WO2022270454A1 - 精製過酸化水素水溶液の製造方法 - Google Patents

精製過酸化水素水溶液の製造方法 Download PDF

Info

Publication number
WO2022270454A1
WO2022270454A1 PCT/JP2022/024484 JP2022024484W WO2022270454A1 WO 2022270454 A1 WO2022270454 A1 WO 2022270454A1 JP 2022024484 W JP2022024484 W JP 2022024484W WO 2022270454 A1 WO2022270454 A1 WO 2022270454A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen peroxide
peroxide solution
aqueous hydrogen
osmosis membrane
reverse osmosis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/024484
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
耕平 茂田
泰宏 櫛田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to KR1020237039310A priority Critical patent/KR20240023024A/ko
Priority to US18/570,142 priority patent/US20240279060A1/en
Priority to CN202280040236.0A priority patent/CN117425619A/zh
Priority to JP2023530453A priority patent/JPWO2022270454A1/ja
Publication of WO2022270454A1 publication Critical patent/WO2022270454A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C01B15/013—Separation; Purification; Concentration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/12—Controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/06—Surface irregularities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range

Definitions

  • the present invention relates to a method for producing a purified aqueous hydrogen peroxide solution, and more particularly to a method for producing a purified aqueous hydrogen peroxide solution including an osmotic membrane treatment step using a reverse osmosis membrane (RO membrane).
  • RO membrane reverse osmosis membrane
  • Hydrogen peroxide is used as a bleaching agent for paper, pulp, fibers, etc., a disinfectant, a food additive, etc., because of its oxidizing power and strong bleaching/sterilizing action. Furthermore, the amount of hydrogen peroxide used is increasing in the electronics industry, such as cleaning the surface of semiconductor substrates, chemically polishing the surface of copper alloys containing copper and tin, and etching electronic circuits.
  • the anthraquinone method is generally used as a method for producing hydrogen peroxide, but the aqueous hydrogen peroxide solution produced by such a method using an organic solvent contains impurities such as organic substances derived from the organic solvent used.
  • foaming may occur during ultrasonic degassing or the like during the production of an aqueous hydrogen peroxide solution by the anthraquinone method, resulting in the odor peculiar to hydrogen peroxide.
  • the aqueous hydrogen peroxide solution obtained by the anthraquinone method or the like is purified.
  • a general method for purifying an aqueous hydrogen peroxide solution there is a method using distillation, a cyclone, an adsorption resin, an ion exchange resin, a reverse osmosis membrane, or the like (Patent Document 1).
  • the inventors found that the quality of the aqueous hydrogen peroxide solution can be improved by adjusting the conditions in the process of treating the crude aqueous hydrogen peroxide solution brought into contact with the RO membrane.
  • the present invention includes the following.
  • a method for producing a purified aqueous hydrogen peroxide solution comprising an osmotic membrane treatment step of bringing a crude aqueous hydrogen peroxide solution containing impurities into contact with a reverse osmosis membrane,
  • a first integrated value that is the product of the value of the pressure (MPaG) of the reverse osmosis membrane and the value of the linear velocity (m 3 /(m 2 ⁇ h)) of the aqueous hydrogen peroxide solution. adjusting the pressure and the linear velocity such that the is less than 0.15.
  • the second integrated value obtained by multiplying the first integrated value by the viscosity (mPa s) of the crude aqueous hydrogen peroxide solution is less than 0.19.
  • permeated water permeated hydrogen peroxide aqueous solution
  • permeated hydrogen peroxide aqueous solution which is the hydrogen peroxide aqueous solution with reduced impurities obtained by the osmosis membrane treatment step, and the impurities that are not permeated by the reverse osmosis membrane
  • the value of the permeation ratio (%) determined by the following formula (1) is 80% or less with the concentrated hydrogen peroxide solution, which is a concentrated aqueous hydrogen peroxide solution.
  • Permeation ratio (%) (mass of permeated water) / (mass of permeated water + concentrated permeated water) x 100 (1)
  • the transmittance value is 60% or more, and the temperature of the crude aqueous hydrogen peroxide solution in the permeation membrane treatment step is 15 to 35° C. or less.
  • the content of impurities such as organic compounds can be reduced, and an aqueous hydrogen peroxide solution can be produced in which bubbling and odor that can occur mainly in the process of producing hydrogen peroxide are suppressed.
  • FIG. 1 is a schematic diagram of one embodiment of a hydrogen peroxide purification system used in the method for producing a purified aqueous hydrogen peroxide solution of the present invention
  • FIG. Among the results of Examples and Comparative Examples, the value of the product (first product) of the pressure of the RO membrane and the linear velocity of the hydrogen peroxide solution in the refining process, and the amount of organic matter in the hydrogen peroxide solution after refining ( TC value).
  • the value of the product (second product) of the pressure of the RO membrane, the linear velocity of the hydrogen peroxide solution, and the viscosity of the hydrogen peroxide solution in the refining process, and the hydrogen peroxide after refining It is a graph which shows the relationship with the amount (TC value) of organic substances of water.
  • One aspect of the present invention is a method for producing a purified aqueous hydrogen peroxide solution, which includes an osmotic membrane treatment step of bringing a crude aqueous hydrogen peroxide solution containing impurities into contact with a reverse osmosis membrane.
  • the present invention provides a first integration that is the product of the value of the pressure (MPaG) of the reverse osmosis membrane and the value of the linear velocity (m 3 /(m 2 h)) of the aqueous hydrogen peroxide solution. It relates to a method for producing a purified aqueous hydrogen peroxide solution in which the pressure and linear velocity are adjusted so that the value is less than 0.15.
  • a method for producing a purified aqueous hydrogen peroxide solution includes a permeation membrane treatment step for purifying a crude aqueous hydrogen peroxide solution.
  • a reverse osmosis membrane RO membrane
  • the crude aqueous hydrogen peroxide solution is purified in the osmotic membrane treatment step to produce a purified aqueous hydrogen peroxide solution with less impurities.
  • Osmotic membrane treatment step 1-1 Relationship Between Reverse Osmosis Membrane Pressure and Linear Velocity of Crude Hydrogen Peroxide Aqueous Solution
  • a crude hydrogen peroxide aqueous solution is purified.
  • the crude aqueous hydrogen peroxide solution is an aqueous hydrogen peroxide solution that has not been purified by an RO membrane, and the aqueous hydrogen peroxide solution may be produced by any method, such as anthraquinone method, alcohol oxidation method, oxidation-reduction method, Including those produced by the direct method (direct oxidation method), electrolytic method, etc.
  • the crude aqueous hydrogen peroxide solution may contain either or both of organic impurities and inorganic impurities.
  • concentration of hydrogen peroxide contained in the crude aqueous hydrogen peroxide solution is not particularly limited, and may be, for example, 20-90% by weight, 30-80% by weight, 35-70% by weight, 40-60% by weight, and the like.
  • the pressure of the reverse osmosis membrane, the linear velocity of the aqueous hydrogen peroxide solution, and the like are adjusted within a preferable range. Specifically, the first integrated value ( MPaG ⁇ m The pressure and linear velocity are adjusted such that 3 /(m 2 ⁇ h)) is less than 0.15.
  • the first integrated value (MPaG ⁇ m 3 /(m 2 ⁇ h)) is preferably 0.12 or less, more preferably 0.10 or less, and further preferably 0.08 or less. It is preferably 0.06 or less, and particularly preferably 0.06 or less.
  • the lower limit of the first integrated value (MPaG ⁇ m 3 /(m 2 ⁇ h)) is not particularly limited, but is, for example, 0.01 or more.
  • the value of the pressure applied to the reverse osmosis membrane and the first integrated value which is a parameter related to the value of the linear velocity of the crude aqueous hydrogen peroxide solution to be treated.
  • the second integrated value (MPaG ⁇ m 3 /(m 2 ⁇ h) ⁇ cP; or MPaG ⁇ m 3 ⁇ cP/(m 2 ⁇ h) or (MPaG ⁇ m 3 /(m 2 ⁇ h) ⁇ mPa ⁇ s) is preferably less than 0.19.
  • the second integrated value (MPaG ⁇ m3/ ( m2 ⁇ h) ⁇ mPa ⁇ s) is preferably 0.17 or less, more preferably 0.15 or less, and 0.13 or less. is more preferably 0.10 or less, and the lower limit of the second integrated value (MPaG ⁇ m 3 /(m 2 ⁇ h) ⁇ mPa ⁇ s) is not particularly limited. 0.01 or more, for example.
  • the second By adjusting the range of the integrated value of , a purified aqueous hydrogen peroxide solution containing few impurities can be obtained.
  • the pressure (gauge pressure: MPaG) in the reverse osmosis membrane for purifying the crude aqueous hydrogen peroxide solution in the osmotic membrane treatment step that is, the value of the pressure (MPaG) for the crude aqueous hydrogen peroxide solution passing through the reverse osmosis membrane is 0. 0.02 to 8.0, more preferably 0.10 to 6.5, still more preferably 0.30 to 5.5, particularly preferably 0.40 to 4.7, It may be 0.80 to 4.5, 1.0 to 4.0, and the like.
  • the value of the gauge pressure (MPaG) in the osmotic membrane treatment step corresponds to the value obtained by subtracting 0.1 from the absolute pressure (MPaA (or MPa)).
  • a value for gauge pressure can be converted to a value for absolute pressure (MPaA (or MPa)) by adding 0.1.
  • MPaG a value for gauge pressure
  • MPaA or MPa
  • the preferred range of the pressure of the above-mentioned reverse osmosis membrane defined by the value of gauge pressure is preferably 0.12 to 8.1, more preferably 0.12 to 8.1 as the value of absolute pressure (MPaA (or MPa)). is 0.20 to 6.6, more preferably 0.40 to 5.6, particularly preferably 0.50 to 4.5, 0.90 to 4.6, 1.1 to 4.6. 1 and so on.
  • the value of the linear velocity (m 3 /(m 2 ⁇ h)) of the crude hydrogen peroxide aqueous solution in the permeation membrane treatment step is preferably 0.005 to 0.050, and the linear velocity (m 3 /(m 2 ⁇ The value of h)) is more preferably 0.007 to 0.040, more preferably 0.010 to 0.030.
  • the value of the flow rate (L/min) of the crude aqueous hydrogen peroxide solution in the permeation membrane treatment step is preferably 0.03 to 3.0, and the value of the flow rate (L/min) is more preferably 0.1. to 2.5, more preferably 0.3 to 2.0, and particularly preferably 0.5 to 1.5.
  • the permeation flux of pure water under conditions of a temperature of 25° C. and an effective pressure of 2.0 MPa is less than 0.6 (m 3 /m 2 /day), as will be described later in detail. It is preferable to adopt a reverse osmosis membrane that can be adjusted to
  • the viscosity (cP or mPa s) value of the crude hydrogen peroxide aqueous solution in the permeation membrane treatment step is preferably 0.05 to 3.0, and the viscosity (cP or mPa s) value is more It is preferably 0.1 to 2.7, more preferably 0.3 to 2.5, and particularly preferably 0.5 to 2.0 or 0.9 to 1.5.
  • the temperature of the crude hydrogen peroxide aqueous solution to be treated is, for example, -20 to 40°C, preferably 5 to 25°C. It may be a temperature range.
  • the temperature range of the crude aqueous hydrogen peroxide solution to be treated may be 10-30°C, 12-27°C, 15-25°C, and the like.
  • the range of the value (MPaG/°C) obtained by dividing the value of the pressure (MPaG) applied to the crude aqueous hydrogen peroxide solution by the value of the temperature (°C) of the crude aqueous hydrogen peroxide solution is preferably 0.01 to 0.50, and the above value (MPaG/° C.) is more preferably 0.03 to 0.40, still more preferably 0.05 to 0.35. , particularly preferably 0.10 to 0.30.
  • Permeation ratio Permeate permeate, which is an aqueous hydrogen peroxide solution in which impurities are reduced, obtained by the osmotic membrane treatment process, and concentrated permeate, which is an aqueous hydrogen peroxide solution in which impurities are concentrated without being permeated by the reverse osmosis membrane.
  • the value of the permeation ratio (permeation liquid ratio; %) determined by the following formula (1) regarding the mass ratio is preferably 80% or less, and may be 85% or less or 90% or less.
  • Permeation ratio (%) (mass of permeated water) / (mass of permeated water + concentrated permeated water) x 100 (1)
  • the above transmission ratio is more preferably 75% or less, still more preferably 70% or less, and particularly preferably 60% or less.
  • the value of the transmittance ratio is, for example, 20% or more, preferably 25% or more, or 35% or more.
  • the value of the permeation ratio in the above formula (1) is set to 40% or less, 35% or less, or 30% or less, and the temperature of the crude hydrogen peroxide aqueous solution in the permeation membrane treatment step, that is, the liquid temperature is set to 25 ° C. or less.
  • the temperature is preferably 20°C or lower, such as 5 to 25°C or 10 to 20°C.
  • the value of the permeation ratio in the above formula (1) is set to 60% or more, 65% or more, or 70% or more, and the temperature of the crude aqueous hydrogen peroxide solution in the permeation membrane treatment step, that is, the liquid temperature is 15 to 35%. °C or within the range of 10 to 30°C.
  • permeated water which is an aqueous hydrogen peroxide solution in which the impurities of the crude hydrogen peroxide aqueous solution have been reduced, is obtained. /L or less.
  • permeated water substantially free of impurities can be efficiently produced, and the concentration of impurities can be kept low as described above.
  • the impurity concentration in the permeated water is more preferably 16 mg/L or less, still more preferably 12 mg/L or less, and particularly preferably 10 mg/L or less, or 8 mg/L or less.
  • Impurities in the crude aqueous hydrogen peroxide solution that is the object of purification usually include organic compounds generated in the process of producing hydrogen peroxide, such as by the anthraquinone method.
  • organic compounds generated in the process of producing hydrogen peroxide such as by the anthraquinone method.
  • examples of such an organic compound include, for example, a working solution composition and its degraded product, as long as it is a crude hydrogen peroxide aqueous solution containing hydrogen peroxide produced by an anthraquinone method.
  • degraded products examples include nonpolar solvent-degraded products (e.g., benzaldehydes, benzoic acids, phenols, benzyl alcohols, etc.), polar solvent-degraded products (e.g., 2-ethylhexanol, 2-ethylhexanal, etc.), and anthraquinone-degraded products.
  • nonpolar solvent-degraded products e.g., benzaldehydes, benzoic acids, phenols, benzyl alcohols, etc.
  • polar solvent-degraded products e.g., 2-ethylhexanol, 2-ethylhexanal, etc.
  • anthraquinone-degraded products for example, anthrone, oxyanthrone, tetrahydrooxyantrone, anthraquinone epoxide, tetrahydroanthraquinone epoxide, etc.
  • the impurities contained in the crude aqueous hydrogen peroxide solution may include inorganic compounds.
  • inorganic impurities include compounds derived from anthraquinone process catalysts, such as copper, zinc, chromium, palladium, rhodium, ruthenium, platinum, iron, nickel, aluminum, sodium, potassium, calcium, chlorine, sulfur, silica, boron and the like. These inorganic compounds can also be subject to purification.
  • Form of Reverse Osmosis Membrane The type of reverse osmosis membrane used in the osmosis membrane treatment step is not particularly limited as long as it has the ability to remove impurities contained in the crude aqueous hydrogen peroxide solution.
  • Forms of reverse osmosis membranes include flat membranes, pleated membranes, spiral membranes, tube membranes, rod membrane fine tube membranes, spaghetti membranes or hollow fiber membranes or combinations thereof.
  • a reverse osmosis membrane device incorporating a reverse osmosis membrane may be used, for example, a cylindrical device incorporating reverse osmosis membranes of various shapes as described above may be used.
  • a reverse osmosis membrane device having a reverse osmosis membrane may be used alone, or may be used by connecting a plurality of them in series or in parallel. For example, two or more or ten or more reverse osmosis membrane devices may be connected in parallel and used.
  • Materials for reverse osmosis membranes include polyethylenimine condensate, cellulose acetate, modified polyacrylonitrile, polybenzimidapyrone, polyetheramide, cellulose triacetate, polyamidecarboxylic acid, crosslinked polyether, crosslinked polyamide, Polyimide, polybenzimidazole, sulfonated phenylene oxide, polypiperazinamide, polyethyleneiminthol, enediisocyanate, polyethyleneisic acid chloride, sulfonated polyfurfuryl alcohol, sulfonated polysulfone, polyether urea, polyvinyl alcohol, polysulfone, polyamide polyvinyl alcohol, Examples include sulfonated polyethersulfone or polyamide.
  • the reverse osmosis membrane may be an asymmetric membrane or a composite membrane. Composite membranes made of polyamide are preferred as reverse osmosis membranes.
  • the material for the reverse osmosis membrane it is preferable to use a material with a mass ratio of oxygen content/nitrogen content of less than 40. That is, the value of the above ratio corresponding to the weight ratio of oxygen atoms and nitrogen atoms in the material member forming the surface of the reverse osmosis membrane through which the aqueous hydrogen peroxide solution permeates is preferably less than 40, and less than 35. is more preferably less than 25, less than 20, or less than 10, and particularly preferably less than 2, for example, 0.1 or more and less than 2.
  • the above-mentioned RO film with a high oxygen/nitrogen ratio coated with polyvinyl alcohol (PVA) can suppress the adhesion of organic impurities, but polyvinyl alcohol may be decomposed by hydrogen peroxide.
  • PVA polyvinyl alcohol
  • the average surface roughness is preferably 0.240 ⁇ m or more. Moreover, the average value of the surface roughness of the reverse osmosis membrane is preferably 1.000 ⁇ m or less. It was confirmed that the use of a reverse osmosis membrane having such an average roughness value increases the TC rejection to the permeated water, that is, the TC value in the permeated water is efficiently reduced. .
  • the average value of the surface roughness of the reverse osmosis membrane is more preferably 0.300 ⁇ m to 0.900 ⁇ m, further preferably 0.400 ⁇ m to 0.850 ⁇ m, 0.450 ⁇ m to 0.800 ⁇ m, for example 0 0.500 ⁇ m to 0.750 ⁇ m is particularly preferred.
  • the initial value of the surface roughness of the RO membrane is often 0.600 to 0.700 ⁇ m, but the surface tends to become smoother with use and the surface roughness value tends to decrease. Therefore, it is important to confirm and adjust the average roughness value of the reverse osmosis membrane.
  • the surface roughness value of the reverse osmosis membrane is the arithmetic roughness average Ra based on the JIS standard (JIS B 0601-2001).
  • the treatment pressure applied to the reverse osmosis membrane when the crude aqueous hydrogen peroxide solution is brought into contact with the reverse osmosis membrane may be within a range that the reverse osmosis membrane allows. It can withstand pressure in the range of 0.02 to 8.0 (MPaG) applied to
  • the range of pressure that can be applied to the reverse osmosis membrane in this manner is more preferably the pressure range described above in the osmosis membrane treatment step, or 0.10 to 7.0 (MPaG), and more preferably 0.30 to 6.0 MPaG. More preferably 0 (MPaG), 0.50 to 5.0 (MPaG), for example 1.0 to 4.5 (MPaG).
  • the value of the pressure (absolute pressure: MPaA (or MPa)) permissible for the reverse osmosis membrane is preferably 0.12 to 8.1 (MPaG), and 0.20 to 7.1 (MPa). is more preferably 0.40 to 6.1 (MPa), more preferably 0.60 to 5.1 (MPa), for example 1.1 to 4.6 (MPa).
  • the reverse osmosis membrane is preferably one that can adjust the permeation flux of pure water to less than 0.6 (m 3 /m 2 /day) when the temperature is 25° C. and the effective pressure is 2.0 MPa. Specifically, 0.1 or more and less than 0.6 (m 3 /m 2 /day), 0.2 or more and less than 0.6 (m 3 /m 2 /day), 0.3 or more and 0.5 (m It is preferable to use a material capable of permeating pure water with a flux of 3 /m 2 /day) or less.
  • the temperature mentioned above is the temperature of the pure water permeating the reverse osmosis membrane and the temperature of the reverse osmosis membrane itself.
  • the effective pressure is the effective pressure acting on the reverse osmosis membrane obtained by subtracting the osmotic pressure difference and the secondary side pressure from the average operating pressure
  • the average operating pressure is the pressure of the feed water on the primary side of the reverse osmosis membrane.
  • (operating pressure) and the pressure of concentrated water (concentrated water outlet pressure) that is, the value of (operating pressure + concentrated water outlet pressure)/2).
  • the reverse osmosis membrane use of a membrane having a water permeability of 300 to 1000 GPD (Gallons per day) under conditions of a feed water temperature of 25°C, a feed pressure of 5.5 MPa and a salinity concentration of feed water of 32000 (ppm (mg/L)).
  • the reverse osmosis membrane preferably has a water permeability of 400 to 800 GPD, more preferably 500 to 700 GPD, and particularly preferably 550 to 650 GPD.
  • the RO membrane can be used by being incorporated into a reverse osmosis membrane module.
  • the reverse osmosis membrane module may comprise a reverse osmosis membrane and a pressure vessel for fixedly supporting the reverse osmosis membrane, and further comprises pressurizing means for bringing the crude aqueous hydrogen peroxide solution into contact with the reverse osmosis membrane. good too.
  • the value of the membrane area of the reverse osmosis membrane that is, the area of the permeation surface of the crude aqueous hydrogen peroxide solution in the reverse osmosis membrane is not particularly limited.
  • the membrane area of the reverse osmosis membrane included in is about 40m2.
  • the method for producing the purified aqueous hydrogen peroxide solution preferably further includes a roughness measuring step of measuring the surface roughness of the reverse osmosis membrane used in the osmotic membrane treatment step.
  • a roughness measuring step of measuring the surface roughness of the reverse osmosis membrane used in the osmotic membrane treatment step As described above, the surface roughness value of the RO membrane usually decreases with use in the osmotic membrane treatment process. Therefore, according to the roughness measurement process, the average surface roughness value This is because it is confirmed whether or not is adjusted.
  • the surface roughness value of the reverse osmosis membrane is preferably measured or at least documented before and after the osmosis membrane treatment step, for example, before the osmosis membrane treatment step.
  • the surface roughness value of the reverse osmosis membrane is measured after it is used in the osmotic membrane treatment step, preferably immediately after the osmotic membrane treatment, the degree of deterioration of the reverse osmosis membrane in the osmotic membrane treatment, the rough permeation
  • TC value impurity concentration
  • the surface roughness value of the RO membrane is measured using a three-dimensional white light interference microscope, an atomic force microscope (AFM), or the like.
  • FIG. 1 is a schematic diagram showing an example of a purification system 10 for an aqueous hydrogen peroxide solution that can be used in a osmotic membrane treatment process for purifying an aqueous hydrogen peroxide solution.
  • the purification system 10 includes an RO membrane vessel 3 and the like, and the RO membrane vessel 3 is provided with an RO membrane 3a.
  • a tank 1 for raw material hydrogen peroxide (crude aqueous hydrogen peroxide solution, hereinafter also referred to as crude hydrogen peroxide solution), a metering pump 2, an RO membrane vessel 3, a back pressure valve 4, first and second flow rates Sensors 6a and 6b, purification side and non-purification side processing liquid tanks 8a and 8b are connected by piping as shown.
  • the crude permeated water is a permeated liquid (permeated water) sent to the purification side treated liquid tank 8a by the RO membrane 3a arranged inside the RO membrane vessel 3, and a non-refined side treated liquid tank 8b. It is separated and purified into a concentrate (concentrated filtrate) sent to
  • a predetermined raw material hydrogen peroxide solution is put into the raw material hydrogen peroxide tank 1, and the chiller/heater is heated to a predetermined temperature (for example, as shown in the following table showing the results of the examples). Adjust the liquid temperature so that it reaches the stated temperature (20° C., etc.). After sending the raw material hydrogen peroxide to the RO membrane vessel 3 side with the metering pump 2 and confirming the flow of hydrogen peroxide to the concentrated liquid side piping, the back pressure valve 4 connected to the concentrated liquid side piping is gradually closed.
  • the inside of the RO membrane vessel 3 is raised to a predetermined pressure (for example, the pressure (2.20 MPaG, etc.) shown in the table below showing the results of the examples). Then, when the osmotic pressure of the crude permeate inside the RO membrane vessel 3 exceeds the predetermined pressure, hydrogen peroxide begins to flow into the permeate side pipe.
  • a predetermined pressure for example, the pressure (2.20 MPaG, etc.
  • the back pressure valve 4 is adjusted so that the concentration liquid (non-permeated liquid): 0.5 L / min and the permeated liquid: 0.5 L / min. .
  • the hydrogen peroxide-depleted solution is collected while maintaining a predetermined permeate/concentrate flow rate ratio.
  • the TC value was obtained by measuring the TOC value using a TOC (total organic carbon) meter.
  • Apparatus TOC-L manufactured by Shimadzu Corporation Measurement method: A sample was heated to 680°C together with a platinum catalyst in a combustion furnace filled with purified air, and burned and decomposed to convert to carbon dioxide. The TC (total carbon) concentration in the sample was obtained by cooling and dehumidifying the converted carbon dioxide and comparing with the calibration curve. Next, the same sample was separately acidified and aerated to convert IC (inorganic carbon) in the sample to carbon dioxide, which was then detected to determine the IC concentration. The TOC concentration was calculated by subtracting the IC concentration from the obtained TC concentration.
  • ⁇ Purification by RO membrane> A commercially available 582 GPD reverse osmosis membrane was used as the RO membrane. Conditions such as permeation ratio (sampling ratio), supply liquid temperature, supply liquid flow rate, and treatment pressure were set as shown in Table 1 below to purify the aqueous hydrogen peroxide solution.
  • ⁇ Surface Roughness of RO Membrane> The surface roughness of the RO film was measured with a three-dimensional white light interference microscope as follows. Device: "Contour GT-K" manufactured by Bruker Japan Co., Ltd. Each sample of the RO membrane was cut into a square of about 2 cm, placed on a slide glass of the above apparatus, and subjected to analysis while moistened with water.
  • Apparatus Contour GT-K made by Bruker Measurement Mode: Vertical Scan (VSI) Objective lens: 50x Measurement range: (XY) 126 x 95 ⁇ m 2 (Z) 30 ⁇ m Back Scan: 5 ⁇ m Threshold: 5% (threshold of CCD detector sensitivity) Correction: Cylindrical + tilt correction Measurement method: Measurement was performed in a mode in which interference fringes were measured by scanning 30 ⁇ m in the Z direction while illuminating the RO film sample with white light. ⁇ Bubbling of hydrogen peroxide solution> 50 ml of purified aqueous hydrogen peroxide solution was added to a 50 ml volumetric flask and heated in a boiling bath for 5 hours.
  • aqueous solution was cooled to room temperature and subjected to an ultrasonic cleaner for degassing, and foaming was visually judged. Those with no foaming were judged as "good”, and those with foaming were judged as "bad”.
  • ⁇ Odor of hydrogen peroxide solution> A purified aqueous hydrogen peroxide solution was weighed into a 50 ml volumetric flask, stoppered and shaken 10 times, and then the odor was determined by the operator's sense of smell. A sample with no odor was judged to be "good", and a sample with an odor was judged to be "bad".
  • Example 1 A 45% hydrogen peroxide solution (unwashed crude peroxide solution) prepared from hydrogen peroxide obtained by the anthraquinone method was subjected to RO membrane purification under the conditions shown in Table 1 below.
  • the membrane area is 2.4 (m 2 )
  • the average surface roughness value is 0.60 ⁇ m
  • the temperature is 25 ° C.
  • the effective pressure is 2.0 MPa.
  • a commercial product having a permeation flux of 0.5 (m 3 /m 2 /day) and a mass ratio of oxygen amount/nitrogen amount of less than 2 was used.
  • Table 1 shows the results of TOC concentration (TC concentration), foaming evaluation, and odor evaluation of the obtained aqueous solution of purified hydrogen peroxide (permeated water).
  • Example 2-11 and Comparative Examples 1 and 2 The same 45% hydrogen peroxide solution (unwashed crude permeate) as in Example 1 was purified under the conditions shown in Table 1 above.
  • the flow rate of the raw material pump was 1.00 L/min
  • the flow rate of the concentrated liquid (non-permeated liquid) was 0.3 L/min
  • the flow rate of the permeated liquid was 0.3 L/min.
  • the back pressure valve 4 was adjusted to 7 L/min.
  • Example 7 the linear velocity, that is, the value obtained by dividing the raw material pump flow velocity by the membrane area was 0.025 (m 3 /(m 2 ⁇ h), so that the flow velocity was 1.00 L / min, the membrane area Using an RO membrane of 2.4 (m 2 ), raw material hydrogen peroxide (crude hydrogen peroxide aqueous solution, hydrogen peroxide) with a viscosity of 1.17 (mPa ⁇ s) was used as a purification target.
  • Example 8 and 9 and Comparative Example 1 the same RO membrane as used in other Examples such as Example 7 was used, and the surface roughness value was small due to long-term use. Using. Table 2 shows the average roughness values on the surface of the RO membrane.
  • the TC value of the obtained purified hydrogen peroxide solution can be sufficiently lowered, while foaming and Odor generation was suppressed.
  • the first integrated value which is the product of the value of the reverse osmosis membrane pressure (MPaG) and the value of the linear velocity (m 3 /(m 2 ⁇ h)) of the aqueous hydrogen peroxide solution, is 0.15.
  • the TC value is less than that, the TC value is sufficiently lowered, and the organic compounds as impurities are removed more efficiently than in the comparative examples that do not satisfy these requirements, and foaming and odor generation are prevented.
  • RO membrane vessel 3a RO membrane 10: Purification system (purification system for aqueous hydrogen peroxide solution)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/JP2022/024484 2021-06-22 2022-06-20 精製過酸化水素水溶液の製造方法 Ceased WO2022270454A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020237039310A KR20240023024A (ko) 2021-06-22 2022-06-20 정제과산화수소 수용액의 제조방법
US18/570,142 US20240279060A1 (en) 2021-06-22 2022-06-20 Method for producing purified aqueous hydrogen peroxide solution
CN202280040236.0A CN117425619A (zh) 2021-06-22 2022-06-20 精制过氧化氢水溶液的制造方法
JP2023530453A JPWO2022270454A1 (https=) 2021-06-22 2022-06-20

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021103228 2021-06-22
JP2021-103228 2021-06-22

Publications (1)

Publication Number Publication Date
WO2022270454A1 true WO2022270454A1 (ja) 2022-12-29

Family

ID=84545672

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/024484 Ceased WO2022270454A1 (ja) 2021-06-22 2022-06-20 精製過酸化水素水溶液の製造方法

Country Status (6)

Country Link
US (1) US20240279060A1 (https=)
JP (1) JPWO2022270454A1 (https=)
KR (1) KR20240023024A (https=)
CN (1) CN117425619A (https=)
TW (1) TW202313456A (https=)
WO (1) WO2022270454A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024190575A1 (ja) * 2023-03-10 2024-09-19 三菱瓦斯化学株式会社 精製された過酸化水素水溶液及びその製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0733408A (ja) * 1993-07-14 1995-02-03 Sumitomo Chem Co Ltd 過酸化水素水の精製方法
JPH09102480A (ja) * 1995-10-06 1997-04-15 Taiyo Toyo Sanso Co Ltd シリコンウエハ洗浄用の過酸化水素水
JPH09271647A (ja) * 1996-01-24 1997-10-21 Nitto Denko Corp 高透過性複合逆浸透膜及びこれを用いた逆浸透膜モジュール
JPH10330102A (ja) * 1997-05-29 1998-12-15 Nitto Denko Corp 過酸化水素水の精製方法
JP2004089962A (ja) * 2002-09-04 2004-03-25 Mitsubishi Gas Chem Co Inc 逆浸透膜の処理方法
JP2007014878A (ja) * 2005-07-07 2007-01-25 Kurita Water Ind Ltd 膜分離装置の汚染状態の診断方法、診断装置、および膜分離装置の洗浄方法
US20170113932A1 (en) * 2014-06-30 2017-04-27 Arkema France Hyrogen peroxide purification process and hyrogen peroxide

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4206556B2 (ja) 1999-04-15 2009-01-14 三菱瓦斯化学株式会社 精製過酸化水素水溶液の製造方法
JP7187839B2 (ja) * 2018-06-29 2022-12-13 三菱瓦斯化学株式会社 過酸化水素の製造方法
KR102051841B1 (ko) * 2019-08-27 2019-12-04 태광산업주식회사 과산화수소 수용액의 정제 방법
CN112957925B (zh) * 2021-03-11 2022-11-11 浙江工业大学 一种以减小聚酰胺层本征厚度的高渗透性复合反渗透膜的制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0733408A (ja) * 1993-07-14 1995-02-03 Sumitomo Chem Co Ltd 過酸化水素水の精製方法
JPH09102480A (ja) * 1995-10-06 1997-04-15 Taiyo Toyo Sanso Co Ltd シリコンウエハ洗浄用の過酸化水素水
JPH09271647A (ja) * 1996-01-24 1997-10-21 Nitto Denko Corp 高透過性複合逆浸透膜及びこれを用いた逆浸透膜モジュール
JPH10330102A (ja) * 1997-05-29 1998-12-15 Nitto Denko Corp 過酸化水素水の精製方法
JP2004089962A (ja) * 2002-09-04 2004-03-25 Mitsubishi Gas Chem Co Inc 逆浸透膜の処理方法
JP2007014878A (ja) * 2005-07-07 2007-01-25 Kurita Water Ind Ltd 膜分離装置の汚染状態の診断方法、診断装置、および膜分離装置の洗浄方法
US20170113932A1 (en) * 2014-06-30 2017-04-27 Arkema France Hyrogen peroxide purification process and hyrogen peroxide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024190575A1 (ja) * 2023-03-10 2024-09-19 三菱瓦斯化学株式会社 精製された過酸化水素水溶液及びその製造方法

Also Published As

Publication number Publication date
KR20240023024A (ko) 2024-02-20
CN117425619A (zh) 2024-01-19
JPWO2022270454A1 (https=) 2022-12-29
US20240279060A1 (en) 2024-08-22
TW202313456A (zh) 2023-04-01

Similar Documents

Publication Publication Date Title
JP4996925B2 (ja) 浸透膜蒸留のための装置及び方法
CA2783545A1 (en) Method for washing separation membrane module and method for generating fresh water
KR20140071943A (ko) 과산화수소 수용액의 정제 방법 및 정제 장치
WO2022270454A1 (ja) 精製過酸化水素水溶液の製造方法
Nataraj et al. Cellulose acetate-coated α-alumina ceramic composite tubular membranes for wastewater treatment
Aryanti et al. Modified polysulfone ultrafiltration membrane for humic acid removal during peat water treatment
WO2019188965A1 (ja) 超純水製造システム及び超純水製造方法
JP3712225B2 (ja) 脱塩水の水質監視方法
Fakhfekh et al. Removal of iron using an oxidation and ceramic microfiltration hybrid process for drinking water treatment
JP7662994B2 (ja) フッ素含有排水の処理方法
JP7333865B2 (ja) 水処理方法および水処理装置
Mei et al. Application of airlift ceramic ultrafiltration membrane ozonation reactor in the degradation of humic acids
JP6699681B2 (ja) 逆浸透膜装置の運転管理方法および逆浸透膜処理システム
JP4825932B2 (ja) 水処理方法
CA2084589A1 (en) Process for the purifying working-up of reaction media and/or wash media obtained during preparation of cellulose ethers
JP3780734B2 (ja) 複合半透膜
CN116422151A (zh) 用于反渗透膜系统的黏泥剥离剂的使用方法
JP3638426B2 (ja) 脱気用セラミック複合部材並びにそれを用いた脱気方法
JP2022057429A (ja) フッ素含有排水の処理方法及び装置
JP2009291708A (ja) 逆浸透膜およびその表面処理方法
Hofman-Bieniek et al. Synthesis of polymer membranes of different porosity and their application for phenol removal from liquid phase
KR102867926B1 (ko) 초순수 제조 방법, 초순수 제조 장치 및 초순수 제조 시스템
JP7824914B2 (ja) 純水用水の製造方法及び製造装置、純水製造方法及び純水製造システム
WO2026028678A1 (ja) 精製された過酸化水素水の製造方法
JP7171671B2 (ja) 超純水製造システム及び超純水製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22828371

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023530453

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202280040236.0

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 18570142

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22828371

Country of ref document: EP

Kind code of ref document: A1