KR20140071943A - Method and device for refining of purification of hydrogen peroxide - Google Patents
Method and device for refining of purification of hydrogen peroxide Download PDFInfo
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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Abstract
The present invention provides a method for purifying an aqueous hydrogen peroxide solution containing impurities, the method comprising: a primary treatment step of removing organic impurities from an aqueous hydrogen peroxide solution containing the impurities; A secondary treatment step of using an aqueous hydrogen peroxide solution after the primary treatment step using a reverse osmosis membrane; And a tertiary treatment step of using the aqueous hydrogen peroxide solution after the secondary treatment using at least one of a cation exchange resin, an anion exchange resin and a chelating resin.
Description
TECHNICAL FIELD The present invention relates to a method for purifying an aqueous solution of hydrogen peroxide, and more particularly, to a method and apparatus for purifying an aqueous solution of hydrogen peroxide which can be purified to ultra-high purity hydrogen peroxide to a degree that can be used in semiconductor fields.
Generally, hydrogen peroxide is a compound of hydrogen and oxygen, colorless and water-like liquid. Its formula is H 2 O 2 and its molecular weight is 34. In addition, the melting point of the commercial 35 wt% product is -34 DEG C, the boiling point is 108 DEG C, and the specific gravity has the characteristic of rising with increasing concentration. Such hydrogen peroxide dissolves well in water, ethanol, and ether. Hydrogen ions are partially dissociated from the aqueous solution and have a weak acidity. Since concentrated hydrogen peroxide is toxic and strongly irritant, it must be handled very carefully. It is mainly used in the laboratory to observe the reaction rate because it is easily decomposed into oxygen and water by an inorganic substance such as alkali metal, heavy metal and manganese dioxide as a catalytic reaction. Decomposition reaction is easily decomposed in alkaline, but relatively stable in acidity, so phosphoric acid and uric acid suppress decomposition of hydrogen peroxide.
Hydrogen peroxide has strong oxidizing power and the product after reaction is harmless with water and oxygen and is widely used as an oxidation reaction agent in propylene oxide and caprolactam production process. It is also used as oxidizing agent for reagents, silk / wool / paper / pulp Bleaching agent in the plastics industry, as a catalyst for vinyl polymerization, and as a disinfectant, and 90% aqueous solution is used for the propulsion of rocket propellants and submarine engines. In addition to the above-mentioned uses, it is also used in etching of semiconductor wafer cleaning, liquid crystal display (LCD), and electronic printed circuit board (PCB) The technique of cleaning the surface of the material is similar to the etching process in that it removes the material on the surface of the semiconductor wafer, but the object is that the impurities (film, individual particles or particles, adsorbed gas, etc.) They have the characteristics of materials such as atoms, ions, molecules, etc.), and chemical wetting method using hydrogen peroxide is used as a typical wet cleaning method.
Particularly, when hydrogen peroxide is used to clean the surface of a semiconductor wafer as described above, if commercially available hydrogen peroxide is used as it is, since it contains impurities, if used as it is, it reacts with impurities existing on the surface of the semiconductor wafer, , Pure hydrogen peroxide should be used, which has been stripped of impurities using a purification column. The hydrogen peroxide quality requirement level (on a cation basis) in the known semiconductor industry is shown in Table 1 below.
Hydrogen peroxide is mostly prepared by the alkyl anthraquinone auto-oxidation method. The alkyl anthraquinone auto-oxidation method is a method in which an alkyl anthraquinone and / or a working solution of tetrahydroalkylanthraquinone dissolved in a diluent are hydrogenated to produce alkyl anthrahydroquinone / RTI > and / or alkyltetrahydroanthraquinone. The diluent that can be used is a liquid which can be used as an organic solvent. The working solution leaving the hydrogenation step is oxidized with oxygen, air or oxygen enriched air to obtain hydrogen peroxide, and the alkyl anthraquinone and / or alkyltetrahydro anthraquinone is reformed. The hydrogen peroxide formed is recovered from the working solution in the form of aqueous hydrogen peroxide solution in the extraction process, for example in a column equipped with a perforated plate, using water. The hydrogen peroxide production cycle is restarted by recycling the working solution leaving the extraction process to the hydrogenation process. An alkyl anthraquinone means a 9,10-anthraquinone substituted at position 1, 2 or 3 with at least one alkyl side chain of a linear or branched aliphatic type having at least one carbon atom. Typically such alkyl chains contain up to 9 carbon atoms, preferably up to 6 carbon atoms. Examples of such alkyl anthraquinones are 2-ethyl anthraquinone, 2-isopropyl anthraquinone, 2-sec- and 2-tert-butyl anthraquinone, 1,3-, 2,3-, 2,7-dimethyl anthraquinone, 2-iso- and 2-tert-amylanthraquinone and mixtures of these quinones. Alkyl anthrahydroquinone refers to 9,10-hydroquinone corresponding to the above-mentioned 9,10-alkyl anthraquinone.
The crude hydrogen peroxide solution thus extracted at a concentration of 25 to 40% by weight is purified / concentrated by distillation in a column made of aluminum or special steel containing a normal filler, but it does not meet the purity required by the electronics industry. The distillate thus distilled contains a metal material by contact with aluminum or stainless steel, but may also contain other metal ions besides aluminum. In addition to refined hydrogen peroxide, hydrogen peroxide also contains limit residues in the process of solvents (alcohols, ketones, aliphatic hydrocarbons, acids), organic carbon compounds (organic carbon) and anthraquinone derivatives. Therefore, to use such hydrogen peroxide in the electronics industry such as semiconductor processing, efficient post-treatment methods must be developed that can reduce cations, anions, and carbon content.
In addition, the conventional distillation process of hydrogen peroxide requires many complicated devices such as distillation column, a large number of heat exchangers (cooler, evaporator, etc.), intermediate storage and separation facilities, filters and vacuum generating devices, And a large amount of energy is required for the vaporization process of hydrogen peroxide, which is disadvantageous in terms of investment and economic cost because of high operating cost. In addition, it is common to install and operate a plant that directly produces hydrogen peroxide as a purification method that is difficult to install and operate in the demand of the electronic industry, such as requiring a large site and a high-rise steel structure in terms of facility site. In addition, during the distillation process, the hydrogen peroxide is vaporized at a concentration of 20 to 40 wt%, and the evaporation residue (generally, 10 to 70 wt% of the entirely supplied hydrogen peroxide remains and is mainly used for industrial purposes which do not require high purity , And when it is difficult to commercialize because of its high concentration, it is also discarded), and since the impurities are concentrated, decomposition by high temperature lowers the efficiency of recovery of hydrogen peroxide, and the risk of explosion becomes very high from the safety point of view.
In addition, the method of purifying the aqueous hydrogen peroxide solution by the conventional distillation method described above can not adjust the metal impurities and the carbon content to the hydrogen peroxide purity required in the electronic industry. For example, it is almost impossible to maintain an economical efficiency and lower the organic carbon compound in an aqueous hydrogen peroxide solution to 20 ppm or less through distillation. That is, the hydrogen peroxide produced by the anthraquinone process necessarily contains an organic carbon compound having a boiling point corresponding to a low boiling point or water. Therefore, the content of this impurity can be up to 150 mg / L as an organic carbon compound dissolved in aqueous hydrogen peroxide solution. It is very difficult to lower the concentration of carbon compounds to 5 ppm or less even after the organic adsorbent resin is passed through the distillation. Therefore, the concentration is partially lowered through dilution with ultrapure water.
As the ion exchange materials of the current technical level, an aromatic hydrocarbon cation exchange resin substituted with a sulfonate in the nucleus is required for removing the cation, and a tertiary amine such as an aromatic hydrocarbon including a quaternary ammonium or pyridine And an anion exchange resin. Since most of the functional groups in the ion exchange resin are sensitive to oxidation, purification of the aqueous hydrogen peroxide solution with this ion exchange resin should be carried out with special care at a relatively low temperature of about -10 to 15 ° C. The high oxidation sensitivity of ion exchange resins makes this method commercially difficult to apply. In fact, hydrogen peroxide can make hazardous hydroxyl radicals by heavy metals such as iron or copper and oxidize the carbon of ion exchange resins to form epoxides or hydroperoxides that can be easily broken down. The resulting epoxide or hydroperoxide not only explodes explosively, but may also explode on its own. Therefore, the use of a cation or anion exchange resin for purifying an aqueous solution of hydrogen peroxide is a concern and particularly cautious in terms of safety. Therefore, decomposing hydrogen peroxide in ion exchange resins can be very dangerous. In addition, the heavy metal components accumulated in the manufacturing process and the purification process of the ion exchange resin further accelerate the decomposition of hydrogen peroxide, and the bubbles generated at this time have a great deal of difficulty in operation such as the ion exchange efficiency is rapidly lowered.
In addition to the above-mentioned methods, various methods for purifying hydrogen peroxide to remove impurities are known as follows.
(a) Japanese Patent Publication No. 28-003816 (hereinafter referred to as Patent Document 1)
Patent Document 1 discloses a method in which an aqueous hydrogen peroxide solution is contacted with a cation exchange resin in the form of a sulfonated aromatic hydrocarbon to remove metal cations mainly contained in aqueous hydrogen peroxide solution.
(b) U.S. Patent No. 3,297,404 (hereinafter referred to as Patent Document 2)
Patent Document 2 discloses a method for removing an anion impurity contained in an aqueous hydrogen peroxide solution by using an anion exchange resin having a quaternary ammonium group in the form of carbonate and / or bicarbonate.
(c) Japanese Patent Publication No. 46-026095 and French Patent No. 329,4448 (hereinafter referred to as Patent Document 3)
Patent Document 3 discloses a method of adsorbing and removing organic impurities contained in an aqueous hydrogen peroxide solution by using a resin having a network-like molecular structure obtained by crosslinking with divinylbenzene but not having an ion-exchange group.
(d) JP-A-63-156004 and U.S. Patent No. 4,792,403 (hereinafter referred to as Patent Document 4)
Patent Document 4 discloses a method of adsorbing and removing organic impurities contained in an aqueous hydrogen peroxide solution by using a halogen-containing porous resin having a specific gravity of 1.1 to 1.3.
(e) Korean Patent Publication No. 1998-0032700 (hereinafter referred to as Patent Document 5)
Patent Document 5 discloses a method for purifying organic impurities using a halogen-containing porous adsorbent resin.
(f) Korean Patent No. 0426435 (hereinafter referred to as Patent Document 6)
Patent Document 6 discloses a method for purifying an ultrahigh-purity hydrogen peroxide aqueous solution by sequentially passing through an adsorption resin and then passing through a cation-type ion-exchange resin, an anion-type ion-exchange resin, and a cation-type ion-exchange resin sequentially.
In the method using the cation exchange resin in the above patent documents, since some of the SO 3 H groups which are the ion exchange groups of the resin are decomposed by the action of hydrogen peroxide and dissolved in the form of SO 4 2 - , the metal cation impurities can be removed However, anion impurities increase.
In addition, in the method using the halogen-containing porous resin, the organic impurities can be removed advantageously, but a part of the halogen in the resin is dissolved, so that the anion impurities increase and the stability is greatly reduced. It has been known that an accident that the resin filled tower is exploded occurs.
Also, as in Patent Document 6, a method for purifying an ultrahigh-purity aqueous hydrogen peroxide solution by passing through an adsorption resin and then sequentially passing through a cation type ion exchange resin, an anion type ion exchange resin, and a cation type ion exchange resin, The amount of sodium is greatly increased in the process of aging with sodium phosphate. When the ion-exchanged resin is used as a raw material having a high ion content, the cost of using the expensive ion-exchange resin It is very difficult to regenerate the product with high purity due to the residual and pollution problem of recycled chemical agent in the regeneration process, so it is very difficult to commercialize it. And the cost of the refining is high, There is an inadequate problem to use.
In other words, none of the known hydrogen peroxide purification methods described above could obtain a high-purity aqueous hydrogen peroxide solution having a high enough quality to be used for the production of semiconductors, particularly, ultra-high purity LSI. That is, none of the known purification methods described above can provide a high purity aqueous hydrogen peroxide solution containing various metal ions at 100 ppt or less and organic impurities at 2 ppm or less.
Therefore, there is a need for a new method for purifying industrial hydrogen peroxide containing impurities to produce a high-purity high-purity aqueous hydrogen peroxide solution.
Accordingly, an object of the present invention is to purify industrial aqueous hydrogen peroxide solution containing various impurities to obtain a high-purity high-purity aqueous hydrogen peroxide solution which can be applied to electronic industries such as the semiconductor industry.
That is, the present invention provides a hydrogen peroxide purification method and purification apparatus for obtaining a high-quality aqueous hydrogen peroxide solution that can be used for the production of semiconductors, particularly LSI.
It is another object of the present invention to provide an efficient and economical method for purifying hydrogen peroxide and a purification device by sufficiently increasing the lifetime of the reverse osmosis membrane in the use of the reverse osmosis membrane for purification of hydrogen peroxide.
In order to solve the above problems, the present invention provides a method for purifying an aqueous hydrogen peroxide solution containing impurities, the method comprising: a primary treatment step of removing organic matter from an aqueous hydrogen peroxide solution containing the impurities; A secondary treatment step of treating the aqueous hydrogen peroxide solution after the primary treatment step using a reverse osmosis membrane; And a tertiary treatment step of using the aqueous hydrogen peroxide solution after the secondary treatment step using a resin for treatment of at least one of a cation exchange resin, an anion exchange resin and a chelating resin.
According to an embodiment of the present invention, at least one of the adsorption resin for removing organic substances and the hollow fiber membrane, or the adsorbent resin for desorbing the organic solvent and the hollow fiber membrane, .
More specifically, the adsorbent for removing organic matter may be a styrene-based adsorbent, and the hollow fiber membrane may be made of at least one of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), borosilicate glass, polyvinylidene fluoride PVdF) and high density polyethylene (HDPE).
It is also preferable that the total amount of organic carbon in the aqueous hydrogen peroxide solution after the primary treatment step is 60 ppm or less.
According to one embodiment of the present invention, a stabilizer that forms a complex with the impurity ion is added to an aqueous hydrogen peroxide solution containing the impurity.
More specifically, the stabilizer is selected from the group consisting of hydroxylethylenediaminetricarboxylic acid, nitrilotricarboxylic acid, hydroxylethylenediaminetricarboxylic acid, nitrilotricarboxylic acid, ethylenediaminetetracarboxylic acid, diethylenetriaminepentacarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxyethyleneglycine-1,1-diphosphonic acid, pentasodium pentenoic acid, ethylenediaminetetraacetic acid tetrasodium salt, acrylic acid polymer At least one selected from the group consisting of sodium salt dihydroxyethylglycine and hydroxyethyleneglymdicarboxylic acid.
Further, the stabilizer may be added in an amount of 1 to 100 mg per 1 liter of the aqueous hydrogen peroxide solution containing the impurities.
According to an embodiment of the present invention, the method of purifying the aqueous hydrogen peroxide solution may further include a step of performing a reverse osmosis process using the reverse osmosis membrane used in the second treatment step according to the lifetime of the reverse osmosis membrane used in the second treatment step And replacing the membrane with a new reverse osmosis membrane.
In this formula,
TOC is the amount of total organic carbon in aqueous hydrogen peroxide solution after the first treatment step.
t is the lifetime of the reverse osmosis membrane (error range ± 2 days)
fs is the stabilizer factor, fs value is 1.2
The concentration of HP is the concentration of the aqueous hydrogen peroxide solution containing impurities, and the aqueous hydrogen peroxide solution of 60% or less is used.
According to one embodiment of the present invention, the cation exchange resin is an H + ion-type strong acid cation exchange resin, a) a particle size range of 0.3 to 1.25mm, b) the apparent density of 0.7 to 0.78g / ㎖ and c) an ion exchange capacity 1.2eq / ℓ or more of polystyrene-divinylbenzene copolymer or a porous type and the anion exchange resin is OH - ions, and alternating basic cation exchange resin, a) a particle size range of 0.3 to 1.25mm, b) the apparent density of 0.65 to 0.70g / ㎖ and c) a polystyrene-divinylbenzene copolymer porous type having an ion exchange capacity of 1.2 eq / L or more. The chelate resin is preferably a polystyrene-divinylbenzene copolymer porous or epoxy resin type having a particle size range of 0.3 to 2.0 mm, an apparent density of 0.63 to 0.79 g / ml and an ion exchange capacity of 0.35 eq / .
According to one embodiment of the present invention, the tertiary treatment step may further include one or more steps of treating with a treatment resin of at least one of a cation exchange resin, an anion exchange resin and a chelate resin. Further, in the case where at least two kinds of processing resins selected from the cation exchange resin, the anion exchange resin and the chelate resin are used in the tertiary treatment step, a separation type in which two or more kinds of processing resins are separated, And the mixture may be mixed.
According to an embodiment of the present invention, the method may further include adding ultrapure water to the hydrogen peroxide solution introduced into the ion exchange resin or the ion exchange resin, and treating the aqueous hydrogen peroxide solution diluted with the ultrapure water with an ion exchange resin . In this case, washing in front of the anion exchange resin is preferable in terms of overall facility and size.
In addition, according to an embodiment of the present invention, the step of analyzing the aqueous hydrogen peroxide solution after the secondary treatment may further include monitoring the performance of the reverse osmosis membrane device. This monitoring is possible to analyze the total organic carbon.
Also, according to one embodiment of the present invention, it is an integrated production method wherein the hydrogen peroxide solution can be purified at once with VLSI grade, ULSI grade, SLSI grade and XLSI grade purified hydrogen peroxide.
According to an embodiment of the present invention, all containers used in the method of purifying the aqueous hydrogen peroxide solution include polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy (PFA), ethylene fluoride At least one of ethylene copolymer (ETFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), borosilicate glass, polyvinylidene fluoride (PVdF) and high density polyethylene (HDPE).
According to another aspect of the present invention, there is provided a method for purifying an aqueous hydrogen peroxide solution, comprising: a primary processing unit for removing organic impurities contained in an aqueous hydrogen peroxide solution containing impurities; A secondary processing unit using a reverse osmosis membrane connected to one side of the primary processing unit; And a tertiary treatment unit using at least one of a cation exchange resin, an anion exchange resin and a chelating resin, the cation exchange resin and the chelating resin being connected to the secondary treatment unit.
The present invention can purify an impure industrial aqueous hydrogen peroxide solution to provide a very high-quality aqueous hydrogen peroxide solution. In particular, it is possible to provide a stable purification method for obtaining a high-quality aqueous hydrogen peroxide solution that can be used for the production of LSI. That is, even a hydrogen peroxide aqueous solution containing impurities can be purified to such an extent that the content of cations and / or anions in the raw material reaches as high as several tens of ppm, and it is possible to purify various metal cations to 1 ppb and various anions to 1 ppb and organic impurities to organic carbon A high purity aqueous hydrogen peroxide solution containing not more than 5 ppm in terms of the total amount can be obtained. Further, it is possible to provide a method of obtaining a high-purity aqueous hydrogen peroxide solution containing not more than 100 ppt of various metal ions, which are the highest level of purified hydrogen peroxide, and 2 ppm or less of the organic impurities as the total amount of organic carbon through selective addition of some refining facilities. In addition, in the conventional purification technology, hydrogen peroxide produced through a vacuum distillation column is used as a raw material, but the present invention can exhibit economical economic effects even when a vacuum distillation column is not used.
BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments of the invention and, together with the description of the invention, It should not be construed as limited.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of a purification apparatus embodying a method of manufacture according to an embodiment of the present invention.
2 is a schematic diagram of a purification apparatus embodying a manufacturing method according to another embodiment of the present invention.
Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the constitutions described in the drawings are merely the most preferred embodiments, and not all of the technical ideas of the present invention are described. Therefore, various equivalents which can be substituted at the time of the present application It should be understood that variations can be made.
The present invention relates to a process for removing organic matter from an aqueous hydrogen peroxide solution containing various impurities; A secondary treatment step of using the reverse osmosis membrane as the aqueous hydrogen peroxide solution after the primary treatment; And a tertiary treatment step of using the aqueous hydrogen peroxide solution after the secondary treatment using at least one of a cation exchange resin, an anion exchange resin and a chelating resin.
The aqueous hydrogen peroxide solution before purification used in the purification method of the present invention is obtained, for example, from a hydrogen peroxide production process by an anthraquinone process, and the concentration of hydrogen peroxide may be 25 to 50 wt% or 30 to 40 wt%. The aqueous hydrogen peroxide solution contains Na, Cr, Ca, Al, Fe, and Zn as the metal cation, and NO 3 - , PO 4 3 - . On the other hand, small amounts of organic carbon impurities include, for example, marginal residues that occur in the process of solvents such as anthraquinone derivatives.
The purification method of the present invention is characterized by using a reverse osmosis device. When the reverse osmosis device is used for purification of hydrogen peroxide, the content of ionic inorganic impurities and organic impurities can be removed by 90% or more, and the amount of the adsorbent can be greatly reduced in the subsequent purification process.
In using the reverse osmosis device for purifying the hydrogen peroxide, the aqueous solution of hydrogen peroxide (hereinafter abbreviated as " crude hydrogen peroxide solution ") containing impurities is lowered to increase the period of use of the reverse osmosis device Therefore, the present invention adopts a first treatment step of lowering the total organic carbon of the crude hydrogen peroxide introduced before using the reverse osmosis apparatus. After removing the organic impurities through the first treatment step, A second treatment step using an osmotic membrane and a third treatment step using at least one treatment resin selected from a cation exchange resin, an anion exchange resin and a chelating resin. It can be refined with higher purity.
Hereinafter, the lifetime of the reverse osmosis membrane refers to a period of time sufficient to effectively exhibit the effectiveness of the reverse osmosis membrane. The period may be easily confirmed by a person skilled in the art, The period is the result measured at the inlet temperature of aqueous hydrogen peroxide solution of about 10 ° C.
Hereinafter, the purification method of the aqueous hydrogen peroxide solution of the present invention will be described in more detail.
[Primary treatment step for removing organic impurities from crude hydrogen peroxide solution]
In the present invention, it is recognized that lowering the content of the organic impurities contained in the crude hydrogen peroxide aqueous solution before injecting the aqueous hydrogen peroxide solution into the reverse osmosis membrane is important for extending the service life of the reverse osmosis membrane, The first processing step is performed. The primary treatment step for removing such organic impurities uses at least one of an adsorption resin for removing organic matter and a hollow fiber membrane. It is effective to connect the hollow fiber membrane and the adsorbent resin for removing organic matter in series and remove the organic impurities by passing the aqueous hydrogen peroxide solution through the hollow fiber membrane and the adsorbent resin for removing the organic matter in this order. Such a combination can more effectively remove the organic matter than other organic matter removal systems, and can further improve the lifetime of the reverse osmosis membrane.
The adsorbent for removing organic matter may lower the concentration of organic impurities with the styrene-based adsorbent. Typical applicable adsorbent resins are DIAION HP20, which is a product manufactured by Mitsubishi Chemical Co., Ltd., which has relatively large pore characteristics, and has a very large specific surface area and uniform pore size distribution as compared with DIAION HP20. The pore radius is very small, DIAION SP825 and SP850, which can selectively adsorb, and DIAION SP700, which has a relatively large pore radius, a very large specific surface area and pore volume, and excellent adsorption capacity and good solubility. In addition, DIAION SP207, which has high hydrophobicity and high selectivity for nonpolar materials, can be applied as a synthetic adsorption resin chemically adjusted with a halogen compound in a highly porous styrenic system. When the component of the organic impurity is polar, DIAION HP2MG which does not contain an aromatic compound can be applied as a methacrylic synthetic adsorbent. As the adsorbent resin of the present invention, it is also possible to use commercially available Amberlite-XAD4, Amberlite-XAD2, Amberlite-XAD1180N, etc., which are commercially available from Rohm & The temperature at which the aqueous hydrogen peroxide solution containing the impurity passes through the adsorption resin exemplified above is preferably about 20 캜 or less, more preferably from -0 캜 to 20 캜. At this time, if the treatment temperature exceeds 20 占 폚, the amount of dissolved halogen increases, which is not preferable. The space velocity SV when the aqueous hydrogen peroxide solution passes through the adsorbent layer is advantageously about 1 to 200, particularly preferably about 5 to 100. It is required that the volume of the aqueous solution in contact with the resin with respect to the resin volume in the adsorbent layer is, for example, about 100 to 10,000 times, preferably about 200 to 3,000 times. In addition, the linear velocity when the crude hydrogen peroxide solution passes through the adsorbent layer is preferably about 1 to about 100 m / hr.
A more preferable example of the adsorbent for removing organic matter is a cross-linking polymer of styrene resin and divinylbenzene, which has no washable components such as monomers and polymerization control agents. This adsorbent resin is prepared by copolymerizing about 5-15%, more specifically 8-12%, of divinylbenzene with the styrene resin. This adsorbent resin has no ionic functional groups and is a completely nonionic hydrophobic resin. Thus, the adsorption properties are manifested by large netting, wider pores, larger surface area than usual, and aromatic properties of the surface. Since the styrene-divinylbenzene-copolymer adsorbent resin contains a functional group sensitive to the oxidation reaction, unlike the cation exchange resin and the anion exchange resin described later, the styrene-divinylbenzene-copolymer adsorption resin can be used without particular care even at a low temperature of 0 ° C or below. All the adsorbent resins usable in the present invention are stable to oxidation and can be easily used at room temperature of 20-25 ° C.
The styrene-divinylbenzene-copolymer adsorbent resin is a bead-shaped white insoluble resin having the following characteristics. When measured in a dry state, the pore volume is about 1.3 ml / ml; Surface area of about 600 m < 2 > / g; The pore size is 200-300 nm in diameter; The diameter of the particle size is about 0.25-0.35mm and the specific gravity is about 1g / ml. This styrene-divinylbenzene-copolymer adsorbent resin has a high affinity for hydrophobic organic substances as a hydrophobic adsorbent, while it has a low affinity for hydrophilic substances such as water and hydrogen peroxide.
It is preferable to wash impurities such as monomers and polymerization regulators with a lower alcohol, preferably pure methanol, before using the styrene-divinylbenzene-copolymer adsorbent resin. Otherwise, these impurities may decompose hydrogen peroxide, which is undesirable. All the adsorbent resins used in the present invention can be regenerated by a known method after completion of tablet fixing.
In the first treatment step of the present invention, a hollow fiber membrane may be used instead of the adsorbent resin for removing the organic matter.
When the crude hydrogen peroxide solution contains a large amount of volatile solvent components and low vapor pressure substances, it is possible to remove organic impurities by gasification under a vacuum condition using a gas membrane composed of a hollow fiber membrane. The membrane degassing technology is filled with polypropylene hollow fibers with thousands of micropores. During the operation, the liquid flows out of the hollow fiber at a high velocity, and while the nitrogen gas is purged, the internal conditions of the hollow fiber membrane It is made into vacuum. Due to the hydrophobicity of the hollow fiber, the gas separation membrane can be contacted without mixing gas and water. The interface between the gas and the liquid is fixed near the micropores of the membrane surface due to the pressure of the liquid being greater than that of the gas. The liquid and the gas flow in countercurrent contact with each other. As a result, dissolved gas or low boiling point substances in the liquid are vaporized and diffused into the hollow fiber membrane, and organic impurities are reduced. Conventional industrial membrane degassing technology has been widely used for removing dissolved oxygen and carbon dioxide during pure water production, but has also been effective in removing organic impurities from aqueous hydrogen peroxide solution. The material of the hollow fiber membrane is selected from the group consisting of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), borosilicate glass, perfluoroalkoxy (PFA), ethylene fluoroethylene copolymer (ETFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVdF), and high density polyethylene (HDPE).
The above-mentioned first treatment step is a step of treating an industrial crude hydrogen peroxide aqueous solution containing hydrogen peroxide at about 10 to about 70 wt%, preferably about 20 to about 60 wt%, so as to adjust the concentration of the organic impurities from 150 ppm or more to 60 ppm or less, Preferably 50 ppm or less, or 20 to 50 ppm. When the total organic carbon is 60 ppm or less, the lifetime of the reverse osmosis device can be improved. That is, the refining efficiency of the reverse osmotic pressure device used can be increased, economical operation is possible, and rapid leakage of the total organic carbon and ion content occurs over time, which makes it difficult to obtain a stable high purity product.
The present inventors have found that the lifetime of the reverse osmosis membrane is inversely proportional to the amount of total organic carbon in the aqueous hydrogen peroxide solution after the first treatment step. Particularly, in the case of 100 ppm or more, the lifetime of the reverse osmosis membrane is limited to 70 ppm, preferably 65 ppm It was confirmed that the phenomenon was remarkably prolonged. Particularly, when it was less than 50 ppm, the life extension was confirmed to be 3 times or more as compared with the case where it was 100 ppm or more.
Using the fact that the lifetime characteristic of the reverse osmosis pressure is remarkably improved from the starting point of the total organic carbon amount in the aqueous hydrogen peroxide solution to 70 ppm, preferably 65 ppm as described above, when the amount of the total organic carbon in the aqueous hydrogen peroxide solution after the first treatment step is 60 ppm or less , Preferably 50 ppm or less, the lifetime of the reverse osmosis pressure device is improved so that the lifetime of the hydrogen peroxide solution can be maximized in the purifying step of the aqueous hydrogen peroxide solution, and thus the aqueous hydrogen peroxide solution refining apparatus can be economically used.
That is, through the first treatment step, the efficiency of the subsequent purification treatment process is greatly improved, the total purification cost is significantly lowered, and the size of the facility can be greatly reduced, which can greatly contribute to improvement of the commercial purification process and quality improvement.
Further, a stabilizer may be further added to the crude hydrogen peroxide solution used in the first treatment step, It is more preferable to carry out the simultaneous removal of the organic substance in the aqueous hydrogen peroxide solution and the addition of the stabilizer as described above, rather than proceeding to each of the two steps. The stabilizer is suitable as long as it is a substance that forms a complex with an impurity ion. Suitable stabilizers that can be used include, for example, hydroxylethylenediamine tricarboxylic acid, nitrilotricarboxylic acid, ethylenediaminetetracarboxylic acid, diethylenetriaminepentacarboxylic acid, 1-hydroxyethylidene-1 , 1-diphosphonic acid, 1-hydroxyethyleneglycine-1, 1-diphosphonic acid, pentasodium pentenoic acid, ethylenediaminetetraacetic acid tetrasodium salt, acrylic acid polymer sodium salt dihydroxyethylglycine and hydrolyzed Xylenimidicarboxylic acid, and the like, but are not limited thereto. More preferably, a mixed composition of pentasodium pentenoic acid, ethylenediaminetetraacetic acid tetrasodium salt and acrylic acid polymer sodium salt is suitable. When such a combination of three stabilizers is used, the hydrogen peroxide decomposition can be suppressed, and the pH can be purified under a condition in which the pH of the hydrogen peroxide is not greatly decreased, so that the lifetime of the reverse osmosis membrane can be further extended. At this time, the stabilizer is preferably added in an amount of 1 to 100 mg per 1 liter.
[Secondary treatment step using reverse osmosis membrane]
The aqueous hydrogen peroxide solution that has undergone the primary treatment step is subjected to the secondary treatment through the reverse osmosis membrane.
Examples of the shape of the reverse osmosis membrane include a flat membrane, a pleats membrane, a spiral membrane, a tube membrane, a rod membrane, a fine tube membrane, and a plurality of combinations thereof But not limited to this. Examples of the material of the reverse osmosis membrane include a polyethylene imine condensate, cellulose acetate, modified polyacrylonitrile, polybenzimidapyrone, polyether amide, cellulose triacetate, poly Polyamide, polybenzimidazole, sulfonated phenylene oxide, polypiperazinamide, polyphenylene sulfide, polyphenylene sulfide, polyphenylene sulfide, polyphenylene sulfide, but are not limited to, polypyrrolidone, polypiperazine amide, polyethylene imine toll, diisocyanate, polyketylene diacid chloride, sulfonated poly furfuryl alcohol, sulfonated polysulfone, poly Polyether sulfone, polyether ether, polyvinyl alcohol, polysulfone, polyamide polyvinyl alcohol, polyether sulfones, e) or polyamide. The reverse osmosis membrane may be an asymmetric membrane or a composite membrane. The reverse osmosis membrane of the present invention is preferably a composite membrane made of polyamide.
In the reverse osmosis membrane device according to the present invention, an apparatus for purifying a liquid by a reverse osmosis method having a pressure vessel and a pressure vessel for fixing and supporting a reverse osmosis membrane is used. The processing pressure is not particularly limited as long as it is within a range permissible for the reverse osmosis membrane, and is usually 5 MPa or less, preferably 0.3 to 2.5 MPa. The temperature at the time of the treatment is not particularly limited unless it is the temperature at which the decomposition reaction of hydrogen peroxide may be promoted. The preferred range is -20 to 40 占 폚. And more preferably in the range of 5 캜 to 25 캜.
By using the reverse osmosis device, the content of ionic inorganic impurities and organic impurities can be removed by 90% or more. That is, the reverse osmotic pressure device may have a metal ion content of 10 ppb or less, more specifically 5 ppb or less, and an anion content of 300 ppb or less. Also, the content of the organic carbon impurity may be 5 mg / l at a maximum value of about 5 ppm based on the total amount, more specifically about 2 to 5 mg / l.
[Third-step treatment step using at least one kind of processing resin of cation exchange resin, anion exchange resin and chelate resin]
The hydrogen peroxide solution after the secondary treatment step is subjected to tertiary treatment using at least one treatment resin selected from a cation exchange resin, an anion exchange resin and a chelate resin.
Wherein the cation exchange resin is a strongly ionic cation exchange resin having a H + ionic strength, wherein a) a particle size range of from 0.3 to 1.25 mm, b) an apparent density of from 0.7 to 0.78 g / ml and c) an ion exchange capacity of at least 1.2 eq / Copolymer porous type is preferred.
Further, the anion exchange resin is OH - ions, and alternating basic anion exchange resin, a) a particle size range of 0.3 to 1.25mm, b) the apparent density of 0.65 to 0.70g / ㎖ and c) an ion exchange capacity of more than 1.2eq / ℓ polystyrene- A divinylbenzene copolymer porous type is preferred.
It is preferable that the cation exchange resin and the anion exchange resin are washed with pure water before use.
A chelating resin may also be applied in place of the cation exchange resin or anion exchange resin, which is selected from the group consisting of a) a particle size range of 0.3 to 2.0 mm, b) an apparent density of 0.63 to 0.79 g / ml, and c) / L or more of a polystyrene-divinylbenzene copolymer porous type or an epoxy resin type is preferable.
In the third step, the treatment using at least one of the cation exchange resin, the anion exchange resin, and the chelate resin may be further performed one or more times depending on the purification degree of the aqueous hydrogen peroxide solution and the purpose thereof. For example, a cation exchange resin and an anion exchange resin, and then repeating the treatment using a cation exchange resin and an anion exchange resin to complete a third treatment step. In this case, the order of the cation exchange resin and the anion exchange resin may be changed and is not limited to the above example.
Further, in the case of using at least two kinds of processing resins of a cation exchange resin, anion exchange resin and chelate resin, for example, a cation exchange resin and an anion exchange resin may be used so as to separate two or more kinds of processing resins, Or a mixed type such as a mixed bed tower in which two or more kinds of treating resins are mixed, for example, a cation exchange resin and an anion exchange resin together.
When the processing resin is contained more than once, the process resin is treated in the lower stream and the process of washing with the upper stream in the ultra pure water can be regenerated at least once or more, preferably 2 to 12 times have. By repeating the regenerant / ultrapure water flow, the exchange resin can be effectively regenerated uniformly and can be washed to the inside of the resin due to the shrinkage and expansion of the resin. In the case of a cation exchange resin, a regenerant is an aqueous solution of a mineral acid, and in the case of an anion exchange resin, a strongly basic aqueous solution is used as a regenerant. In this case, an ion exchange resin having a total organic carbon content of 100 ppb or less may be used through one or more washing steps with ultrapure water.
Further, when an anion exchange resin is used, it is diluted with ultrapure water to a concentration of 1 to 100 ppm with phosphoric acid and its salt, and the diluted water is treated with a value of SV (space velocity) of 1 to 20 for 1 to 10 hours, It is preferable to use an anion exchange resin in which the content of PO 4 is lowered to 10 ppb or less by washing treatment for 1 to 24 hours.
In addition, when the hydrogen peroxide is not less than 31 wt% before the treatment with the anion exchange resin, the ultrapure water for electronic grade may be added to the hydrogen peroxide concentration diluent before application of the anion exchange resin.
The amount of total organic carbon in the aqueous hydrogen peroxide solution after the first treatment step and the lifetime of the reverse osmosis membrane used in the second treatment step have the relationship represented by the following equation (1) And replacing the reverse osmosis membrane used in the second treatment step with a new reverse osmosis membrane according to the lifetime of the reverse osmosis membrane used in the second treatment step according to Equation 1 below.
[Equation 1]
- TOC> 70 ppm
t (days) = [20 占 60 / TOC 占 0.3) 占 0.8- HP concentration (%) / 35 占 1.5]
- 60 ppm <TOC ≤ 70 ppm
t (days) = [25 ⅹ (60 / TOC ⅹ 0.5) 0. 0.85 - HP concentration (%) / 35 ⅹ 1.5]
- 30 ppm <TOC ≤ 60 ppm
t (days) = [30 × (60 / TOC × 0.7) ^ 0.7 - HP concentration (%) / 35ⅹ2] x fs
In this formula,
TOC is the amount of total organic carbon in aqueous hydrogen peroxide solution after the first treatment step.
t is the lifetime of the reverse osmosis membrane (error range ± 2 days)
fs is the stabilizer factor, fs value is 1.2
The concentration of HP is the concentration of the aqueous hydrogen peroxide solution containing impurities, and the aqueous hydrogen peroxide solution of 60% or less is used.
At this time, the fs value as the stabilizer factor is a value when the preferred stabilizer according to the present invention is added.
Further, the hydrogen peroxide purification method according to the present invention can include the step of analyzing the aqueous hydrogen peroxide solution after the secondary treatment step, thereby improving the reliability of the purification process by monitoring the performance of the reverse osmosis device. The performance analyzer preferably uses a total organic carbon analyzer.
In addition, in the present invention, the positions of the cation exchange resin and the anion exchange resin can be changed according to the properties of the raw hydrogen peroxide, and the performance of the obtained hydrogen peroxide is also different. Through this modification, various kinds of hydrogen peroxide can be obtained as a single plant process. For example, in consideration of the characteristics of raw hydrogen peroxide, VLSI purified hydrogen peroxide is produced at the outlet of the cation exchange resin when the cation content is high. When the anion content is high, the anion exchange resin is positioned in front of the cation exchange resin to produce the VLSI grade . When the anion and cation impurities are high, various cation exchange resin and anion exchange resin can purify the VLSI grade ULSI grade, SLSI grade and XLSI grade purified hydrogen peroxide into one facility and various kinds of hydrogen peroxide at the same time.
It is also important that all vessels used in the purifying method of the aqueous hydrogen peroxide solution are made of a suitable material so that impurities such as metal ions are not contaminated again from the vessel or tube. Examples of materials that can be used include polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), borosilicate glass , perfluoroalkoxy (PFA), ethylene fluoroethylene copolymer (ETFE), ethylene chlorotrifluoride But is not limited to, at least one of ethylene copolymer (ECTFE), clean-PVC, polyvinylidene fluoride (PVdF) and high density polyethylene (HDPE).
Thus, the content of each metal ion in the aqueous hydrogen peroxide solution purified by the purification method according to the present invention is 10 ppb or less, more specifically 5 ppb or less. The combined content of the anions is in the range of 300 ppb or less. The content of organic carbon impurities is about 5 to 5 mg / l, and more specifically about 0.5 to 3 ppm, of about 0.5 to 3 mg / l.
A purification apparatus for implementing the above-described manufacturing method according to the present invention is shown in Figs. 1 and 2. Fig. According to FIG. 1, the stabilizer prepared in the N. stabilizer tank was mixed with the A. raw hydrogen peroxide using an O. stabilizer pump to remove organic impurities from the B2. After passing through the adsorption resin tower to remove organic impurities, it is collected in C. intermediate tank of Teflon material and supplied to E. reverse osmosis device using D. transfer pump to remove ions and residual organic impurities. The impurities are separated into F. concentrate and the purified hydrogen peroxide passes through G. cation exchange resin and H. anion exchange resin to produce purified hydrogen peroxide. The purified hydrogen peroxide thus produced is collected in a Teflon I. intermediate tank and sequentially passed through a K. cation exchange resin and an L. anion exchange resin using a J. transfer pump and collected in a final M. product tank. At this time, the R. performance meter is installed in the purified product piping of the reverse osmosis device to remotely monitor the deterioration degree of the reverse osmosis device. The final product passes through the P. transfer pump and the Q. product filter and supplies it to the customer after the final filtration. The above Q. product filters are applied to final filtration of VLSI, ULSI, SLSI and XLSI products of each refining grade. However, in order to prevent the decomposition of hydrogen peroxide during the arbitrary purification process and to prevent the deterioration of the purification efficiency by the oxygen bubbles, the anion exchange resin of H. and L. is preliminarily washed with diluted ultrapure water and then supplied with hydrogen peroxide do.
2 is a schematic diagram of a hydrogen peroxide purification apparatus according to another embodiment of the present invention. Referring to FIG. 2, the hydrogen peroxide purification apparatus according to the present embodiment includes the above B2. In front of adsorption resin tower B1. Except that the gas separation membrane is applied to perform the primary treatment, the configuration of the apparatus of Fig. 1 is substantially the same. More specifically, when the amount of the cation is large considering the properties of the raw hydrogen peroxide, the purified hydrogen peroxide is produced at the outlet of the G. cation exchange resin. When the anion content is high, the anion exchange resin is positioned in front of the cation exchange resin VLSI grade. When the anion and cation impurities are all high, VLSI grade or ULSI grade purified hydrogen peroxide is produced at the outlet of H. anion exchange resin. The purified hydrogen peroxide of SLSI and XLSI grade produces L. anion exchange resin outlet It can be used as an on-skid type that can produce various grades of purified hydrogen peroxide.
In addition, the purification apparatuses shown in FIGS. 1 and 2 include a hydrogen peroxide feedstock including an impurity; An organic impurity removal primary processing unit connected to the hydrogen peroxide feed unit including the impurities; A secondary processing unit using a reverse osmosis membrane connected to one side of the primary processing unit; And a tertiary treatment unit using at least one of a cation exchange resin, an anion exchange resin and a chelating resin connected to the one side of the secondary treatment unit. The purifying method according to the present invention can be reproduced by using the hydrogen peroxide purification apparatus, and the present invention is not limited to the above-described apparatus.
Hereinafter, embodiments of the present invention will be described in detail to facilitate understanding of the present invention. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art,
Example
In order to purify hydrogen peroxide according to the present invention, materials and apparatus of the following conditions were prepared.
[Hydrogen peroxide]
The starting solution for the hydrogen peroxide refining process was an aqueous solution of hydrogen peroxide sold for industrial use having a hydrogen peroxide content of 35% by weight. This starting solution was an aqueous hydrogen peroxide solution prepared by the anthraquinone method. However, the concentration of the crude hydrogen peroxide is not particularly limited. A 35% industrial aqueous hydrogen peroxide solution has a carbon content of 183 mg / l which is used as the starting solution for the purification process of the present invention.
[Adsorption resin]
As the adsorbent resin, a styrene-divinylbenzene copolymer, which is a nonion exchange resin containing divinylbenzene, is used. This resin has the following characteristics:
- Average particle diameter of 0.25 mm or more (90% or more)
- wet specific gravity of about 1.01 g / ml, pore volume of 1.3 ml / ml (based on the dried copolymer)
- surface area of about 600 m 2 / g (based on dry copolymer)
- average pore diameter 200 - 300nm (based on dried copolymer)
Styrene-divinylbenzene copolymer resins having such properties can be easily obtained commercially. Prior to use as an adsorbent resin, the styrene-divinylbenzene copolymer is washed with pure methanol or diluted methanol, isopropyl alcohol, or other eluents, such as monomers and polymerization control agents, remaining in the styrene-divinylbenzene copolymer. Next, rinse once more to remove carbon from the metal ion-free water (ie, until the eluant such as organic matter or methanol is completely removed).
[Ion exchange resin]
As the cation exchange resin, a polystyrene-divinylbenzene copolymer porous type H + ion type strongly acidic cation exchange resin is used. This resin has the following characteristics:
- Particle size range 0.3 ~ 1.25 mm
- Apparent density 0.7 to 0.78 g / ml
- ion exchange capacity 1.2 eq / ℓ or more
As the anion exchange resin, a polystyrene - divinylbenzene copolymer porous type OH - ion type strongly basic anion exchange resin is used. This resin has the following characteristics:
- Particle size range 0.3 ~ 1.25 mm
- Apparent density of 0.65 ~ 0.70 g / ㎖ inside and outside
- ion exchange capacity 1.2 eq / ℓ or more
Cation exchange resins and anion exchange resins having such properties are readily available on the market. Before being applied to the purification process, the cation and anion exchange resin sufficiently wash away the remaining organic components with pure water.
[Gas separation membrane]
A hollow fiber membrane was used as a gas separation membrane, and a hollow fiber membrane made of a Teflon material and a high density polyethylene material was applied. This gas film has the following characteristics
- Dimensions are 102mm in diameter and 180mm in height
- The size of hollow fiber is 1.1mm outer diameter, 0.9mm inner diameter
- Fluorine resin is adopted as material
- Vacuum pressure is 5.4 kPa (abs)
[Reverse osmotic pressure device]
The reverse osmotic membrane used in the reverse osmosis device is Products were used.
- Type of reverse osmosis membrane: Polyamide Thin-film Composite
- Maximum operating temperature / pressure: 40 degrees / 55 bar
- Maximum supply flow rate: 1.4 m 3 / hr
- Dimensions: 2.4 inches in outer diameter - Length 14 inches
- Salt Removal Rate: 99.5% (based on 2,000ppm NaCl, 5% recovery rate)
[analysis]
The content of metal cations in the purified hydrogen peroxide solution is measured by mass spectrometry (IPC-MS) and atomic absorption spectrometer (AA) combined with the induction plasma. The organic carbon content is measured by a total organic carbon analyzer.
Example One
The styrene-divinylbenzene copolymer prepared above is filled in a polyethylene-made cylinder. Next, the column was immersed in a 35 wt% aqueous solution containing 10 mg / l pentasodium pentenoate (maximum 10%), ethylenediamine tetraacetate tetrasodium salt (maximum 10%), and acrylic acid polymer sodium salt (maximum 20% Hydrogen peroxide solution. The flow rate of the aqueous hydrogen peroxide solution is adjusted so that 20 ml flows per hour per 1 ml of the copolymer. The average value after the total organic carbon was removed was maintained at 60 ppm or less. The hydrogen peroxide thus produced was supplied to a pre-prepared reverse osmosis device to measure the period during which commercial operation was possible to maintain a removal rate of 5 ppm or less based on total organic carbon. The supplied hydrogen peroxide was operated at a temperature of about 10 ° C.
The hydrogen peroxide passed through the reverse osmosis device was recycled back to the raw material tank, and the performance of the reverse osmosis device was compared and analyzed. During the test run, the copolymer is not dispersed and no exothermic reaction takes place between the resin and hydrogen peroxide. Purified hydrogen peroxide is housed in a high-purity container made of high-density polyethylene or polyvinylidene fluoride. The metal cations are analyzed by a mass spectrometer and the organic carbon by an infrared spectrometer. The analysis results are shown in Table 2 below. There was no significant change except for the total organic carbon as an average value after passing through the adsorption resin. The analysis results after passing through the reverse osmosis device were based on the representative value after 24 hours.
Driving days
In Example 1, operation was possible for about 26 days while stable purification efficiency was maintained.
Example 2
As in the case of Example 1, as the first refining facility, a hollow fiber membrane made of a high-density polyethylene material was applied in front of the styrene-divinylbenzene copolymer resin tower described above, and the total organic carbon content after passing through the hollow fiber membrane was first adjusted And adjusted to 47 ppm through the adsorbent resin under the same conditions. The results of the analysis are shown in Table 3.
Driving days
In Example 2, the lifespan of the reverse osmosis device was extended by 23% as compared to Example 1, and the operation was continued for more than one month, and the purification efficiency remained constant. The quality of the purified product was improved by using only the adsorbed water. In particular, it can be seen that the lifetime of the reverse osmosis membrane is greatly improved to about 15 times as compared with the following example 3.
Example 3
The same procedure as in Example 1 was carried out but raw hydrogen peroxide was directly supplied to the reverse Osmosis apparatus without first organic carbon purification. The results of the analysis are shown in Table 4.
Driving days
In Example 3, the operation of the reverse osmosis apparatus without the first organic carbon purification resulted in a rapid increase in the total organic carbon and an inadequate refining efficiency due to a rapid increase in total organic carbon without exceeding the operating time of 2 days. It was confirmed that the residual amount of total organic carbon greatly influences the service life of the membrane of the reverse osmosis device.
Example 4
The same tests as in Example 1 were carried out except that pentanedion pentenoic acid (up to 10%), ethylenediaminetetraacetic acid tetrasodium salt (up to 10%), and acrylic acid polymer sodium salt (up to 20% . The results of the analysis are shown in Table 5.
Driving days
In Example 4, the purification efficiency remained at a similar level, but the total number of days was shortened by about 20%, and dispersion and bubbles were observed in the adsorbent layer. It can be seen that the addition of the stabilizer contributes to prolongation of life of the membrane of the reverse osmosis membrane and inhibition of hydrogen peroxide decomposition.
Example 5
The same as Example 1, but the total organic carbon concentration of the feed water was varied to compare the lifetime of the membrane of the reverse osmosis membrane. The test results are shown in Table 6.
(ppm)
(Days)
In Example 5, when the lifetime according to the content of total organic carbon was compared at the level of maintaining the refining efficiency, it was surprisingly confirmed that a remarkable life time difference was observed at about 70 ppm, especially about 65 ppm. That is, at 70 ppm or more, particularly 100 ppm or more, the period of replacement of the membrane of the reverse osmosis membrane membrane was too short to be commercial operation impossible, and the total organic carbon content of 60 ppm or less showed a period of 3 weeks to 4 weeks or more. It is understood that when the reverse osmosis membrane is used, it is advantageous to add a raw material of 60 ppm or less, preferably 50 ppm or less.
Example 6
The purified hydrogen peroxide produced in the same manner as in Example 1 was diluted with 31 wt% of ultra pure water from which an ion component was removed, and passed through H + type cation exchange resin to conduct ion purification. The inlet temperature should be reduced to below 10 ℃. The flow rate of the aqueous hydrogen peroxide solution is adjusted to 40 ml per hour per 1 ml of the ion exchange resin. Passed through the column filled with cation exchange resin of the H + type continuously and, OH - in the same flow rate to the anion exchange resin of the ion type of OH - and pass through the column filled with the anion exchange resin of the ion type in a row, the middle tank of Teflon , The second H + type cation exchange resin and the OH - ion type anion exchange resin flow through the aqueous hydrogen peroxide solution at a rate of 60 ml per 1 ml of ion exchange resin per hour. Continuously pass through a column filled with anion exchange resin of the OH - ion type at the same flow rate. Additional purified hydrogen peroxide was collected in an intermediate tank of Teflon and analyzed. The results of the analysis are shown in Table 6.
In Example 6, an ultra-high purity hydrogen peroxide product satisfying SLSI grade was produced. It was confirmed that after the first purification through the purification process of Example 1, the production of ultrahigh purity hydrogen peroxide was possible through the combination of ion exchange resins.
Example 7
The purified hydrogen peroxide produced in the same manner as in Example 6 was further passed through a mixed column including an H + type cation exchange resin and an OH - ion type anion exchange resin to analyze the purified product. The inlet temperature should be reduced to below 10 ℃. The flow rate of the aqueous hydrogen peroxide solution is adjusted to 60 ml per 1 ml of ion exchange resin per hour. Additional purified hydrogen peroxide was collected in an intermediate tank of Teflon and analyzed. The results of the analysis are shown in Table 8.
It means that the ND does not exceed the limit of the analyzer. Through the analysis, purified hydrogen peroxide can be obtained with high purity to the XLSI quality requirement level. It can be seen that the total organic carbon content is improved to 2 ppm or less.
A: raw hydrogen peroxide B1: gas separation membrane
B2: adsorption resin column C, I: intermediate tank
D, J, P: feed pump E: reverse osmosis device
F: concentrate G, K: cation exchange resin
H, L: Anion exchange resin M: Product tank
N: Stabilizer tank O: Stabilizer pump
Q: Product Filter R: Performance Analyzer
Claims (26)
A primary treatment step of removing organic matter from an aqueous hydrogen peroxide solution containing the impurities;
A secondary treatment step of treating the aqueous hydrogen peroxide solution after the primary treatment step using a reverse osmosis membrane; And
And a tertiary treatment step of treating the aqueous hydrogen peroxide solution after the secondary treatment step with a treatment resin of at least one of a cation exchange resin, an anion exchange resin and a chelate resin.
Wherein the first treatment step removes organic matter by using at least one of an adsorption resin for removing organic matter and a hollow fiber membrane.
Wherein the first treatment step comprises passing the hollow fiber membrane through the hollow fiber membrane, and then removing the organic matter from the aqueous hydrogen peroxide solution using the adsorbent resin for removing the organic matter.
Wherein the adsorbent resin for removing organic matter is a styrene adsorbent resin.
Characterized in that the hollow fiber membrane is at least one of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), borosilicate glass, polyvinylidene fluoride (PVdF) and high density polyethylene (HDPE) ≪ / RTI >
Wherein the total amount of organic carbon in the aqueous hydrogen peroxide solution after the primary treatment step is 60 ppm or less.
Further comprising adding a stabilizer that forms a complex with an impurity to the aqueous hydrogen peroxide solution containing the impurity before the primary treatment step.
The stabilizer is selected from the group consisting of hydroxylethylenediaminetricarboxylic acid, nitrilotricarboxylic acid, ethylenediaminetetracarboxylic acid, diethylenetriaminepentacarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxyethylenevinylene-1,1-diphosphonic acid, pentanethene pentenoic acid, ethylenediaminetetraacetic acid tetrasodium salt, acrylic acid polymer sodium salt dihydroxyethylglycine and hydroxyethyleneglycidicarboxylate Wherein the hydrogen peroxide solution is at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, and acetic acid.
Wherein the stabilizer is added in an amount of 1 to 100 mg per 1 liter of an aqueous hydrogen peroxide solution containing the impurity.
The method of purifying the aqueous hydrogen peroxide solution may be carried out in accordance with the lifetime of the reverse osmosis membrane used in the second treatment step according to Equation (1)
Further comprising the step of replacing the reverse osmosis membrane used in the second treatment step with a new reverse osmosis membrane.
[Equation 1]
- TOC> 70 ppm
t (days) = [20 占 60 / TOC 占 0.3) 占 0.8- HP concentration (%) / 35 占 1.5]
- 60 ppm <TOC ≤ 70 ppm
t (days) = [25 ⅹ (60 / TOC ⅹ 0.5) 0. 0.85 - HP concentration (%) / 35 ⅹ 1.5]
- 30 ppm <TOC ≤ 60 ppm
t (days) = [30 × (60 / TOC × 0.7) ^ 0.7 - HP concentration (%) / 35ⅹ2] x fs
In this formula,
TOC is the amount of total organic carbon in aqueous hydrogen peroxide solution after the first treatment step.
t is the lifetime of the reverse osmosis membrane (error range ± 2 days)
fs is the stabilizer factor, fs value is 1.2
The concentration of HP is the concentration of the aqueous hydrogen peroxide solution containing impurities, and the aqueous hydrogen peroxide solution of 60% or less is used.
Wherein the cation exchange resin is a strongly ionic cation exchange resin having a H + ionic strength, wherein a) a particle size range of from 0.3 to 1.25 mm, b) an apparent density of from 0.7 to 0.78 g / ml and c) an ion exchange capacity of at least 1.2 eq / A method for purifying an aqueous hydrogen peroxide solution which is a copolymer porous type.
Wherein the anion exchange resin is an OH - ion type strong basic anion exchange resin, and is selected from the group consisting of a) a particle size range of 0.3-1.25 mm, b) an apparent density of 0.65-0.70 g / ml, and c) an ion exchange capacity of 1.2 eq / Benzene copolymer porous type aqueous hydrogen peroxide solution.
The chelate resin is a polystyrene-divinylbenzene copolymer porous type or an epoxy resin type aqueous hydrogen peroxide solution having an average particle size of 0.3 to 2.0 mm, an apparent density of 0.63 to 0.79 g / ml and an ion exchange capacity of 0.35 eq / ≪ / RTI >
Wherein the tertiary treatment step further comprises at least one step of treating the aqueous solution with at least one of a cation exchange resin, an anion exchange resin and a chelating resin.
Wherein the resin for treatment of the step further comprising one or more times is an ion exchange resin having a total organic carbon content of 100 pbb or less.
In the case where at least two kinds of processing resins of the cation exchange resin, the anion exchange resin and the chelate resin are used in the tertiary treatment step, a separation type in which two or more processing resins are separated or two or more kinds of processing resins are mixed A method of purifying an aqueous hydrogen peroxide solution.
Wherein the method for purifying the aqueous hydrogen peroxide solution further comprises monitoring the performance of the reverse osmosis membrane device of the second treatment portion.
A secondary processing unit using a reverse osmosis membrane connected to one side of the primary processing unit; And
And a tertiary treatment unit including at least one of a cation exchange resin, an anion exchange resin and a chelate resin, the cation exchange resin being connected to the secondary treatment unit,
Wherein the hydrogen peroxide is purified while sequentially moving the primary processing unit, the secondary processing unit, and the tertiary processing unit.
Wherein the primary treatment section comprises at least one of an adsorption resin tower including an adsorbent resin for removing organic matter and a gas separation membrane composed of a hollow fiber membrane.
The primary treatment part sequentially includes an adsorption resin tower including a gas separation membrane made of a hollow fiber membrane and an adsorption resin for removing organic matter, and the aqueous hydrogen peroxide solution containing impurities in this order passes through the primary treatment part to remove organic impurities Wherein the aqueous solution of hydrogen peroxide is at least one selected from the group consisting of water,
Wherein the tertiary treatment section includes a first ion treatment section including a cation exchange resin and an anion exchange resin and a second ion treatment section including a cation exchange resin and an anion exchange resin continuously disposed in the first ion treatment section Wherein the hydrogen peroxide solution is an aqueous solution of hydrogen peroxide.
Wherein the tertiary treatment section includes a first ion treatment section including a cation exchange resin and an anion exchange resin, a second ion treatment section including a cation exchange resin and an anion exchange resin continuously disposed in the first ion treatment section, And a third ion treatment section including an exchange resin separation type or a mixed type.
Wherein the apparatus for purifying the aqueous hydrogen peroxide solution comprises a performance analyzer for monitoring the performance of the reverse osmosis membrane system of the secondary processing unit.
Further comprising a stabilizer incorporating apparatus which mixes a stabilizer that forms a complex with an impurity ion into an aqueous hydrogen peroxide solution containing the impurity introduced into the primary treatment unit.
Characterized by further comprising a stabilizer incorporating device which incorporates a stabilizer which forms a complex with an impurity ion in the anion exchange resin An apparatus for purifying an aqueous hydrogen peroxide solution.
Wherein the amount of total organic carbon in the aqueous hydrogen peroxide solution after the primary treatment step and the lifetime of the reverse osmosis membrane used in the secondary treatment step in the apparatus for purifying an aqueous solution of hydrogen peroxide have the relationship represented by the following formula An apparatus for purifying an aqueous hydrogen peroxide solution.
[Equation 1]
- TOC> 70 ppm
t (days) = [20 占 60 / TOC 占 0.3) 占 0.8- HP concentration (%) / 35 占 1.5]
- 60 ppm <TOC ≤ 70 ppm
t (days) = [25 ⅹ (60 / TOC ⅹ 0.5) 0. 0.85 - HP concentration (%) / 35 ⅹ 1.5]
- 30 ppm <TOC ≤ 60 ppm
t (days) = [30 × (60 / TOC × 0.7) ^ 0.7 - HP concentration (%) / 35ⅹ2] x fs
In this formula,
TOC is the amount of total organic carbon in aqueous hydrogen peroxide solution after the first treatment step.
t is the lifetime of the reverse osmosis membrane (error range ± 2 days)
fs is the stabilizer factor, fs value is 1.2
The concentration of HP is the concentration of the aqueous hydrogen peroxide solution containing impurities, and the aqueous hydrogen peroxide solution of 60% or less is used.
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| KR1020120139885 | 2012-12-04 |
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| KR20140071943A true KR20140071943A (en) | 2014-06-12 |
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| KR20180029173A (en) * | 2016-09-09 | 2018-03-20 | 오씨아이 주식회사 | Purification of hydrogen peroxide |
| CN109772168A (en) * | 2019-02-25 | 2019-05-21 | 苏州晶瑞化学股份有限公司 | Utilize the method for reverse osmosis membrane Coupling Adsorption resin separation dioxygen Organic substance in water |
| KR102029955B1 (en) * | 2019-08-27 | 2019-10-08 | 태광산업주식회사 | Method for purifying aqueous hydrogen peroxide solution |
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| CN110577195A (en) * | 2019-09-23 | 2019-12-17 | 杭州精欣化工有限公司 | Preparation method of semiconductor-grade hydrogen peroxide aqueous solution |
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| KR102639039B1 (en) * | 2022-12-29 | 2024-02-22 | 오씨아이 주식회사 | Method for purifying hydrogen peroxide |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180029173A (en) * | 2016-09-09 | 2018-03-20 | 오씨아이 주식회사 | Purification of hydrogen peroxide |
| WO2020028651A1 (en) * | 2018-08-02 | 2020-02-06 | Evonik Corporation | Process for preparing a stabilized aqueous hydrogen peroxide solution |
| CN112533864A (en) * | 2018-08-02 | 2021-03-19 | 赢创有限公司 | Method for producing stabilized aqueous hydrogen peroxide solution |
| US20210363008A1 (en) * | 2018-08-02 | 2021-11-25 | Evonik Corporation | Process for preparing a stabilized aqueous hydrogen peroxide solution |
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| KR102029955B1 (en) * | 2019-08-27 | 2019-10-08 | 태광산업주식회사 | Method for purifying aqueous hydrogen peroxide solution |
| KR102051841B1 (en) * | 2019-08-27 | 2019-12-04 | 태광산업주식회사 | Method for purifying aqueous hydrogen peroxide solution |
| CN110577195A (en) * | 2019-09-23 | 2019-12-17 | 杭州精欣化工有限公司 | Preparation method of semiconductor-grade hydrogen peroxide aqueous solution |
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| KR102639039B1 (en) * | 2022-12-29 | 2024-02-22 | 오씨아이 주식회사 | Method for purifying hydrogen peroxide |
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