exchangers (hydrogen-rich gas use)
16 adjust the device of hydrogen flowing quantity
17 pans (working solution use after hydrogenation process)
18 pans (working solution use after oxidation operation)
19 pans (working solution use after abstraction process)
20 make the microdispersed device of water
101 supply the conduit of working solution to hydrogenation reactor
102 the conduit of the working solution comprising oxanthranol class is discharged from hydrogenation reactor
103 supply the conduit of hydrogen-rich gas to hydrogenation reactor
104 the conduit of hydrogen depleted gas is discharged from hydrogenation reactor
105 supply the conduit of hydrogenation catalyst to hydrogenation reactor
106 the conduit of hydrogenation catalyst is discharged from hydrogenation reactor
At least part for the working solution for being extracted hydrogen peroxide is back to the cycle of hydrogenation reactor with leading by 107
Pipe
108 conduits for supplying freshly prepd working solution into circulation technology
109 supply the conduit of working solution to step for regeneration
110 conduits for supplying regenerated working solution into circulation technology
＜ processes (A) ＞
In process (A), working solution and hydrogenation catalyst containing Anthraquinones and solvent are supplied to hydrogenation reactor (1).
The hydrogenation reactor used in method as the present invention can use the catalyst reaction of common gas-liquid-solid
The reactor of device, i.e. fixed bed form, fluid bed form, mechanical agitation form and bubble column form etc..Hydrogenation reactor can be with
Be one, can also two or more connect in series or in parallel.
The working solution used in the method for the present invention at least contains Anthraquinones and solvent.
The Anthraquinones used in the present invention are not particularly limited, preferably alkyl-anthraquinone, alkyl tetrahydro anthraquinone or they
Mixture.Alkyl-anthraquinone and alkyl tetrahydro anthraquinone can also be respectively the mixture of a variety of alkyl-anthraquinones or alkyl tetrahydro anthraquinone.
In the case where using Anthraquinones as the mixture of alkyl-anthraquinone and alkyl tetrahydro anthraquinone, mixing molar ratio is preferably 2：1
~50：1.
Alkyl-anthraquinone refers to using the aliphatic substitution of the linear chain or branched chain containing at least one carbon atom, and substitution is at least
9,10- anthraquinones after one 1,2 or 3.In general, these alkyl substituents contain 9 carbon atoms below, 6 are preferably comprised
Carbon atom below.As the concrete example of this alkyl-anthraquinone, can enumerate：2-methylanthraquinone, 1,3- dimethyl anthraquinone, 2,3- bis-
Tectoquinone, 1,4- dimethyl anthraquinone or 2,7- dimethyl anthraquinone, 2- ethyl hydrazine, 2- n-propyls anthraquinone, 2- isopropyls anthraquinone,
2- sec-butyls anthraquinone or 2- tertiary butyls anthraquinone or 2- amylanthraquinones or 2- tertiary pentyl anthraquinones etc..Alkyl in working solution
The concentration of Anthraquinones is controlled according to the situation of technique, is usually used with 0.4~1.0mol/l.
Solvent used in the working solution of the present invention is preferably the nonpolar solvent and dissolving oxanthranol for dissolving Anthraquinones
The mixed solution of the polar solvent of class.As nonpolar solvent, by least one alkyl-substituted aromatic hydrocarbon, especially to contain
Or mixtures thereof the alkylbenzene of 8~12 carbon atoms.As polar solvent, be alcohol (for example, diisobutyl carbinol (DIBC), sec-n-octyl alcohol),
Four substituted ureas, phosphate, 2-Pyrrolidone or acetic acid alkyl ester.As the combination of preferred solvent, can enumerate：Aromatic hydrocarbon
With the combination of alcohol, aromatic hydrocarbon and acetic acid alkyl ester, aromatic hydrocarbon and phosphate and aromatic hydrocarbon and four substituted ureas.
Hydrogenation catalyst used in the present invention contains usual physical absorption or chemisorption in the active metal on carrier
The mixture of element or active metallic element.As active metallic element, usually one is selected from nickel, rhenium, ruthenium, rhodium, palladium and platinum
Kind or more.As active metallic element, preferably at least contain palladium.The content of active metallic element is typically not greater than 10 weight %,
Preferably more than 5 weight %, more preferably no more than 3 weight %.Carrier can be used：Titanium dioxide as common catalyst carrier
Silicon, silica alumina, aluminium oxide, oxidation aluminium magnesia, magnesia, silicon dioxide and titanium dioxide, titanium dioxide, oxidation
Zirconium, zeolite, activated carbon or organic polymer or their mixture etc..Wherein, preferably silica, titanium dioxide silica
Change aluminium, oxidation aluminium magnesia and gama-alumina, preferably silica and silica alumina.
Grain size, size distribution and the grain shape of carrier are not particularly limited, according to the reactor for using hydrogenation catalyst
Shape is selected, can example is amorphous, spherical, cylinder, three leaves, four leaves and ring etc..For example, as mechanical agitation type or suspension
The reactor of bubble column is used, and the meso-position radius of usual carrier is 1 μm~200 μm, preferably 20~180 μm, more preferably 30~
150 μm, grain shape is preferably amorphous or spherical.It is used as the hydrogenation reactor of fixed-bed type or fluidized bed type, in being
The spherical particle or crushed particles of position diameter 0.1~10mm, preferably 0.5~3mm, preferably pellet.
The amount of the hydrogenation catalyst used is controlled according to the situation of technique at concentration range appropriate, usually with 5~100g/
L is used.
In working solution, in addition to the foregoing, tertiary amine compound, N as trioctylamine, N- dialkyl group carboxylics can also be contained
The adding ingredients such as amide compound as sour amide.
The means (conduit 101) of working solution are supplied to hydrogenation reactor and supply the means (conduit of hydrogenation catalyst
105) it can be conventional means, be not particularly limited.
＜ processes (B) ＞
In process (B), hydrogen-rich gas is supplied in hydrogenation reactor, the Anthraquinones for being included by working solution restore, raw
At oxanthranol class.The means (conduit 103) that hydrogen-rich gas is supplied to hydrogenation reactor can be conventional means, not limit especially
It is fixed.
In the method for the present invention, in order to which the gas for using anthraquinone type hydrogenation can be 100% hydrogen, or by hydrogen
Gas after being diluted using inactive gas.As inactive gas, the rare of nitrogen, fluoro-gas or argon etc. can be enumerated
Gas.In general, using most cheap nitrogen.In addition, in present specification, referred to as " hydrogen-rich gas ", " hydrogen depleted gas " when be only
Refer to, the former hydrogen concentration is relatively higher than the hydrogen concentration of the latter.Simple hydrogen can be described as " hydrogen-rich gas ", but be not to say that
" hydrogen-rich gas " has the lower limit of hydrogen concentration, nor saying that " hydrogen depleted gas " has the upper limit of hydrogen concentration." if hydrogen-rich gas "
In hydrogen be consumed due to the hydrogenation of Anthraquinones, then become hydrogen concentration " hydrogen depleted gas " that relatively reduces.If from " poor hydrogen
Unreacted hydrogen is recycled, is concentrated by gas ", then becomes " hydrogen-rich gas ", and can recycle and be used in hydrogenation process.
Anthraquinones are utilized into hydrogen reduction, the reaction for generating oxanthranol class is well-known.
The temperature of hydrogenation process in the method for the present invention is usually 10~100 DEG C, preferably 20 DEG C~80 DEG C, more preferably
It is 25 DEG C~70 DEG C.Hydrogenation reactor pressure in the method for the present invention is typically set at 100kPa~500kPa.
＜ processes (C) ＞
In process (C), working solution and hydrogen depleted gas containing oxanthranol class and solvent is discharged from hydrogenation reactor.
The means (conduit 102) of working solution are discharged from hydrogenation reactor and the means (conduit 104) of hydrogen depleted gas are discharged
It can be conventional means, be not particularly limited.
＜ processes (D) ＞
Process (D) is to convert the oxanthranol class in the working solution being discharged in process (C) to Anthraquinones, generates peroxidating
The oxidation operation of hydrogen.
The oxidation operation of the method for the present invention can be carried out using conventional means.Oxidation unit (2) can be conventional means,
It is not particularly limited.For example, it can be set as oxidizing tower.The temperature of oxidation operation is usually 10~100 DEG C, preferably 20 DEG C~
80 DEG C, more preferably 25 DEG C~70 DEG C.
＜ processes (E) ＞
Process (E) is that the abstraction process of hydrogen peroxide is detached from working solution.
The abstraction process of the method for the present invention can be carried out using conventional means.Extraction element (3) can be conventional means,
It is not particularly limited.The temperature of abstraction process is usually 10~100 DEG C, preferably 20 DEG C~80 DEG C, more preferably 25 DEG C~70
℃。
＜ processes (F) ＞
Process (F) is that at least part for the working solution for being extracted hydrogen peroxide in process (E) is back to process (B)
In circulating process.
The means (conduit 107) that working solution is back to process (B) from process (E) can be conventional means, without spy
It does not limit.
The cycling rate of working solution can arbitrarily be set between 0~100%.
＜ processes (G) ＞
In process (G), the concentration of the water in the working solution in process (B) is maintained at 20% relative to saturation capacity~
160%, preferably maintain into 70%~130%.
Here, " saturation capacity " refer to the weight of per unit volume indicate in the working solution of composition requirement room temperature,
The maximum amount of amount for the water that can be dissolved under normal pressure.
Water in working solution can be quantified by karl Fischer titration.Other than karl Fischer titration,
Also the water in working solution can be quantified by GC, HPLC, NMR, NIR and IR etc..Moisture transducer is preferably hydrogenating
In the front and back and/or hydrogenation reactor of reactor more than setting at least one.In addition, other positions (conduit) can be also set to,
Position may be multiple.
In general, becoming saturation using the water in the working solution after abstraction process in anthraquinone hydrogen peroxide manufacturing process
More than amount, the water more than the part of saturation capacity is present in as free water in working solution.In the present invention, relative to hydrogenation
The saturation capacity of the water in working solution in device, is adjusted to 20%~160% concentration, is preferably adjusted to 70%~130%
Concentration.In the present invention, it can also be adjusted to 100% relative to the saturation capacity of the water in the working solution in hydrogenation reactor~
160% concentration is preferably adjusted to 100%~130% concentration.Specifically, using above-mentioned sizing technique, with it is defined when
Between moisture in the working solution that is supplied to hydrogenation reactor of measuring space moisture control is selected according to obtained measured value
Method is simultaneously adjusted.
In the case where as soon as hydrogenation reactor is, for the hydrogen depleted gas being discharged from it, can be included by it
After unreacted hydrogen recycling, the concentration for concentrating and adjusting water, it is supplied again to hydrogenation reactor.In two or more hydrogenation reactors
In the case of being connected in series with, the working solution being discharged from a hydrogenation reactor after the concentration of water that adjustment is contained therein,
Can either by it, all or part of is supplied to initial hydrogenation reactor, the hydrogenation before or after capable of being also supplied to
Device.In addition, the hydrogen depleted gas being discharged from a hydrogenation reactor is recycled, concentrated and is adjusted in the unreacted hydrogen for being included by it
After the concentration of whole water, it can either be supplied to initial hydrogenation reactor, the hydrogenation reactor before or after capable of being also supplied to.
In the case where two or more hydrogenation reactors connect side by side, from the working solution of hydrogenation reactor discharge
After the concentration of water that adjustment is contained therein, can either by it, all or part of is supplied to initial hydrogenation reactor,
Other hydrogenation reactors arranged side by side can be supplied to.In addition, the hydrogen depleted gas being discharged from a hydrogenation reactor is wrapped by it
After the unreacted hydrogen contained is recycled, concentrated and adjusted the concentration of water, it can either be supplied to initial hydrogenation reactor, also can
It is supplied to other hydrogenation reactors arranged side by side.
The method (system) of moisture content as the working solution in adjustment hydrogenation reactor, can enumerate：1) it adjusts adjoint
The means (device) of the moisture of the working solution supplied to hydrogenation reactor；2) adjustment is with the work being discharged from hydrogenation reactor
The means (device) of the moisture of solution；3) means (device) of the moisture of the adjoint gas supplied to hydrogenation reactor of adjustment；4)
The means (device) of the moisture of the adjoint gas being discharged from hydrogenation reactor of adjustment；5) adjustment with to hydrogenation reactor supply
The means (device) of the moisture of hydrogenation catalyst；6) means of the moisture of the adjoint working solution in hydrogenation reactor cycle of adjustment
(device)；Or the means (device) of water 7) are introduced directly into hydrogenation reactor, further from 1)~7) in the multiple arbitrary hands of combination
The method (system) that section (device) obtains.
1) as adjustment with to hydrogenation reactor supply working solution moisture means (device), 2) adjustment it is adjoint
The means (device) of the moisture for the working solution being discharged from hydrogenation reactor, 6) the adjoint work in hydrogenation reactor cycle of adjustment
The means (device) of the moisture of solution can be enumerated and implement to remove with the process of the water of working solution or add water to working solution
Process.Specifically, can be carried out by following process (device)：A) adjustment is before hydrogenation, oxidation or extraction each process
The process (device) of the displacement of the tank lower part separation for the working solution being arranged afterwards；B) using in hydrogenation process, oxidation operation
Or the process (device) of the heat exchanger adjustment moisture of the working solution of the front and back setting of abstraction process；C) working solution is used
Filter adjusts the process (device) of moisture by Liquid liquid Separation；D) process (device) of coalescer adjustment moisture is utilized；
E) process (device) of water is adjusted by so that working solution and solution of potassium carbonate is contacted；F) work of moisture is adjusted by evaporating
Sequence (device)；Or g) adjust moisture by distilling process (device).
Here, when considering equipment cost and safety, more preferably pass through following work with the moisture adjustment of working solution
Sequence (device) carries out：A) adjustment tank lower part of the working solution of setting before and after hydrogenation, oxidation or extraction each process detaches
Displacement process (device)；B) working solution of the setting before and after hydrogenation process, oxidation operation or abstraction process is utilized
Heat exchanger adjusts the process (device 4,5,6,7) of moisture.
The process (device) that water is added to working solution can include making the microdispersed process of water (device 20).In order not to make
The water of addition plays a role in hydrogenation reactor as the free water for making catalyst agglomerate, and water is preferably made to carry out micro disperse.
After adding water to working solution, in order to make water carry out micro disperse, the mixing in various pumps can be utilized, pass through mechanical agitation
Mixing, the mixing etc. by pipe-line mixer.The temperature of the process of moisture adjustment is usually 10~100 DEG C, preferably 20 DEG C
~80 DEG C, more preferably 25 DEG C~70 DEG C.In the case where removing water, preferably shorter than adjust moisture process before hydrogenation,
Oxidation or abstraction process temperature, in the case where add water, preferably higher than adjust moisture process before hydrogenation, aoxidize or
The temperature of abstraction process.
In means of the adjustment with the moisture of gas, the device, cyclone separator, spray of adjustment hydrogenated gas flow can be used
Gas-liquid separation device, activated carbon adsorption desorption apparatus etc. well known to mist separator etc..
In means of the adjustment with the moisture of hydrogenation catalyst, using well known drying, firing or vacuum treatment installation, adjust
The moisture content of renewing hydrogenation catalyst or regenerated hydrogenation catalyst.Here, new hydrogenation catalyst is once also not for hydrogen
Change the hydrogenation catalyst of reaction, regenerated hydrogenation catalyst is that it is clear to implement solvent after hydrogenation supplies more than primary
Wash and steam the hydrogenation catalyst that the regeneration treatments such as baking obtain.The tune of the moisture content of new hydrogenation catalyst or regenerated hydrogenation catalyst
It is whole to use the progress such as well known drier, vacuum desiccator, baking furnace.The replacement of hydrogenation catalyst connects according to batch type, in batches
It carries out with continuing formula or continous way.Also two or more hydrogenation reactors can be connected side by side, a side is made to work, and in
Only another party is replaced the maintenance of hydrogenation catalyst etc..The means (conduit 106) of hydrogenation catalyst are discharged from hydrogenation reactor
It may be conventional means, be not particularly limited.
It is introduced directly into the means of water to hydrogenation reactor, makes the microdispersed device of water using sprayer or distributor etc.
(device 20) adjusts the moisture content of the working solution supplied to hydrogenation reactor.
In order to maintain productivity, the stability of practical factory, following process management system is preferably constructed, that is, above-mentioned
On the basis of the implementation means (device) of process (G1)~(G6), in the working solution that setting monitoring is supplied to hydrogenation reactor
The sensor of the concentration of water and start or stop above-mentioned process (G1)~(G6's) according to the output signal from sensor
The control device (8) of implementation maintains the concentration of the water in the working solution in hydrogenation container at 90 relative to saturation capacity
± 70%, 100 ± 30%, other desired ranges.Sensor, device for this etc. can utilize well known device.In addition,
The line of connection moisture transducer (9,10), control device (8), each device (4,5,6,7,11,20) is omitted in Fig. 2.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited to the embodiments.
＜ working solutions ＞
Working solution use is by Swazol 1500 (registered trademark, fragrant hydrocarbon system solvent, the kind petrochemistry strain formula meeting of ball
Society manufactures, CAS NO.64742-94-5,180~185 DEG C of the initial boiling point measured according to JIS-K-2254) 70 volume % and phosphoric acid
The in the mixed solvent that three monooctyl esters (Daihachi Chemical Industry Co., Ltd. manufactures, CAS NO.78-42-2), 30 volume % is constituted dissolves
The solution of ethyl hydrazine (Weifang Menjie Chemicals Co., Ltd. manufactures, CAS NO.84-51-5) 0.6mol/l.
＜ hydrogenation catalysts ＞
Hydrogenation catalyst has been used in 120 DEG C of 2 dry weight %Pd/ silica or 1 weight %Pd/ titanium dioxide silica
Change aluminium.
The quantitative ＞ of water in ＜ working solutions
Amount of moisture in working solution uses titrating solution (Mitsubishi Chemical (Co., Ltd.) karl Fischer reagent SS 3mg) simultaneously
It is measured using karl Fischer moisture meter (capital of a country electronics (Co., Ltd.) MKS-520).
The saturation capacity ＞ of the water of ＜ working solutions
It is added to the water of the amount of saturation or more into working solution, after being vibrated 50 times or so with hand, is being placed at room temperature for
Diel.Supernatant is taken using micropipettor, and is measured using karl Fischer moisture meter, its value is set as being saturated
Amount.The saturation capacity of water in the working solution this time prepared is 3.055g/l.
＜ test methods ＞
Water phase in working solution is adjusted saturation capacity in 10%~200% concentration range, is used for hydrogen
Change the activity rating of catalyst.
Hydrogenation catalyst and working solution are added into the twoport flask of 100ml.Blender is connected in a mouth of flask,
Another mouth is connected to hydrogen supply unit.In addition, flask is closed.Hydrogen supply unit includes hydrogen measurement pipe, U-tube pressure gauge and water storage
Portion, the height of water storage part is adjusted in hydrogenation according to the variation of the liquid level of U-tube pressure gauge, and flask internal pressure and atmospheric pressure are kept
It is equal.Hydrogen uptake is measured as the difference of the liquid level in hydrogen measurement pipe.
Flask is impregnated in 30 DEG C of water-bath, stands 10 minutes.After the exhaust in 3 flasks and hydrogen import repeatedly,
Blender is set to work.Measure since hydrogen absorb to after 30 minutes until hydrogen uptake.Hydrogen uptake is converted into
In 0 DEG C, the value of 1atm.The activity value of hydrogenation catalyst is with the standard state hydrogen infiltration rate of per unit hydrogenation catalyst weight
(Nml/ (min × g)) is indicated.
Embodiment 1
It uses with 120 DEG C of 2 dry weight %Pd/ silica 0.05g and by the water phase in working solution for saturation
The working solution 25ml for measuring the concentration for being adjusted to 16% is reacted.As a result, the activity value of hydrogenation catalyst is 38.7Nml/
(min×g)。
Embodiment 2
It uses with 120 DEG C of 2 dry weight %Pd/ silica 0.05g and by the water phase in working solution for saturation
The working solution 25ml for measuring the concentration for being adjusted to 33% is reacted.As a result, the activity value of hydrogenation catalyst is 56.8Nml/
(min×g)。
Embodiment 3
It uses with 120 DEG C of 2 dry weight %Pd/ silica 0.05g and by the water phase in working solution for saturation
The working solution 25ml for measuring the concentration for being adjusted to 66% is reacted.As a result, the activity value of hydrogenation catalyst is 81.0Nml/
(min×g)。
Embodiment 4
It uses with 120 DEG C of 2 dry weight %Pd/ silica 0.05g and by the water phase in working solution for saturation
The working solution 25ml for measuring the concentration for being adjusted to 100% is reacted.As a result, the activity value of hydrogenation catalyst is
100.1Nml/(min×g)。
Embodiment 5
It uses with 120 DEG C of 2 dry weight %Pd/ silica 0.05g and by the water phase in working solution for saturation
The working solution 25ml for measuring the concentration for being adjusted to 131% is reacted.As a result, the activity value of hydrogenation catalyst is 81.9Nml/
(min×g)。
Embodiment 6
It uses with 120 DEG C of 2 dry weight %Pd/ silica 0.05g and by the water phase in working solution for saturation
The working solution 25ml for measuring the concentration for being adjusted to 164% is reacted.As a result, the activity value of hydrogenation catalyst is 8.5Nml/
(min×g)。
Embodiment 7
Use with 120 DEG C of 1 dry weight %Pd/ silica aluminas 0.1g and by the water phase in working solution for
The working solution 25ml that saturation capacity is adjusted to 24% concentration is reacted.As a result, the activity value of hydrogenation catalyst is
33.8Nml/(min×g)。
Embodiment 8
It uses with 120 DEG C of 1 dry weight %Pd/ silica aluminas 0.1g and is adjusted to the water in working solution
The working solution 25ml of 33% concentration of saturation capacity is reacted.As a result, the activity value of hydrogenation catalyst is 37.2Nml/
(min×g)。
Embodiment 9
Use with 120 DEG C of 1 dry weight %Pd/ silica aluminas 0.1g and by the water phase in working solution for
The working solution 25ml that saturation capacity is adjusted to 74% concentration is reacted.As a result, the activity value of hydrogenation catalyst is
64.9Nml/(min×g)。
Embodiment 10
Use with 120 DEG C of 1 dry weight %Pd/ silica aluminas 0.1g and by the water phase in working solution for
The working solution 25ml that saturation capacity is adjusted to 104% concentration is reacted.As a result, the activity value of hydrogenation catalyst is
66.1Nml/(min×g)。
Embodiment 11
Use with 120 DEG C of 1 dry weight %Pd/ silica aluminas 0.1g and by the water phase in working solution for
The working solution 25ml that saturation capacity is adjusted to 131% concentration is reacted.As a result, the activity value of hydrogenation catalyst is
64.7Nml/(min×g)。
Embodiment 12
Use with 120 DEG C of 1 dry weight %Pd/ silica aluminas 0.1g and by the water phase in working solution for
The working solution 25ml that saturation capacity is adjusted to 164% concentration is reacted.As a result, the activity value of hydrogenation catalyst is
32.4Nml/(min×g)。
Embodiment 13
Using 120 DEG C of 1 dry weight %Pd/ silica aluminas 0.1g and by the water phase in working solution for full
The working solution 25ml for the concentration for being adjusted to 196% with amount is reacted.As a result, the activity value of hydrogenation catalyst is
10.9Nml/(min×g)。
It the results are shown in Fig. 1.It confirms according to the above embodiments, the water in working solution in hydrogenation reactor
Relative to saturation capacity relative concentration and hydrogenation catalyst activity value have certain correlation.
Industrial availability
The present invention is by reasonably setting in order to which the hydrogenation that should be managed using the activity of hydrogenation catalyst to greatest extent is anti-
The concentration range of the water in the working solution in container is answered, and suitably utilizes and above range is made in the water control in working solution
Moisture adjusting method realizes the accurate and easy process management required in the operation of practical factory.
Claims (22)
1. a kind of peroxidating method for preparing hydrogen, which is characterized in that including：
(A) process for supplying the working solution containing Anthraquinones and solvent and hydrogenation catalyst to hydrogenation reactor；
(B) in hydrogenation reactor, hydrogen-rich gas is supplied, the Anthraquinones that reduction working solution is included generate oxanthranol class
Hydrogenation process；
(C) process that the working solution containing oxanthranol class and solvent and hydrogen depleted gas is discharged from hydrogenation reactor；
(D) it converts the oxanthranol class in the working solution being discharged in process (C) to Anthraquinones, generates the oxidation work of hydrogen peroxide
Sequence；
(E) abstraction process of hydrogen peroxide is detached from working solution；And
(F) at least part for the working solution for being extracted hydrogen peroxide in process (E) is back to the circulation industrial of process (B)
Sequence,
The peroxidating method for preparing hydrogen further includes (G) by the concentration of the water in the working solution in process (B) relative to full
The process at 20%~160% is maintained with amount.
2. peroxidating method for preparing hydrogen according to claim 1, it is characterised in that：
Process (G) is to maintain the concentration of the water in the working solution in process (B) at 70%~130% relative to saturation capacity
Process.
3. peroxidating method for preparing hydrogen according to claim 1, it is characterised in that：
Process (G) is to maintain the concentration of the water in the working solution in process (B) at 100%~160% relative to saturation capacity
Process.
4. peroxidating method for preparing hydrogen described in any one of claim 1 to 3, it is characterised in that：
Process (G) is carried out by least one means below,
(G1) with the means of the moisture of the working solution supplied to hydrogenation reactor in adjustment process (A)；
(G2) with the means of the moisture for the working solution being discharged from hydrogenation reactor in adjustment process (C)；
(G3) with the means of the moisture of the hydrogen-rich gas supplied to hydrogenation reactor in adjustment process (B)；
(G4) with the means of the moisture for the hydrogen depleted gas being discharged from hydrogenation reactor in adjustment process (C)；
(G5) means of water are introduced directly into hydrogenation reactor in process (A)；
(G6) with the means of the moisture for the working solution for being back to process (B) in adjustment process (F).
5. peroxidating method for preparing hydrogen according to claim 4, it is characterised in that：
At least one process of process (G1), process (G2) and process (G6) is implemented by following process：
A) work of the displacement of the tank lower part separation of adjustment working solution of setting before and after hydrogenation, oxidation or abstraction process
Sequence；
B) work of the heat exchanger adjustment moisture of the working solution of setting before and after hydrogenation, oxidation or abstraction process is utilized
Sequence；
C) using the filter of working solution, the process that moisture is adjusted by Liquid liquid Separation；
D) process for utilizing coalescer adjustment moisture；
E) by making working solution and solution of potassium carbonate contact the process to adjust water；
F) process that moisture is adjusted by evaporation；Or
G) process that moisture is adjusted by distillation.
6. peroxidating method for preparing hydrogen according to claim 4, it is characterised in that：
At least one process of process (G1), process (G2) and process (G6) is implemented by following process：
A) adjustment displacement of the tank lower part separation of the working solution of setting before and after hydrogenation, oxidation or extraction each process
Process；Or
B) water is adjusted using the heat exchanger of the working solution of setting before and after hydrogenation process, oxidation operation or abstraction process
The process divided.
7. peroxidating method for preparing hydrogen according to claim 4, it is characterised in that：
Process (G3) and/or process (G4) utilize device, gas-liquid separation device or the activated carbon adsorption for adjusting hydrogenated gas flow
Desorption apparatus is implemented.
8. peroxidating method for preparing hydrogen according to claim 4, it is characterised in that：
Process (G5), which utilizes, makes the microdispersed device of water implement.
9. peroxidating method for preparing hydrogen described in any one of claim 1 to 3, it is characterised in that：
Anthraquinones are 2-methylanthraquinone, 1,3- dimethyl anthraquinone, 2,3- dimethyl anthraquinone, 1,4- dimethyl anthraquinone or 2,7- diformazans
Base anthraquinone, 2- ethyl hydrazine, 2- n-propyls anthraquinone, 2- isopropyls anthraquinone, 2- sec-butyls anthraquinone or 2- tertiary butyls anthraquinone or 2-
Amylanthraquinone or 2- tertiary pentyl anthraquinones.
10. peroxidating method for preparing hydrogen described in any one of claim 1 to 3, it is characterised in that：
Solvent is the mixed solution of the nonpolar solvent for dissolving Anthraquinones and the polar solvent of dissolving oxanthranol class.
11. peroxidating method for preparing hydrogen described in any one of claim 1 to 3, it is characterised in that：
Hydrogenation catalyst contains is used as active metallic element selected from one or more of nickel, rhenium, ruthenium, rhodium, palladium and platinum.
12. a kind of manufacture system of hydrogen peroxide, which is characterized in that including：
(A) conduit of the working solution containing Anthraquinones and solvent and hydrogenation catalyst is supplied to hydrogenation reactor；
(B) conduit and hydrogenation reactor of hydrogen-rich gas, the Anthraquinones which is included by working solution are supplied
It is restored, generates oxanthranol class；
(C) conduit of the working solution containing oxanthranol class and solvent and hydrogen depleted gas is discharged from hydrogenation reactor；
(D) oxidation unit converts the oxanthranol class in the working solution of discharge to Anthraquinones, generates hydrogen peroxide；
(E) extraction element detaches hydrogen peroxide from working solution；And
(F) at least part for the working solution for being extracted hydrogen peroxide is back to hydrogenation reactor by cycle conduit,
The manufacture system of the hydrogen peroxide further include (G) by the concentration of the water in the working solution in hydrogenation reactor relative to
Saturation capacity maintains the device at 20%~160%.
13. the manufacture system of hydrogen peroxide according to claim 12, it is characterised in that：
Device (G) be the concentration of the water in the working solution in hydrogenation reactor (B) is maintained at 70% relative to saturation capacity~
130% device.
14. the manufacture system of hydrogen peroxide according to claim 12, it is characterised in that：
Device (G) be the concentration of the water in the working solution in hydrogenation reactor (B) is maintained at 100% relative to saturation capacity~
160% device.
15. the manufacture system of the hydrogen peroxide according to any one of claim 12~14, it is characterised in that：
Device (G) includes at least one of following device device,
(G1) with the device of the moisture of the working solution supplied to hydrogenation reactor in adjustment conduit (A)；
(G2) with the device of the moisture for the working solution being discharged from hydrogenation reactor in adjustment conduit (C)；
(G3) with the device of the moisture of the hydrogen-rich gas supplied to hydrogenation reactor in adjustment hydrogenation reactor (B)；
(G4) with the device of the moisture for the hydrogen depleted gas being discharged from hydrogenation reactor in adjustment conduit (C)；
(G5) device of water is introduced directly into hydrogenation reactor in conduit (A)；
(G6) with the device of the moisture for the working solution for being back to hydrogenation reactor (B) in adjustment conduit (F).
16. the manufacture system of hydrogen peroxide according to claim 15, it is characterised in that：
At least one device of device (G1), device (G2) and device (G6) includes：
A) before and after hydrogenation, oxidation or extraction element the working solution of setting tank；
B) before and after hydrogenation, oxidation or extraction element the working solution of setting heat exchanger；
C) filter of working solution；
D) coalescer；
E) device of water is adjusted by so that working solution and solution of potassium carbonate is contacted；
F) device of moisture is adjusted by evaporation；Or
G) device of moisture is adjusted by distillation.
17. the manufacture system of hydrogen peroxide according to claim 15, it is characterised in that：
At least one device of device (G1), device (G2) and device (G6) includes：
A) dress of the displacement of the tank lower part separation of adjustment working solution of setting before and after hydrogenation, oxidation or extraction element
It sets；Or
B) dress of the heat exchanger adjustment moisture of the working solution of setting before and after hydrogenation, oxidation or extraction element is utilized
It sets.
18. the manufacture system of hydrogen peroxide according to claim 15, it is characterised in that：
Device (G3) and/or device (G4) include device, gas-liquid separation device or the activated carbon adsorption for adjusting hydrogenated gas flow
Desorption apparatus.
19. the manufacture system of hydrogen peroxide according to claim 15, it is characterised in that：
Device (G5) includes making the microdispersed device of water.
20. the manufacture system of the hydrogen peroxide according to any one of claim 12~14, it is characterised in that：
Anthraquinones are 2-methylanthraquinone, 1,3- dimethyl anthraquinone, 2,3- dimethyl anthraquinone, 1,4- dimethyl anthraquinone or 2,7- diformazans
Base anthraquinone, 2- ethyl hydrazine, 2- n-propyls anthraquinone, 2- isopropyls anthraquinone, 2- sec-butyls anthraquinone or 2- tertiary butyls anthraquinone or 2-
Amylanthraquinone or 2- tertiary pentyl anthraquinones.
21. the manufacture system of the hydrogen peroxide according to any one of claim 12~14, it is characterised in that：
Solvent is the mixed solution of the nonpolar solvent for dissolving Anthraquinones and the polar solvent of dissolving oxanthranol class.
22. the manufacture system of the hydrogen peroxide according to any one of claim 12~14, it is characterised in that：
Hydrogenation catalyst contains is used as active metallic element selected from one or more of nickel, rhenium, ruthenium, rhodium, palladium and platinum.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867507A (en) * | 1958-05-08 | 1959-01-06 | Du Pont | Hydrogenation of alkylanthraquinones |
| CN1334235A (en) * | 2000-07-15 | 2002-02-06 | 中国石油化工股份有限公司巴陵分公司 | Post-treating process for prepairng hydrogen peroxide by anthraquinone method |
| JP2003002620A (en) * | 2001-06-18 | 2003-01-08 | Mitsubishi Gas Chem Co Inc | Method for manufacturing hydrogen peroxide |
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| DE10336852A1 (en) * | 2003-08-11 | 2005-03-10 | Degussa | Process for the preparation of hydrogen peroxide by the anthraquinone cyclic process |
| JP4973041B2 (en) * | 2006-07-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Method for producing hydrogen peroxide |
| WO2015025735A1 (en) * | 2013-08-23 | 2015-02-26 | 三菱瓦斯化学株式会社 | Method for regenerating working solution used for production of hydrogen peroxide and method for producing hydrogen peroxide using regenerated working solution |
| CN106395755B (en) * | 2016-11-02 | 2019-12-10 | 上海睿思化工科技有限公司 | Method for preparing hydrogen peroxide by anthraquinone process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867507A (en) * | 1958-05-08 | 1959-01-06 | Du Pont | Hydrogenation of alkylanthraquinones |
| CN1334235A (en) * | 2000-07-15 | 2002-02-06 | 中国石油化工股份有限公司巴陵分公司 | Post-treating process for prepairng hydrogen peroxide by anthraquinone method |
| JP2003002620A (en) * | 2001-06-18 | 2003-01-08 | Mitsubishi Gas Chem Co Inc | Method for manufacturing hydrogen peroxide |
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