CN208471534U - The manufacture system of hydrogen peroxide - Google Patents
The manufacture system of hydrogen peroxide Download PDFInfo
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- CN208471534U CN208471534U CN201820217691.4U CN201820217691U CN208471534U CN 208471534 U CN208471534 U CN 208471534U CN 201820217691 U CN201820217691 U CN 201820217691U CN 208471534 U CN208471534 U CN 208471534U
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- hydrogenation
- hydrogenation reactor
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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 utility model relates to a kind of manufacture systems of hydrogen peroxide comprising: the conduit A of working solution and hydrogenation catalyst is supplied to hydrogenation reactor；The conduit and hydrogenation reactor B of hydrogen-rich gas are supplied, the Anthraquinones which is included by working solution restore, and generate oxanthranol class；The conduit C of working solution and hydrogen depleted gas is discharged from hydrogenation reactor；Oxidation unit D converts Anthraquinones for the oxanthranol class in the working solution of discharge, generates hydrogen peroxide；Extraction element E separates hydrogen peroxide from working solution；And circulation conduit F, at least part for being extracted the working solution of hydrogen peroxide is back to hydrogenation reactor, the manufacture system of the hydrogen peroxide further includes the device G of the concentration of the water in the working solution adjusted in hydrogenation reactor.
Description
Technical field
The utility model relates to use the manufacture system of the hydrogen peroxide of Anthraquinones.
Background technique
Hydrogen peroxide is with oxidizing force and there is powerful bleaching, bactericidal effect to be therefore 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, especially as being concerned instead of material for chlorine system bleaching agent.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.It is turned in the oxidation reaction of representative in addition, being widely used in 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 separated 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 the hydrogenation catalyst as 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 separates dispersed phase 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 hydrogen peroxide inexpungible 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, after needing to dry
Working solution removes potassium carbonate for processes such as sedimentation, separation, filterings as a result, but as a result, just forms complicated technique.Separately
Outside, according to patent document 2, solution of potassium carbonate is reduced by absorbing the water in working solution, specific gravity repeatedly, and water separation capability reduces,
Therefore, it needs that solution of potassium carbonate is concentrated 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, disclosing in patent document 3 a kind of will be 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 extremely low value, although the inactivation in hydrogenation catalyst prevents having a degree of effect, considers hydrogenating catalytic
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 to prevent hydrogen indirectly by reducing the water being extracted in the working solution of hydrogen peroxide in abstraction process
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
Reasonably to set the concentration model of the water in the working solution that should be managed to utilize 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 in the moisture adjusting method of above range.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 63-100002 bulletin
Patent document 2:CN101353158A
Patent document 3:CN103641073A
Utility model content
Utility model project to be solved
The purpose of this utility model is that solving the above subject in the prior art, one kind is provided and utilizes hydrogen to greatest extent
The system for changing the activity of catalyst to manufacture hydrogen peroxide.
Solution for solving the problem
The inventor of the utility model has made intensive studies in order to solve the above problems, as a result, it has been found that, by that will hydrogenate
The relative concentration relative to saturation capacity of the water in working solution in reactor is set in a specific range, can be to greatest extent
Using the intrinsic activity of hydrogenation catalyst, so as to complete the utility model.That is, the utility model relates to a kind of hydrogen peroxide
Manufacture system, by anthraquinone manufacture hydrogen peroxide, which is characterized in that, further includes in adjustment hydrogenation reactor
The device G of the concentration of water in working solution.
The utility model includes the following contents.
[1] a kind of peroxidating method for preparing hydrogen characterized by comprising
The process A of the working solution containing Anthraquinones and solvent and hydrogenation catalyst is supplied to hydrogenation reactor；
In hydrogenation reactor, hydrogen-rich gas is supplied, the Anthraquinones that reduction working solution is included generate oxanthranol class
Hydrogenation process B；
The process C of the working solution containing oxanthranol class and solvent and hydrogen depleted gas is discharged from hydrogenation reactor；
Anthraquinones are converted by the oxanthranol class in the working solution being discharged in process C, generate the oxidation work of hydrogen peroxide
Sequence D；
From the abstraction process E of working solution separation hydrogen peroxide；And
At least part that the working solution of hydrogen peroxide is extracted in process E is back to the circulating process F of process B,
Above-mentioned peroxidating method for preparing hydrogen further includes the concentration by the water in the working solution in process B relative to saturation
Amount maintains the process G at 20%~160%.
[2] the peroxidating method for preparing hydrogen as documented by [1], wherein
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] the peroxidating method for preparing hydrogen as documented by [1], wherein
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] the peroxidating method for preparing hydrogen as documented by any one of [1]~[3], wherein
Process G is carried out by least one following means,
Adjust the means G1 of the moisture in process A with the working solution supplied to hydrogenation reactor；
Adjust the means G2 of the moisture in process C with the working solution being discharged from hydrogenation reactor；
Adjust the means G3 of the moisture in process B with the hydrogen-rich gas supplied to hydrogenation reactor；
Adjust the means G4 of the moisture in process C with the hydrogen depleted gas being discharged from hydrogenation reactor；
The means G5 of water is introduced directly into hydrogenation reactor in process A；
With the means G6 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 documented by [4], wherein
At least one process of process G1, process G2 and process G6 are implemented by following process:
A) displacement of the tank lower part separation for the working solution that adjustment is arranged before and after hydrogenation, oxidation or abstraction process
Process；
B) the heat exchanger adjustment moisture for the working solution being arranged 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 of coalescer adjustment moisture is utilized；
E) by making working solution and solution of potassium carbonate contact the process to adjust water；
F) pass through the process of evaporation adjustment moisture；Or
G) pass through the process of distillation adjustment moisture.
[6] the peroxidating method for preparing hydrogen as documented by [4], wherein
At least one process of process G1, process G2 and process G6 are implemented by following process:
A) draining of the tank lower part separation for the working solution being arranged before and after hydrogenation, oxidation or extraction each process is adjusted
The process of amount；Or
B) the heat exchanger tune for the working solution being arranged 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 documented by [4], wherein
Process G3 and/or process G4 utilizes device, gas-liquid separation device or the activated carbon adsorption for adjusting hydrogenated gas flow
Desorption apparatus is implemented.
[8] the peroxidating method for preparing hydrogen as documented by [4], wherein
Process G5, which is utilized, implements the microdispersed device of water.
[9] the peroxidating method for preparing hydrogen as documented by 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-propyl anthraquinone, 2- isopropyl anthraquinone, 2- sec-butyl anthraquinone or 2- tert-butyl anthraquinone or
Person 2- amylanthraquinone or 2- tertiary pentyl anthraquinone.
[10] the peroxidating method for preparing hydrogen as documented by any one of [1]~[3], wherein
Solvent is the mixed solution of the nonpolar solvent for dissolving Anthraquinones and the polar solvent of dissolution oxanthranol class.
[11] the peroxidating method for preparing hydrogen as documented by any one of [1]~[3], wherein
Hydrogenation catalyst contains selected from one or more of nickel, rhenium, ruthenium, rhodium, palladium and platinum as active metallic element.
[12] a kind of manufacture system of hydrogen peroxide characterized by comprising
The conduit A of the working solution containing Anthraquinones and solvent and hydrogenation catalyst is supplied to hydrogenation reactor；
Supply the conduit and hydrogenation reactor B of hydrogen-rich gas, the anthraquinone which is included by working solution
Class is restored, and oxanthranol class is generated；
The conduit C of the working solution containing oxanthranol class and solvent and hydrogen depleted gas is discharged from hydrogenation reactor；
Oxidation unit D converts Anthraquinones for the oxanthranol class in the working solution of discharge, generates hydrogen peroxide；
Extraction element E separates hydrogen peroxide from working solution；And
Circulation conduit F, is back to hydrogenation reactor for at least part for being extracted the working solution of hydrogen peroxide,
The manufacture system of above-mentioned hydrogen peroxide further includes that the concentration of the water in the working solution in hydrogenation reactor is opposite
The device G at 20%~160% is maintained in saturation capacity.
[13] manufacture system of the hydrogen peroxide as documented by [12], wherein
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] manufacture system of the hydrogen peroxide as documented by [12], wherein
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] manufacture system of the hydrogen peroxide as documented by any one of [12]~[14], wherein
Device G includes at least one device in following device,
Adjust the device G1 of the moisture in conduit A with the working solution supplied to hydrogenation reactor；
Adjust the device G2 of the moisture in conduit C with the working solution being discharged from hydrogenation reactor；
Adjust the device G3 of the moisture in hydrogenation reactor B with the hydrogen-rich gas supplied to hydrogenation reactor；
Adjust the device G4 of the moisture in conduit C with the hydrogen depleted gas being discharged from hydrogenation reactor；
The device G5 of water is introduced directly into hydrogenation reactor in conduit A；
With the device G6 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 documented by [15], wherein
At least one device of device G1, device G2 and device G6 includes:
A) tank for the working solution being arranged before and after hydrogenation, oxidation or extraction element；
B) heat exchanger for the working solution being arranged before and after hydrogenation, oxidation or extraction element；
C) filter of working solution；
D) coalescer；
E) device of water is adjusted and contacting working solution and solution of potassium carbonate；
F) pass through the device of evaporation adjustment moisture；Or
G) pass through the device of distillation adjustment moisture.
[17] manufacture system of the hydrogen peroxide as documented by [15], wherein
At least one device of device G1, device G2 and device G6 includes:
A) displacement of the tank lower part separation for the working solution that adjustment is arranged before and after hydrogenation, oxidation or extraction element
Device；Or
B) the heat exchanger adjustment moisture for the working solution being arranged before and after hydrogenation, oxidation or extraction element is utilized
Device.
[18] manufacture system of the hydrogen peroxide as documented by [15], wherein
Device G3 and/or device G4 includes device, gas-liquid separation device or the activated carbon adsorption for adjusting hydrogenated gas flow
Desorption apparatus.
[19] manufacture system of the hydrogen peroxide as documented by [15], wherein
Device G5 includes making the microdispersed device of water.
[20] manufacture system of the hydrogen peroxide as documented by 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-propyl anthraquinone, 2- isopropyl anthraquinone, 2- sec-butyl anthraquinone or 2- tert-butyl anthraquinone,
Or 2- amylanthraquinone or 2- tertiary pentyl anthraquinone.
[21] manufacture system of the hydrogen peroxide as documented by any one of [12]~[14], wherein
Solvent is the mixed solution of the nonpolar solvent for dissolving Anthraquinones and the polar solvent of dissolution oxanthranol class.
[22] manufacture system of the hydrogen peroxide as documented by any one of [12]~[14], wherein
Hydrogenation catalyst contains selected from one or more of nickel, rhenium, ruthenium, rhodium, palladium and platinum as active metallic element.
The effect of utility model
Method according to the present utility model, the activity that can have to greatest extent using hydrogenation catalyst, and reach production
The raising of efficiency, significantly the simplifying of equipment, the rationalization of process management.
Detailed description of the invention
Fig. 1 is the relative concentration and hydrogenation relative to saturation capacity 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 utility model.
Specific embodiment
It suitably refers to Fig. 2 and illustrates the utility model.The meaning of symbol in Fig. 2 is as described below.
1 hydrogenation reactor
2 oxidation units
3 extraction elements
4 moisture adjust device (working solution use before hydrogenation process)
5 moisture adjust device (hydrogen-rich gas use)
6 moisture adjust device (hydrogenation catalyst use)
7 moisture adjust device (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 being extracted the working solution of hydrogen peroxide is back to the circulation 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
< process A >
In process A, working solution and hydrogenation catalyst containing Anthraquinones and solvent are supplied to hydrogenation reactor (1).
Hydrogenation reactor used in method as the utility model, the catalyst for being able to use common gas-liquid-solid are anti-
Answer device, the i.e. reactor of fixed bed form, fluidized bed form, mechanical stirring form and bubble column form etc..Hydrogenation reactor can
Think one, can also two or more connect in series or in parallel.
Working solution used in the method for the utility model at least contains Anthraquinones and solvent.
Anthraquinones used in the utility model are not particularly limited, preferably alkyl-anthraquinone, alkyl tetrahydro anthraquinone or it
Mixture.Alkyl-anthraquinone and alkyl tetrahydro anthraquinone can also be respectively the mixing of a variety of alkyl-anthraquinones or alkyl tetrahydro anthraquinone
Object.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 the aliphatic substitution using the linear chain or branched chain containing at least one carbon atom, replaces at least
9,10- anthraquinone after one 1,2 or 3.In general, these alkyl substituents contain 9 carbon atoms below, 6 are preferably comprised
Carbon atom below.It 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-propyl anthraquinone, 2- isopropyl anthracene
Quinone, 2- sec-butyl anthraquinone or 2- tert-butyl anthraquinone or 2- amylanthraquinone or 2- tertiary pentyl anthraquinone etc..Alkane in working solution
The concentration of base Anthraquinones is controlled according to the situation of technique, usually with 0.4~1.0mol/l use.
Solvent used in the working solution of the utility model is preferably the nonpolar solvent and dissolution anthracene for dissolving Anthraquinones
The mixed solution of the polar solvent of diphenols.It is by least one alkyl-substituted aromatic hydrocarbon, especially as nonpolar solvent
Or mixtures thereof alkylbenzene containing 8~12 carbon atoms.It is that (for example, diisobutyl carbinol (DIBC), 2- is pungent for alcohol as polar solvent
Alcohol), four substituted ureas, phosphate, 2-Pyrrolidone or acetic acid alkyl ester.It as the combination of preferred solvent, can enumerate: virtue
The combination of fragrant hydrocarbon and alcohol, aromatic hydrocarbon and acetic acid alkyl ester, aromatic hydrocarbon and phosphate and aromatic hydrocarbon and four substituted ureas.
Hydrogenation catalyst used in the utility model contains usual physical absorption or chemisorption in the activity on carrier
The mixture of metallic element or active metallic element.As active metallic element, usually selected from nickel, rhenium, ruthenium, rhodium, palladium and platinum
Select more than one.As active metallic element, preferably at least contain palladium.The content of active metallic element is typically not greater than 10 weights
Measure %, preferably more than 5 weight %, more preferably no more than 3 weight %.Carrier can be used: as common catalyst carrier
Silica, silica alumina, aluminium oxide, oxidation aluminium magnesia, magnesia, silicon dioxide and titanium dioxide, titanium dioxide,
Zirconium oxide, zeolite, active carbon or organic polymer or their mixture etc..Wherein, preferably silica, titanium dioxide
Silicon aluminium oxide, oxidation aluminium magnesia and gama-alumina, preferably silica and silica alumina.
Partial 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, and 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, is
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 carboxylic can also be contained
The adding ingredients such as amide compound as sour amide.
To the means (conduit 101) of hydrogenation reactor supply working solution and the means (conduit of supply hydrogenation catalyst
105) it can be conventional means, be not particularly limited.
< process B >
In process B, hydrogen-rich gas is supplied in hydrogenation reactor, the Anthraquinones for being included by working solution restore, and generate
Oxanthranol class.Means (conduit 103) to hydrogenation reactor supply hydrogen-rich gas can be conventional means, be not particularly limited.
It, can also be in order to which the gas that uses anthraquinone type hydrogenation can be 100% hydrogen in the method for the utility model
For the gas after being diluted hydrogen using inactive gas.As inactive gas, nitrogen, fluoro-gas or argon etc. can be enumerated
Rare gas.In general, using most cheap nitrogen.In addition, in present specification, referred to as " hydrogen-rich gas ", " hydrogen depleted gas "
When simply mean 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 not
It is 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
Hydrogen in body " due to Anthraquinones hydrogenation and be consumed, then become " hydrogen depleted gas " that hydrogen concentration relatively reduces.If from
Unreacted hydrogen is recycled, is concentrated by " hydrogen depleted 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 utility model is usually 10~100 DEG C, and preferably 20 DEG C~80 DEG C,
More preferably 25 DEG C~70 DEG C.Hydrogenation reactor pressure in the method for the utility model be typically set at 100kPa~
500kPa。
< process C >
In process C, working solution and hydrogen depleted gas containing oxanthranol class and solvent is discharged from hydrogenation reactor.
From the means (conduit 102) of hydrogenation reactor discharge working solution and the means (conduit 104) of discharge hydrogen depleted gas
It can be conventional means, be not particularly limited.
< step D >
Step D is to convert Anthraquinones for the oxanthranol class in the working solution being discharged in process C, generates hydrogen peroxide
Oxidation operation.
The oxidation operation of the method for the utility model can be carried out using conventional means.Oxidation unit (2) can be conventional
Means are 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.
< process E >
Process E is the abstraction process from working solution separation hydrogen peroxide.
The abstraction process of the method for the utility model can be carried out using conventional means.Extraction element (3) can be routine
Means are 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 DEG C.
< process F >
Process F is that at least part for the working solution that hydrogen peroxide is extracted in process E is back to following in process B
Ring process.
Working solution can especially not limited for conventional means from the means (conduit 107) that process E is back to process B
It is fixed.
The cycling rate of working solution can arbitrarily be set between 0~100%.
< process G >
In process G, the concentration of the water in the working solution in process B is maintained relative to saturation capacity at 20%~160%,
It is preferred that maintaining at 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 energy in working solution enough passes through karl Fischer titration and is quantified.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 of reactor and/or hydrogenation reactor more than setting at least one.In addition, it can be also set to other positions (conduit),
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 working solution as free water.In the utility model, relative to hydrogenation
The saturation capacity of the water in working solution in reactor, is adjusted to 20%~160% concentration, preferably it is adjusted to 70%~
130% concentration.In the utility model, it can also be adjusted relative to the saturation capacity of the water in the working solution in hydrogenation reactor
At 100%~160% concentration, it is preferably adjusted to 100%~130% concentration.Specifically, using above-mentioned sizing technique,
The moisture into the working solution that hydrogenation reactor supplies is measured with predetermined time interval, according to obtained measured value, selection
The method of moisture control is simultaneously adjusted.
As soon as the hydrogen depleted gas being discharged from it, can be included by it in the case where hydrogenation reactor is
Unreacted hydrogen recycling after being concentrated and adjusting the concentration of water, is supplied again to hydrogenation reactor.In two or more hydrogenation reactors
In the case where series connection, 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, being recycled, being concentrated and being adjusted in the unreacted hydrogen for being included by it from the hydrogen depleted gas that a hydrogenation reactor is discharged
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, being wrapped from the hydrogen depleted gas that a hydrogenation reactor is discharged by it
After the unreacted hydrogen contained is recycled, is 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) adjusting adjoint
The means (device) of the moisture of the working solution supplied to hydrogenation reactor；2) it adjusts with the work being discharged from hydrogenation reactor
Make the means (device) of the moisture of solution；3) means (device) of the moisture with the gas supplied to hydrogenation reactor are adjusted；
4) means (device) of the moisture with the gas being discharged from hydrogenation reactor are adjusted；5) adjustment is supplied with to hydrogenation reactor
Hydrogenation catalyst moisture means (device)；6) hand of the moisture with the working solution in hydrogenation reactor circulation is adjusted
Section (device)；Or the means (device) of water 7) are introduced directly into hydrogenation reactor, further from 1)~7) in combination it is multiple any
The method (system) that means (device) obtain.
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 circulation of adjustment
The means (device) for making the moisture of solution can be enumerated and implement to remove with the process of the water of working solution or add to working solution
The process of water.Specifically, can be carried out by following process (device): a) adjusting in hydrogenation, oxidation or extract each process
The process (device) of the displacement of the tank lower part separation of the working solution of front and back setting；B) using in hydrogenation process, oxidation work
The process (device) of the heat exchanger adjustment moisture of the working solution of the front and back of sequence or abstraction process setting；C) molten using work
The filter of liquid adjusts the process (device) of moisture by Liquid liquid Separation；D) process (dress of coalescer adjustment moisture is utilized
It sets)；E) process (device) of water is adjusted and contacting working solution and solution of potassium carbonate；F) moisture is adjusted by evaporating
Process (device)；Or the process (device) of moisture g) is adjusted by distilling.
Here, more preferably passing through following work with the moisture adjustment of working solution when considering equipment cost and safety
Sequence (device) carries out: a) adjustment is in hydrogenation, oxidation or the tank lower part separation for extracting the working solution being arranged before and after each process
Displacement process (device)；B) working solution being arranged before and after hydrogenation process, oxidation operation or abstraction process is utilized
The process (device 4,5,6,7) of heat exchanger adjustment moisture.
Process (device) to working solution addition water 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 agglomerating catalyst, 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, it can use the mixing in various pumps, pass through mechanical stirring
Mixing, pass through mixing of pipe-line mixer etc..The temperature of the process of moisture adjustment is usually 10~100 DEG C, and preferably 20 DEG C
~80 DEG C, more preferably 25 DEG C~70 DEG C.In the case where removing water, preferably shorter than adjustment moisture process before hydrogenation,
Oxidation or abstraction process temperature, in the case where add water, preferably higher than adjustment moisture process before hydrogenation, aoxidize or
The temperature of abstraction process.
It adjusts in the means with the moisture of gas, device, the cyclone separator, spray of adjustment hydrogenated gas flow can be used
Gas-liquid separation device well known to mist separator etc., activated carbon adsorption desorption apparatus etc..
It adjusts in the means with the moisture of hydrogenation catalyst, using well known drying, firing or vacuum treatment installation, adjusts
The moisture content of renewing hydrogenation catalyst or regenerated hydrogenation catalyst.Here, new hydrogenation catalyst is primary also not for hydrogen
Change the hydrogenation catalyst of reaction, regenerated hydrogenation catalyst is that it is clear to implement solvent after hydrogenation supply more than once
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 be carried out using well known drier, vacuum desiccator, baking furnace etc..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..From the means (conduit of hydrogenation reactor discharge hydrogenation catalyst
106) it may be conventional means, be not particularly limited.
In the means for being introduced directly into water to hydrogenation reactor, make 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, setting monitors the water in the working solution supplied to hydrogenation reactor
The sensor of concentration and started or stopped according to the output signal from sensor above-mentioned process G1~G6 implementation control
Device (8) processed, the concentration of the water in the working solution in hydrogenation container is maintained relative to saturation capacity at 90 ± 70%,
100 ± 30%, other desired ranges.Sensor, device for this etc. can utilize well known device.In addition, being saved in Fig. 2
The line of connection moisture transducer (9,10), control device (8), each device (4,5,6,7,11,20) is omited.
Embodiment
Hereinafter, specifically describing the utility model by embodiment, but the utility model is not limited to the embodiment.
< working solution >
Working solution use is by Swazol 1500, (registered trademark, fragrant hydrocarbon system solvent, ball are apt to petrochemistry strain formula meeting
Society's manufacture, 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.'s manufacture, CAS NO.78-42-2) 30 volume % are constituted dissolves
The solution of ethyl hydrazine (Weifang Menjie Chemicals Co., Ltd.'s manufacture, CAS NO.84-51-5) 0.6mol/l.
< hydrogenation catalyst >
Hydrogenation catalyst has been used in 120 DEG C of 2 dry weight %Pd/ silica or 1 weight % Pd/ silica
Aluminium oxide.
The quantitative > of water in < working solution
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 solution
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.This time the saturation capacity of the water in the working solution of preparation is 3.055g/l.
< test method >
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 alumina 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 alumina 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 alumina 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 alumina 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 alumina 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 alumina 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 alumina 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 utility model is by reasonably setting to utilize the activity of hydrogenation catalyst to greatest extent and the hydrogen that should manage
Change the concentration range of the water in the working solution in reaction vessel, and suitably utilizes and above-mentioned model is made in the water control in working solution
The moisture adjusting method enclosed realizes the accurate and easy process management required in the operation of practical factory.
Claims (6)
1. a kind of manufacture system of hydrogen peroxide characterized by comprising
The conduit A of working solution and hydrogenation catalyst is supplied to hydrogenation reactor；
Supply hydrogen-rich gas conduit and hydrogenation reactor B, the Anthraquinones which is included by working solution into
Row reduction, generates oxanthranol class；
The conduit C of working solution and hydrogen depleted gas is discharged from hydrogenation reactor；
Oxidation unit D converts Anthraquinones for the oxanthranol class in the working solution of discharge, generates hydrogen peroxide；
Extraction element E separates hydrogen peroxide from working solution；And
Circulation conduit F, is back to hydrogenation reactor for at least part for being extracted the working solution of hydrogen peroxide,
The manufacture system of the hydrogen peroxide further includes the device of the concentration of the water in the working solution adjusted in hydrogenation reactor
G。
2. the manufacture system of hydrogen peroxide according to claim 1, it is characterised in that:
Device G includes at least one device in following device,
Adjust the device G1 of the moisture in conduit A with the working solution supplied to hydrogenation reactor；
Adjust the device G2 of the moisture in conduit C with the working solution being discharged from hydrogenation reactor；
Adjust the device G3 of the moisture in hydrogenation reactor B with the hydrogen-rich gas supplied to hydrogenation reactor；
Adjust the device G4 of the moisture in conduit C with the hydrogen depleted gas being discharged from hydrogenation reactor；
The device G5 of water is introduced directly into hydrogenation reactor in conduit A；
With the device G6 of the moisture for the working solution for being back to hydrogenation reactor B in adjustment conduit F.
3. the manufacture system of hydrogen peroxide according to claim 2, it is characterised in that:
At least one device of device G1, device G2 and device G6 includes:
A) tank for the working solution being arranged before and after hydrogenation, oxidation or extraction element；
B) heat exchanger for the working solution being arranged before and after hydrogenation, oxidation or extraction element；
C) filter of working solution；
D) coalescer；
E) device of water is adjusted and contacting working solution and solution of potassium carbonate；
F) pass through the device of evaporation adjustment moisture；Or
G) pass through the device of distillation adjustment moisture.
4. the manufacture system of hydrogen peroxide according to claim 2, 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 for the working solution that adjustment is arranged before and after hydrogenation, oxidation or extraction element
It sets；Or
B) dress of the heat exchanger adjustment moisture for the working solution being arranged before and after hydrogenation, oxidation or extraction element is utilized
It sets.
5. the manufacture system of hydrogen peroxide according to claim 2, it is characterised in that:
Device G3 and/or device G4 includes device, gas-liquid separation device or the activated carbon adsorption desorption for adjusting hydrogenated gas flow
Device.
6. the manufacture system of hydrogen peroxide according to claim 2, it is characterised in that:
Device G5 includes making the microdispersed device of water.
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| JP2017029789A JP2018135229A (en) | 2017-02-21 | 2017-02-21 | Production method of hydrogen peroxide |
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| CN201820217691.4U Active CN208471534U (en) | 2017-02-21 | 2018-02-07 | The manufacture system of hydrogen peroxide |
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| CN113039154B (en) * | 2018-11-20 | 2023-11-03 | 三菱瓦斯化学株式会社 | Working solution treatment method |
| CN109665497A (en) * | 2019-01-09 | 2019-04-23 | 无锡日月水处理有限公司 | A kind of modified hydrogen peroxide preparation method |
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| 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 |
| 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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