Hydrogen peroxide manufacturing process and manufacturing system based on photochemical reaction

Abstract

The present invention relates to a photochemical reaction-based hydrogen peroxide manufacturing process and manufacturing system. Specifically, it relates to a series of hydrogen peroxide manufacturing processes that generate, extract, and purify hydrogen peroxide by photochemical reactions, and a hydrogen peroxide manufacturing system to which the manufacturing process is applied, comprising a photoreactor, an extractor, and a purifier.

Description

Technology Field

[0001] The present invention relates to a photochemical reaction-based hydrogen peroxide manufacturing process and manufacturing system. Specifically, it relates to a series of hydrogen peroxide manufacturing processes that generate, extract, and purify hydrogen peroxide by photochemical reactions, and a hydrogen peroxide manufacturing system to which the manufacturing process is applied, comprising a photoreactor, an extractor, and a purifier. Background Technology

[0002] In the industrial production of hydrogen peroxide, more than 90% of total production is achieved through the anthraquinone oxidation / reduction process. This anthraquinone oxidation / reduction process is a method that generates hydrogen peroxide by reducing oxygen molecules within a repetitive oxidation / reduction cycle of anthraquinone molecules. Since this process is carried out under reaction conditions of high temperatures above 50°C and high pressures above 4 bar, it requires a large amount of energy and high costs. Furthermore, the use of rare metal catalysts, such as palladium (Pd), in this process can also be a factor in increasing costs. In particular, the rare metals used as catalysts may not be easy to procure due to the high dependence on resource imports.

[0003] The anthraquinone oxidation / reduction process poses problems not only from an economic perspective but also from an environmental perspective. The high temperature and high pressure process generates large amounts of carbon, and the use of metal catalysts can produce toxic reaction byproducts, potentially causing environmental issues. Additionally, the use of hydrogen (H2) gas in the process poses a risk of explosion.

[0004] In addition to problems inherent in the process itself, there is a growing need for effective, eco-friendly, low-carbon hydrogen peroxide production technologies in industrial settings. In fact, since relatively low concentrations (less than 2 wt%) of hydrogen peroxide are used in major hydrogen peroxide demand centers such as water treatment plants and semiconductor cleaning processes, technologies for producing hydrogen peroxide on-site in a dispersed manner can be highly effective. Currently, eco-friendly technologies for producing hydrogen peroxide include electrochemical and photocatalytic technologies, but they face difficulties in commercialization due to clear limitations in performance, production scale, and purification costs.

[0005] There is a need for hydrogen peroxide production technology that can be utilized in industrial settings, which produces hydrogen peroxide in an eco-friendly, low-carbon manner while satisfying the production scale required by actual industries and ensuring high safety. The problem to be solved

[0006] The technical problem that the present invention aims to solve is to provide a hydrogen peroxide manufacturing process capable of producing hydrogen peroxide with high efficiency using a photochemical reaction.

[0007] Another technical problem that the present invention aims to solve is to provide a hydrogen peroxide manufacturing system that can apply a hydrogen peroxide manufacturing process having the aforementioned advantages and comprises a photoreactor, an extractor, and a purifier in a series. means of solving the problem

[0008] A hydrogen peroxide manufacturing process according to one embodiment of the present invention comprises: a production step of generating hydrogen peroxide by supplying oxygen and irradiating light to an organic reaction solution; an extraction step of separating the hydrogen peroxide into an aqueous solution phase by mixing the organic reaction solution in which hydrogen peroxide has been generated with water; and a purification step of filtering the extracted aqueous hydrogen peroxide solution using a reverse osmosis membrane; wherein the organic reaction solution may contain a hydrophobic organic solvent in a range of 50 volume% or more based on the total volume of the organic reaction solution.

[0009] A hydrogen peroxide manufacturing system according to another embodiment of the present invention comprises: a reactor capable of producing hydrogen peroxide by a photo-auto-oxidation reaction using an organic reaction solution; an extractor for extracting the hydrogen peroxide produced in the reactor into an aqueous solution using a large amount of water; and a purifier for separating and purifying the hydrogen peroxide in the aqueous solution; wherein the reactor, the extractor, and the purifier are sequentially connected, and a catalyst regenerator connected to the reactor through a circulation pipe is located between the reactor and the extractor, and a mixer for mixing the organic reaction solution from which the polymer photocatalyst has been separated with water for extraction is located between the extractor and the catalyst regenerator, and the mixer may additionally include a stirrer. Effects of the invention

[0010] A hydrogen peroxide manufacturing process according to one embodiment of the present invention can improve the production efficiency of hydrogen peroxide through a photochemical reaction of an organic reaction solution and provide a method for obtaining hydrogen peroxide with high purity and high concentration.

[0011] In a hydrogen peroxide production system according to another embodiment of the present invention, the production efficiency of hydrogen peroxide can be improved by the photochemical reaction of an organic reaction solution in a photoreactor, and hydrogen peroxide can be obtained with high purity and high concentration by an extractor and a purifier connected in series with the photoreactor. Brief explanation of the drawing

[0012] FIG. 1 is a schematic diagram showing a photochemical reaction-based continuous hydrogen peroxide production system and a production process according to one embodiment of the present invention. Figure 2 shows the production volume of hydrogen peroxide and benzaldehyde (BzCHO), an oxidized organic product, and the photochemical conversion efficiency (SCC efficiency) according to a 50-hour continuous process of an organic reaction solution included in a hydrogen peroxide manufacturing process and manufacturing system according to one embodiment of the present invention. Figure 3 shows the purity and concentration of hydrogen peroxide prepared according to one embodiment of the present invention. Figure 4 shows the water treatment performance of high-concentration and high-purity hydrogen peroxide on organic pollutants produced according to one embodiment of the present invention. Specific details for implementing the invention

[0013] The technical terms used herein are for the reference of specific embodiments only and are not intended to limit the invention. The singular forms used herein include plural forms unless phrases clearly indicate otherwise. As used in the specification, the meaning of "comprising" specifies certain characteristics, areas, integers, steps, actions, elements, and / or components, and does not exclude the presence or addition of other characteristics, areas, integers, steps, actions, elements, and / or components.

[0014] All terms used herein, including technical and scientific terms, have the same meaning as generally understood by a person skilled in the art to which this invention pertains.

[0015] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0016] FIG. 1 is a schematic diagram showing a photochemical reaction-based continuous hydrogen peroxide production system and a production process according to one embodiment of the present invention.

[0017] Referring to FIG. 1 above, a hydrogen peroxide manufacturing process according to one embodiment of the present invention may include a production step of generating hydrogen peroxide by supplying oxygen and irradiating light to an organic reaction solution, an extraction step of separating the hydrogen peroxide into an aqueous solution by mixing the organic reaction solution in which hydrogen peroxide has been generated with water, and a purification step of filtering the extracted hydrogen peroxide aqueous solution using a reverse osmosis membrane, and the organic reaction solution may contain a hydrophobic organic solvent in a range of 50 volume% or more based on the total volume of the organic reaction solution.

[0018] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the organic reaction solution is a mixture of an aromatic alcohol and an organic solvent, and the aromatic alcohol may contain 0.1% to 0.2% by weight of an aromatic carbonyl compound based on the total weight of the aromatic alcohol.

[0019] Specifically, the aromatic carbonyl compound included in the above 0.1% to 0.2% by weight corresponds to one that is contained by self-oxidation within the aromatic alcohol. In addition, the aromatic carbonyl compound contained by the oxidation of a portion of the aromatic alcohol can act as an auto-catalyst, serving as both a catalyst and an oxidation reaction product in the organic reaction solution.

[0020] The production step of the hydrogen peroxide manufacturing process according to one embodiment may include additionally mixing an aromatic carbonyl compound into the organic reaction solution.

[0021] The above aromatic carbonyl compound can be added to promote the production of hydrogen peroxide in the organic reaction solution.

[0022] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the aromatic carbonyl compound additionally mixed may include one or more selected from aromatic ketones or aromatic aldehydes.

[0023] The above aromatic ketones or aromatic aldehydes are benzaldehyde (BzCHO), 9-anthracenecarboxaldehyde, 9-anthraldehyde (9-Anthraldehyde), 9-phenanthrenecarboxaldehyde, fluorene-2-carboxaldehyde, 1-pyrenecarboxaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, biphenyl-4-carboxaldehyde, benzophenone, 4-methylbenzaldehyde (p-Tolualdehyde), 3-methylbenzaldehyde (m-Tolualdehyde), 2-Methylbenzaldehyde (o-Tolualdehyde), 4-Chlorobenzaldehyde, 3-Chlorobenzaldehyde, 2-Chlorobenzaldehyde, 4-Fluorobenzaldehyde, 3-Fluorobenzaldehyde, 2-Fluorobenzaldehyde, 4-Bromobenzaldehyde, 3-Bromobenzaldehyde, 2-Bromobenzaldehyde, 1-(p-Tolyl)ethenone, 1-(4-Fluorophenyl)ethenone, p-anisaldehyde, 4-formylbenzonitrile, 4-methoxyacetophenone,It may include one or more selected from 4-acetylbenzonitrile, anthraquinone, fluorenone, acetophenone, xanthone, and thioxanthone.

[0024] However, the present invention is not limited to the types of aromatic ketones or aromatic aldehydes described above, and can be extended to include substances belonging to aromatic ketones or aromatic aldehydes that can promote the generation of hydrogen peroxide in an organic reaction solution in addition to the substances described above.

[0025] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the aromatic carbonyl compound may be additionally mixed in a range of 0.001 volume% to 30 volume% based on the total volume of the mixture of the aromatic alcohol, the organic solvent, and the additionally mixed aromatic carbonyl compound. Preferably, the range may be 0.001 volume% to 20 volume%. More preferably, the range may be 0.001 volume% to 10 volume%. Even more preferably, the range may be 1 volume% to 10 volume%.

[0026] If the amount of the additionally mixed aromatic carbonyl compound falls within the aforementioned range, there is an advantage in that the light absorption and photo-auto-oxidation reaction of the aromatic carbonyl compound are promoted, thereby improving the hydrogen peroxide production capacity. On the other hand, if the amount of the additionally mixed aromatic carbonyl compound is less than the lower limit of the aforementioned range, there may be a problem in that the effect of photo-auto-oxidation by the aromatic carbonyl is negligible. If the amount of the additionally mixed aromatic carbonyl compound exceeds the upper limit of the aforementioned range, the aromatic radicals generated during the reaction of the organic reaction solution undergo homocoupling to produce organic byproducts rather than hydrogen peroxide, which may be disadvantageous in terms of hydrogen peroxide production efficiency.

[0027] However, even without additionally mixing the above aromatic carbonyl compound, trace amounts of aromatic ketones or aromatic aldehydes inherently contained in aromatic alcohols may act as autocatalysts, and as the specific gravity of the aromatic alcohol increases, the hydrogen peroxide production performance of the organic reaction solution may be improved.

[0028] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the aromatic alcohol may include one or more selected from the group consisting of benzyl alcohols substituted with electron-withdrawing and electron-donating functional groups.

[0029] The group consisting of benzyl alcohols substituted with functional groups having electron-withdrawing and electron-donating properties may include benzyl alcohol (BzOH), 4-fluorobenzyl alcohol (F-BzOH), 3-fluorobenzyl alcohol, 2-fluorobenzyl alcohol, 4-methylbenzyl alcohol (M-BzOH), 3-methylbenzyl alcohol, 2-methylbenzyl alcohol, α-methylbenzyl alcohol (α-M-BzOH), diphenylmethanol (DPM), and cinnamyl alcohol.

[0030] However, the present invention is not limited to the types of aromatic alcohols described above, and can be extended to include substances belonging to aromatic alcohols that can promote the generation of hydrogen peroxide in an organic reaction solution, in addition to the substances described above. In particular, based on the structure of benzyl alcohol, the types of aromatic alcohols applicable to the present invention can be expanded according to the types of 2-, 3-substituents, substituents with electron-withdrawing properties, and substituents with electron-period properties.

[0031] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the aromatic alcohol may be mixed in a volume ratio of 1:99 to 99:1 based on the volume of the organic solvent mixed into the organic reaction solution. Preferably, the volume ratio of the organic solvent to the aromatic alcohol may be 10:90 to 90:10. More preferably, the volume ratio of the organic solvent to the aromatic alcohol may be 30:70 to 90:10. More preferably, the volume ratio of the organic solvent to the aromatic alcohol may be 50:50 to 90:10. Even more preferably, the volume ratio of the organic solvent to the aromatic alcohol may be 50:50 to 70:30.

[0032] When the volume ratio of the organic solvent and the aromatic alcohol falls within the aforementioned range, the productivity of hydrogen peroxide in the organic reaction solution is improved, and optimal production efficiency can be achieved.

[0033] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the oxygen solubility of the organic solvent may be 1 mM to 15 mM based on 1 atm.

[0034] When the oxygen solubility of the organic solvent falls within the aforementioned range, the oxygen concentration in the organic reaction solution is high, which increases the activation of oxygen in the photo-auto-oxidation reaction and has the advantage of accelerating the production rate of hydrogen peroxide. On the other hand, when the oxygen solubility of the organic solvent is below the lower limit of the aforementioned range, there may be a problem in that the production rate of hydrogen peroxide slows down. In addition, when the oxygen solubility of the organic solvent exceeds the upper limit of the aforementioned range, the oxygen gas pressure in the organic reaction solution must be increased, which increases the amount of energy added to the reaction and may reduce energy efficiency.

[0035] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the organic solvent comprises a hydrophobic organic solvent, and the hydrophobic organic solvent may include an octanol-water partition coefficient (log P) value of 0 or greater as represented by Formula 1 below.

[0036] [Equation 1] Octanol-water partition coefficient = log P = log([C oct ] / [C water ])

[0037] (In the above Equation 1, [C oct ] is the molar concentration of the organic solvent dissolved in the octanol layer, [C water ] refers to the molar concentration of the organic solvent dissolved in the water layer.)

[0038] If the above octanol-water partition coefficient satisfies the aforementioned range, the hydrogen peroxide produced after the hydrogen peroxide production reaction can be extracted with water. On the other hand, if the above octanol-water partition coefficient does not fall within the aforementioned range, during the process of extracting hydrogen peroxide formed in the organic reaction solution with water, it is difficult to extract hydrogen peroxide due to mixing between the organic reaction solution and water, and at the same time, there may be a problem in that the purity of the extracted aqueous hydrogen peroxide solution is low.

[0039] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the organic solvent is trifluorotoluene, acetonitrile, methanol, ethanol, tert-butanol, 1-propanol, 2-propanol, acetone, ethyl acetate, tert-amyl alcohol, 1-butanol, petroleum ether, pentane, cyclohexane, n-hexane, dichloromethane, chloroform, tetrahydrofuran, 1,4-dioxane, toluene, dimethyl It may include one or more selected from dimethyl sulfoxide (DMSO), dimethylformamide, 1,2-dichloroethane, 1-octanol, benzonitrile, butanone, cyclohexanone, methyl tert-butyl ether, 2-hexanone, butyl acetate, trichloroethylene, xylene, and ethyl benzene.

[0040] However, the present invention is not limited to the types of organic solvents described above, and may be extended to include the application of any hydrophobic organic solvent that satisfies the octanol-water partition coefficient range described above and allows for the mixing of a small amount of water, even if not mentioned in the types of substances described above.

[0041] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the oxygen supply rate in the production step may be in the range of 10 mL / min to 50 mL / min.

[0042] When the oxygen supply rate falls within the aforementioned range, there is an advantage in that a sufficient amount of oxygen is supplied to the organic reaction solution, thereby maximizing the hydrogen peroxide production capacity. On the other hand, when the oxygen supply rate is below the lower limit of the aforementioned range, there may be a problem in that the amount of oxygen in the reaction solution is low, resulting in low hydrogen peroxide production. Furthermore, when the oxygen supply rate exceeds the upper limit of the aforementioned range, the organic solvent may evaporate during the process of charging oxygen into the organic reaction solution, and the stability of the reaction may be reduced due to the increase in pressure caused by oxygen.

[0043] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the oxygen supply time may be in the range of 15 min to 60 min.

[0044] If the oxygen supply time falls within the aforementioned range, there is an advantage in that a sufficient amount of oxygen is supplied to the organic reaction solution, thereby maximizing the hydrogen peroxide production capacity. On the other hand, if the oxygen supply time is below the lower limit of the aforementioned range, there may be a problem in that the amount of oxygen in the reaction solution is low, resulting in low hydrogen peroxide production. Furthermore, if the oxygen supply time exceeds the upper limit of the aforementioned range, oxygen is supplied in excess while the oxygen concentration in the reaction solution is saturated, which may be disadvantageous in terms of process operation costs.

[0045] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the light wavelength irradiated may include a range of 200 nm to 500 nm. Preferably, it may be a light wavelength in the range of 230 nm to 400 nm. A light source having the light wavelength may be simulated sunlight or a short-wavelength lamp. Specifically, the simulated sunlight source includes a wavelength in the range of 200 nm to 1000 nm, and the short-wavelength lamp includes a range of 200 nm to 400 nm. Additionally, the short-wavelength lamp may be an ultraviolet lamp with an average wavelength of 352 nm, including a UVA region of 315 nm to 400 nm.

[0046] When the above light wavelength falls within the aforementioned range, it corresponds to the light absorption region of aromatic alcohols and aromatic carbonyl compounds in the organic reaction solution, thus offering the advantage of maximizing the performance of the reaction. On the other hand, when the above light wavelength is below the lower limit of the aforementioned range, it falls outside the light absorption region of the organic reaction solution, which may lead to problems of organic matter decomposition caused by strong ultraviolet rays. Furthermore, when the above light wavelength exceeds the upper limit of the aforementioned range, it falls outside the light absorption region of aromatic alcohols and aromatic carbonyl compounds in the organic reaction solution, causing a sharp drop in reaction efficiency, which may be disadvantageous in terms of hydrogen peroxide production.

[0047] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the light irradiation time may be in the range of greater than 0 and less than or equal to 60 hours.

[0048] Since the hydrogen peroxide manufacturing process of the present invention is a photochemical reaction-based process, light must be irradiated onto the organic reaction solution. In the hydrogen peroxide manufacturing process of the present invention, the light irradiation time is preferably proposed within the range described above, but may also include modification and expansion to a range exceeding the upper limit of the range described above as necessary.

[0049] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the radiant intensity is 10 W / m 2Up to 1000 W / m 2 It may include irradiating with phosphorescent light. Specifically, the radiant irradiance may vary depending on the type of light source irradiating the organic reaction solution. When irradiating using simulated sunlight, the radiant irradiance is 900 to 1000 W / m². 2 Phosphorescent light can be irradiated. When using a short-wavelength lamp for light irradiation, the radiant illuminance is 10 W / m² 2 up to 100 W / m 2 Phosphorescent light can be irradiated.

[0050] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, a polymer photocatalyst and water are additionally mixed into an organic reaction solution, and the polymer photocatalyst may include one or more selected from CTF-Ph, CTF-Th, CTF-BPh, and graphitic carbon nitride (g-C3N4).

[0051] In the hydrogen peroxide manufacturing process of the present invention, in order to improve the production efficiency of hydrogen peroxide, it may further include expanding to other types of polymer photocatalysts in addition to the types described above.

[0052] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the concentration of the polymer photocatalyst additionally mixed into the organic reaction solution may be in the range of 0.1 g / L to 4.0 g / L. Specifically, the concentration of the polymer photocatalyst may be in the range of 0.1 g / L to 2.0 g / L. More specifically, the concentration of the polymer photocatalyst may be in the range of 0.1 g / L to 1.0 g / L.

[0053] When the concentration of the polymer photocatalyst falls within the aforementioned range, the reaction in which photoelectrons formed in the photocatalyst selectively reduce oxygen molecules is added to the auto-oxidation of the organic reaction solution, thereby maximizing quantum efficiency. Accordingly, the production volume of hydrogen peroxide can be improved, and optimal production efficiency can be achieved. On the other hand, when the concentration of the polymer photocatalyst falls outside the aforementioned range, the production efficiency of hydrogen peroxide may decrease. In particular, if the upper limit is exceeded, the production efficiency of hydrogen peroxide may decrease rapidly.

[0054] In the production step of the hydrogen peroxide manufacturing process according to one embodiment, the water may be included in a range of 0 to 30 mol% based on the total amount of aromatic alcohol contained in the organic reaction solution.

[0055] When the amount of water in the organic reaction solution to which the photocatalyst is added falls within the aforementioned range, the production efficiency of hydrogen peroxide can be improved because the water lowers the oxidation potential by hydrogen bonding with the organic material to be reacted. On the other hand, when the amount of water exceeds the upper limit of the aforementioned range, the photoelectrons formed by the photocatalyst are also used to reduce the hydrogen ions generated by the decomposition of water, which may reduce the oxygen molecule reduction rate. As the oxygen molecule reduction rate decreases, a problem may arise in which the production volume and production efficiency of hydrogen peroxide are reduced.

[0056] In a hydrogen peroxide manufacturing process according to one embodiment of the present invention, even in the case of an organic reaction solution that does not contain a photocatalyst, a small amount of water may be additionally added. Furthermore, the small amount of water may function to promote the photo-auto-oxidation reaction by forming hydrogen bonds with the target aromatic alcohol or aromatic carbonyl in the photo-auto-oxidation reaction. On the other hand, the small amount of water may function to inhibit the reaction by quenching the aromatic radicals generated in the photo-auto-oxidation reaction. When performing a photo-auto-oxidation reaction that does not contain a photocatalyst in an organic reaction solution according to one embodiment of the present invention, the additional addition of water tended to somewhat inhibit the reaction. However, this is merely one aspect of one embodiment, and if some of the conditions regarding the aromatic alcohol, organic solvent, and additionally mixed aromatic carbonyl compound presented in the present invention are modified, results may be obtained in which the small amount of water promotes the photo-auto-oxidation reaction. That is, the invention presented herein can be applied to a method for producing hydrogen peroxide by modifying some of its contents, but whether or not to add water to the organic reaction solution can be chosen by a person skilled in the art by judging whether it is advantageous for the photo-automatic oxidation reaction.

[0057] The volume ratio of water mixed in the extraction step of the hydrogen peroxide manufacturing process according to one embodiment and the organic reaction solution in which hydrogen peroxide is produced may be 0.1 to 10.

[0058] When the above volume ratio falls within the aforementioned range, hydrogen peroxide generated in the organic reaction solution can be efficiently separated into an aqueous solution. On the other hand, if the above volume ratio is below the lower limit of the aforementioned range, hydrogen peroxide may remain in the organic reaction solution without being separated into an aqueous solution. Furthermore, if the above volume ratio exceeds the upper limit of the aforementioned range, the amount of water is excessive compared to the organic reaction solution, so the organic reaction solution is dispersed in the water, which may result in a problem where the organic reaction solution cannot be easily separated from the water.

[0059] In the extraction step of the hydrogen peroxide manufacturing process according to one embodiment, the process further includes mixing the organic reaction solution in which hydrogen peroxide is generated with water for extraction and stirring, and the stirring speed may be 100 rpm to 1000 rpm.

[0060] When the above stirring speed falls within the aforementioned range, the organic reaction solution and the water for extraction are well physically mixed, making extraction easier.

[0061] In the extraction step of the hydrogen peroxide manufacturing process according to one embodiment, the time for the solution mixed with the organic reaction solution from which hydrogen peroxide is generated and the water for extraction to remain inside the extractor may be 1 minute to 180 minutes.

[0062] If the residence time of the above-mentioned mixed solution falls within the aforementioned range, there may be an advantage of a high extraction amount because the hydrogen peroxide generated in the organic reaction solution is sufficient to move into the water. On the other hand, if the residence time of the above-mentioned mixed solution does not fall within the aforementioned range, there may be a problem of a low extraction amount because hydrogen peroxide remains in the organic reaction solution.

[0063] The extraction step of the hydrogen peroxide manufacturing process according to one embodiment includes separating the hydrogen peroxide aqueous solution layer and the organic solution layer, and the method of discharging the aqueous solution layer and the organic solution layer may include an intermittent method.

[0064] The above intermittent method refers to a method in which a mixture of an organic reaction solution and water is introduced into an extractor, allowed to remain for a certain period of time, and then the valve is opened to discharge the solution once complete phase separation is achieved, repeating this process at a regular interval. However, the present invention is not necessarily limited to the intermittent method and may further include modifications and expansions to a continuous method (a method in which the valve is kept open and the separated layer is continuously discharged at a low flow rate) as necessary.

[0065] In the extraction step of the hydrogen peroxide manufacturing process according to one embodiment, the discharge rate of the aqueous solution layer may be 0.1 L / h to 20 L / h, and the discharge rate of the organic solution layer may be 0.1 L / h to 20 L / h.

[0066] When the discharge rate of the aqueous layer and the discharge rate of the organic solution layer fall within the aforementioned range, the hydrogen peroxide aqueous layer and the organic solution layer can be easily separated without mixing with each other. On the other hand, when the discharge rate of the aqueous layer and the discharge rate of the organic solution layer fall outside the aforementioned range, there may be a problem in that the hydrogen peroxide extraction efficiency is reduced or the interfacial separation between the two solution layers is not properly achieved. In the hydrogen peroxide extraction process of the present invention, the discharge rates of the aqueous layer and the organic solution layer are preferably proposed within the aforementioned range, but may also include modification and expansion to a range exceeding the upper limit of the aforementioned range depending on the capacity of the reactor.

[0067] In the purification step of the hydrogen peroxide manufacturing process according to one embodiment, the reverse osmosis filtration is operated in a crossflow manner, and 20 cm 2 Based on a reverse osmosis membrane having an effective area, the reverse osmosis filtration velocity is 0.05 m / s to 1.0 m / s, and the reverse osmosis membrane may include a polyamide reverse osmosis membrane with a maximum operating pressure of 80 bar. Specifically, the reverse osmosis filtration velocity may be 0.1 m / s to 0.9 m / s. More specifically, the reverse osmosis filtration velocity may be 0.15 m / s to 0.7 m / s.

[0068] The mass ratio of Total Organic Carbon (TOC) contained in the final aqueous hydrogen peroxide solution obtained through the hydrogen peroxide manufacturing process according to one embodiment may be 0.01% to 1% with respect to the total mass of the aqueous hydrogen peroxide solution. Specifically, it may be 0.01% to 0.1%.

[0069] If the mass ratio of total organic carbon (TOC) to the total mass of the above-mentioned aqueous hydrogen peroxide solution falls within the aforementioned range, the purity of the obtained hydrogen peroxide is high, which may have the advantage of being directly applicable to hydrogen peroxide sites requiring ultra-high purity. On the other hand, if the mass ratio of total organic carbon (TOC) to the total mass of the above-mentioned aqueous hydrogen peroxide solution exceeds the upper limit, the purity of the produced hydrogen peroxide is low, and its use may be limited to industrial purposes only.

[0070] After the production step of the hydrogen peroxide manufacturing process according to one embodiment, a catalyst regeneration step may be further included in which a polymer photocatalyst is separated from an organic reaction solution containing hydrogen peroxide discharged from a reactor and circulated to the reactor, and the organic reaction solution containing hydrogen peroxide from which the catalyst has been separated is supplied to an extractor.

[0071] FIG. 1 is a schematic diagram showing a photochemical reaction-based continuous hydrogen peroxide production system and a production process according to one embodiment of the present invention.

[0072] Referring to FIG. 1 above, a hydrogen peroxide manufacturing system according to another embodiment of the present invention is a hydrogen peroxide manufacturing system capable of performing a hydrogen peroxide manufacturing process according to the aforementioned embodiment, and may include a reactor capable of producing hydrogen peroxide by a photo-auto-oxidation reaction using an organic reaction solution, an extractor for extracting hydrogen peroxide produced in the reactor into an aqueous solution using a large amount of water, and a purifier for separating and purifying hydrogen peroxide in the aqueous solution; wherein the reactor, the extractor, and the purifier may be sequentially connected. In addition, a catalyst regenerator connected to the reactor through a circulation pipe may be located between the reactor and the extractor, and a mixer for mixing the organic reaction solution from which the polymer photocatalyst has been separated with water for extraction may be located between the extractor and the catalyst regenerator, and the mixer may additionally include a stirrer.

[0073] In a hydrogen peroxide manufacturing system according to another embodiment, the reactor may include a reaction vessel having at least one reaction liquid outlet at the bottom, an injection part capable of injecting an organic reaction solution and oxygen into the reaction vessel, an irradiation part capable of sealing the reaction vessel while simultaneously transmitting light, and a light source.

[0074] In a hydrogen peroxide manufacturing system according to another embodiment, the extractor may include a solution inlet, a first separation unit for extracting an aqueous hydrogen peroxide solution, and a second separation unit for discharging an organic reaction solution from which hydrogen peroxide has been removed, and the first separation unit and the second separation unit may each include at least one flow control valve.

[0075] The positions of the first and second separation sections may vary depending on the type of organic solvent included in the organic reaction solution.

[0076] In the extractor of the hydrogen peroxide manufacturing system according to another embodiment, the second separation unit may be connected to the reactor through a circulation pipe so that the organic reaction solution from which hydrogen peroxide has been removed is fed back into the reactor to recycle the aromatic carbonyl compound.

[0077] In the extractor of the hydrogen peroxide production system according to another embodiment, a device for separating aromatic ketones from an organic reaction solution from which hydrogen peroxide has been removed may be further included at the downstream end of the second separation unit.

[0078] In a hydrogen peroxide manufacturing system according to another embodiment, the purifier may include a purification tank, at least one reverse osmosis membrane having a cross-section positioned perpendicular to the flow of the hydrogen peroxide aqueous solution inside the purification tank, at least one inlet for introducing the hydrogen peroxide aqueous solution extracted from the organic reaction solution, and at least one outlet for discharging the purified hydrogen peroxide aqueous solution, and may include a hydrogen peroxide concentration regulator provided at the downstream end of the outlet.

[0079] The following are examples and comparative examples regarding a hydrogen peroxide manufacturing system and manufacturing process based on a solar reaction.

[0080] (Example 1)

[0081] (A) Production of hydrogen peroxide

[0082] An organic reaction solution was prepared consisting of 30 ml of benzyl alcohol as an aromatic alcohol, 29.42 ml of trifluorotoluene as an organic solvent, and 0.58 ml of water. Then, 100 mg of the polymer photocatalyst CTF-Ph was dispersed in a total of 60 ml of the above organic reaction solution. Subsequently, the reaction vessel was filled with oxygen gas to perform an aeration process for 30 minutes. At a solar photovoltaic simulator, 980 W / m² 2 The hydrogen peroxide generation reaction was carried out by irradiating with light. The reaction was carried out for a maximum of 50 hours, during which 1 ml of the reaction sample was extracted every 3 hours and additional oxygen was supplied every 9 hours.

[0083] Figure 2 shows the production volume of hydrogen peroxide and benzaldehyde (BzCHO), an oxidized organic product, and the photochemical conversion efficiency (SCC efficiency) according to a 50-hour continuous process of an organic reaction solution included in a hydrogen peroxide manufacturing process and manufacturing system according to one embodiment of the present invention.

[0084] According to Figure 2 above, it can be seen that the concentrations of hydrogen peroxide and organic products obtained over 50 hours increase linearly, and it can be confirmed that 18.5 mmol of hydrogen peroxide and 29.6 mmol of benzaldehyde organic products can be obtained. Furthermore, it can be seen that high concentrations of hydrogen peroxide and organic products can be stably produced in larger reaction scales and long-term experiments. When deriving the solar-to-chemical conversion efficiency based on the production concentration of hydrogen peroxide every 3 hours, it can be seen that a high efficiency of 0.32% is maintained even after 50 hours of reaction. Therefore, it can be seen that stable production of hydrogen peroxide using light is possible in the hydrogen peroxide manufacturing process and system utilizing the organic reaction solution according to the present invention.

[0085] (B) Extraction of hydrogen peroxide

[0086] The organic reaction solution containing hydrogen peroxide obtained in the above hydrogen peroxide production step was mixed with 2000 ml of water. The mixed solution was left for 1 hour until the organic reaction solution and the aqueous hydrogen peroxide solution separated by forming an interface. The aqueous hydrogen peroxide solution formed on the upper layer of the interface was extracted.

[0087] (C) Purification of hydrogen peroxide

[0088] The aqueous hydrogen peroxide solution obtained from the above hydrogen peroxide extraction step was introduced into a purifier equipped with a reverse osmosis membrane. A polyamide membrane (Dow Filmtec, SW30XLE) was used for this reverse osmosis membrane. The polyamide membrane was activated using ultrapure water at a pressure of 20 bar. Subsequently, reverse osmosis filtration was performed using a crossflow method, and the aqueous hydrogen peroxide solution was purified at an operating speed of 0.21 m / s. The obtained aqueous hydrogen peroxide solution was approximately 2 L, with a flow rate of 1.8 L / m³. -2 h -1 bar -1 was.

[0089] Figure 3 shows the purity and concentration of hydrogen peroxide prepared according to one embodiment of the present invention.

[0090] In addition, according to Figure 3 above, the concentration of hydrogen peroxide in the obtained aqueous hydrogen peroxide solution is 103.4 ppm, and the concentration of total organic carbon (TOC) contained in the solution is 32.7 ppm, showing a purity of 99.997%.

[0091] The following is an experimental example confirming the water treatment performance of hydrogen peroxide prepared according to one embodiment of the present invention.

[0092] (Experimental Example 1) Verification of water treatment performance of hydrogen peroxide produced according to the present invention

[0093] Hydrogen peroxide is a substance used as an oxidizing agent to decompose organic pollutants in water purification processes. The organic water treatment mechanism utilizing hydrogen peroxide is characterized by decomposing organic matter using the oxidizing power of OH radicals generated by activating hydrogen peroxide. In order to confirm the potential for utilizing the hydrogen peroxide finally produced according to one embodiment of the present invention, its performance was verified by applying it to a water treatment reaction.

[0094] Fenton oxidation is used to activate hydrogen peroxide in typical water treatment reactions. Fenton oxidation is a method in which divalent iron ions are injected together with hydrogen peroxide to activate hydrogen peroxide into OH radicals through the oxidation of iron ions.

[0095] After administering iron ions (3 mM) and produced hydrogen peroxide (3 mM) to methylene blue (50 ppm, pH 3), an organic pollutant, the decomposition behavior of the pollutant was observed by a color change.

[0096] Figure 4 shows the water treatment performance of high-concentration and high-purity hydrogen peroxide on organic pollutants produced according to one embodiment of the present invention.

[0097] According to Figure 4 above, it can be seen that organic pollutants are completely decomposed and turn colorless in just 10 seconds by high concentrations of hydrogen peroxide. On the other hand, when organic pollutants of the same concentration are treated with hydrogen peroxide alone or UV light, there is no change in concentration. The above results prove that pollutants are decomposed through the activation of hydrogen peroxide. Therefore, it can be confirmed that high concentrations and high purity hydrogen peroxide obtained from the solar reaction-based continuous hydrogen peroxide manufacturing system and manufacturing process of the present invention can be practically utilized, such as for water purification.

Claims

Claim 1 A photochemical reaction-based hydrogen peroxide manufacturing process comprising: a production step of generating hydrogen peroxide by supplying oxygen and irradiating light to an organic reaction solution; an extraction step of separating the hydrogen peroxide into an aqueous solution phase by mixing the organic reaction solution in which hydrogen peroxide has been generated with water; and a purification step of filtering the extracted aqueous hydrogen peroxide solution using a reverse osmosis membrane; wherein the organic reaction solution contains a hydrophobic organic solvent in a range of 50 volume% or more based on the total volume of the organic reaction solution, and further includes mixing a polymer photocatalyst and water into the organic reaction solution in the production step, and wherein the water is contained in a range of 0 to 30 mol% based on the total amount of aromatic alcohol contained in the organic reaction solution. Claim 2 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, wherein the organic reaction solution in the production step is a mixture of an aromatic alcohol and an organic solvent, and the aromatic alcohol comprises 0.1% to 0.2% by weight of an aromatic carbonyl compound based on the total weight of the aromatic alcohol. Claim 3 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, comprising additionally mixing an aromatic carbonyl compound into an organic reaction solution in the production step. Claim 4 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 3, wherein the additionally mixed aromatic carbonyl compound is one or more selected from aromatic ketones or aromatic aldehydes. Claim 5 In claim 4, the aromatic ketone or aromatic aldehyde is benzaldehyde (BzCHO), 9-anthracenecarboxaldehyde, 9-anthraldehyde (9-Anthraldehyde), 9-phenanthrenecarboxaldehyde, fluorene-2-carboxaldehyde, 1-pyrenecarboxaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, biphenyl-4-carboxaldehyde, benzophenone, 4-methylbenzaldehyde (p-Tolualdehyde), 3-methylbenzaldehyde (m-Tolualdehyde), 2-Methylbenzaldehyde (o-Tolualdehyde), 4-Chlorobenzaldehyde, 3-Chlorobenzaldehyde, 2-Chlorobenzaldehyde, 4-Fluorobenzaldehyde, 3-Fluorobenzaldehyde, 2-Fluorobenzaldehyde, 4-Bromobenzaldehyde, 3-Bromobenzaldehyde, 2-Bromobenzaldehyde, 1-(p-Tolyl)ethenone, 1-(4-Fluorophenyl)ethenone, p-anisaldehyde, 4-formylbenzonitrile, 4-methoxyacetophenone,A photochemical reaction-based hydrogen peroxide manufacturing process comprising one or more selected from 4-acetylbenzonitrile, anthraquinone, fluorenone, acetophenone, xanthone, and thioxanthone. Claim 6 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 3, wherein the aromatic carbonyl compound is additionally mixed in a range of 0.001 volume% to 30 volume% based on the total volume of the mixture of the organic reaction solution and the additionally mixed aromatic carbonyl compound. Claim 7 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 2, wherein the aromatic alcohol is one or more selected from the group consisting of benzyl alcohols substituted with electron-withdrawing and electron-donating functional groups. Claim 8 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 7, wherein the group of benzyl alcohols substituted with electron-withdrawing and electron-donating functional groups comprises benzyl alcohol (BzOH), 4-fluorobenzyl alcohol (F-BzOH), 3-fluorobenzyl alcohol (3-fluorobenzyl alcohol), 2-fluorobenzyl alcohol (2-fluorobenzyl alcohol), 4-methylbenzyl alcohol (M-BzOH), 3-methylbenzyl alcohol (3-methylbenzyl alcohol), 2-methylbenzyl alcohol (2-methylbenzyl alcohol), α-methylbenzyl alcohol (α-M-BzOH), and diphenylmethanol (DPM). Claim 9 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 2, wherein the aromatic alcohol is mixed in a volume ratio of 1:99 to 99:1 based on the volume of the organic solvent mixed into the organic reaction solution. Claim 10 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 2, wherein the oxygen solubility of the organic solvent is 1 mM to 15 mM based on 1 atm. Claim 11 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 2, wherein the organic solvent comprises a hydrophobic organic solvent, and the hydrophobic organic solvent has an octanol-water partition coefficient (log P) value represented by the following Equation 1 that is 0 or greater. [Equation 1] Octanol-water partition coefficient = log P = log([C oct ] / [C water ])(In the above Equation 1, [C oct ] is the molar concentration of the organic solvent dissolved in the octanol layer, [C water ] refers to the molar concentration of the organic solvent dissolved in the water layer.) Claim 12 In paragraph 2, the organic solvent is trifluorotoluene, acetonitrile, methanol, ethanol, tert-butanol, 1-propanol, 2-propanol, acetone, ethyl acetate, tert-amyl alcohol, 1-butanol, petroleum ether, pentane, cyclohexane, n-hexane, dichloromethane, chloroform, tetrahydrofuran, 1,4-dioxane, toluene, dimethyl sulfoxide (DMSO), A photochemical reaction-based hydrogen peroxide manufacturing process comprising one or more selected from dimethylformamide, 1,2-dichloroethane, 1-octanol, benzonitrile, butanone, cyclohexanone, methyl tert-butyl ether, 2-hexanone, butyl acetate, trichloroethylene, xylene, and ethyl benzene. Claim 13 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, wherein the oxygen supply rate in the production step is in the range of 10 mL / min to 50 mL / min. Claim 14 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, wherein the oxygen supply time in the production step is in the range of 15 min to 60 min. Claim 15 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, wherein the light wavelength irradiated in the production step is in the 200 nm to 500 nm range. Claim 16 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, wherein the light irradiation time in the production step is in the range of greater than 0 and less than or equal to 60 hours. Claim 17 In paragraph 1, the production step has a radiant intensity of 10 W / m² 2 Up to 1000 W / m 2 A photochemical reaction-based hydrogen peroxide manufacturing process including irradiating phosphorus light. Claim 18 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, comprising additionally mixing a polymer photocatalyst and water into an organic reaction solution in the production step, wherein the polymer photocatalyst comprises one or more selected from CTF-Ph, CTF-Th, CTF-BPh, and graphitic carbon nitride (g-C3N4). Claim 19 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 18, wherein the concentration of the polymer photocatalyst additionally mixed into the organic reaction solution in the above production step is in the range of 0.1 g / L to 4.0 g / L. Claim 20 delete Claim 21 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, wherein the volume ratio of water mixed in the extraction step to the organic reaction solution in which hydrogen peroxide is produced is 0.1 to 10. Claim 22 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, further comprising the step of mixing an organic reaction solution in which hydrogen peroxide is generated in the extraction step with water for extraction and then stirring, wherein the stirring speed is 100 rpm to 1000 rpm. Claim 23 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, wherein the time of residence of the solution mixed with water for extraction and the organic reaction solution in which hydrogen peroxide is generated in the extraction step is 1 minute to 180 minutes. Claim 24 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, wherein the extraction step comprises separating into a hydrogen peroxide aqueous solution layer and an organic solution layer and discharging each, and the method of discharging the aqueous solution layer and the organic solution layer is an intermittent method. Claim 25 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 24, wherein the discharge rate of the aqueous solution layer is 0.1 L / h to 20 L / h and the discharge rate of the organic solution layer is 0.1 L / h to 20 L / h. Claim 26 In paragraph 1, the reverse osmosis filtration in the purification step is operated in a crossflow manner, and 20 cm 2 A photochemical reaction-based hydrogen peroxide manufacturing process, wherein the reverse osmosis filtration velocity is 0.05 m / s to 1.0 m / s based on a reverse osmosis membrane having an effective area, and the reverse osmosis membrane is a polyamide reverse osmosis membrane with a maximum operating pressure of 80 bar. Claim 27 A photochemical reaction-based hydrogen peroxide manufacturing process, wherein the mass ratio of Total Organic Carbon (TOC) contained in the final aqueous hydrogen peroxide solution obtained through the hydrogen peroxide manufacturing process according to claim 1 is 0.01% to 1% with respect to the total mass of the aqueous hydrogen peroxide solution. Claim 28 A photochemical reaction-based hydrogen peroxide manufacturing process according to claim 1, further comprising a catalyst regeneration step in which, after the production step, a polymer photocatalyst is separated from an organic reaction solution containing hydrogen peroxide discharged from a reactor and circulated to the reactor, and the organic reaction solution containing hydrogen peroxide from which the catalyst has been separated is supplied to an extractor. Claim 29 A photochemical reaction-based hydrogen peroxide manufacturing system comprising: a reactor capable of producing hydrogen peroxide by a photo-auto-oxidation reaction using an organic reaction solution; an extractor for extracting the hydrogen peroxide produced in the reactor into an aqueous solution using a large amount of water; and a purifier for separating and purifying the hydrogen peroxide in the aqueous solution; wherein the reactor, the extractor, and the purifier are sequentially connected, a catalyst regenerator connected to the reactor via a circulation pipe is located between the reactor and the extractor, a mixer for mixing the organic reaction solution from which the polymer photocatalyst has been separated with water for extraction is located between the extractor and the catalyst regenerator, and the mixer may additionally include a stirrer. Claim 30 A photochemical reaction-based hydrogen peroxide production system according to claim 29, wherein the reactor comprises: a reaction vessel having at least one reaction liquid outlet at the bottom; an injection part capable of injecting an organic reaction solution and oxygen into the reaction vessel; an irradiation part capable of sealing the reaction vessel while simultaneously transmitting light; and a light source. Claim 31 A photochemical reaction-based hydrogen peroxide production system according to claim 29, wherein the extractor comprises: an inlet; a first separation unit for extracting an aqueous hydrogen peroxide solution; and a second separation unit for discharging an organic reaction solution from which hydrogen peroxide has been removed, wherein the first separation unit and the second separation unit each have at least one flow control valve. Claim 32 A photochemical reaction-based hydrogen peroxide production system according to claim 31, wherein the second separation unit is connected to the reactor through a circulation pipe so that the organic reaction solution from which the hydrogen peroxide has been removed is reintroduced into the reactor to recycle the aromatic carbonyl compound. Claim 33 A photochemical reaction-based hydrogen peroxide production system according to claim 31, further comprising a device for separating aromatic ketones from an organic reaction solution from which hydrogen peroxide has been removed at the downstream end of the second separation unit. Claim 34 A photochemical reaction-based hydrogen peroxide production system according to claim 29, wherein the purifier comprises: a purification tank; at least one reverse osmosis membrane having a cross-section positioned perpendicular to the flow of an aqueous hydrogen peroxide solution inside the purification tank; at least one inlet for introducing an aqueous hydrogen peroxide solution extracted from an organic reaction solution; and at least one outlet for discharging a purified aqueous hydrogen peroxide solution, wherein a hydrogen peroxide concentration regulator is provided at the downstream end of the outlet.

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