• 专利附录
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  • 优先权
    • 专利摘要:
    The present invention relates to a method of chromatographic purification of a novel hydrogen peroxide solution which provides a high purity solution which can be used in semiconductor technology under recent high purity requirements.
    公开号:KR20030036198A
    申请号:KR1020027016046
    申请日:2001-03-29
    公开日:2003-05-09
    发明作者:웨터디트마르；두제문트클라우스；노이만에발트；프라이슬러클라우스；호스탈렉마르틴
    申请人:메르크 파텐트 게엠베하；
    IPC主号:
    专利说明:

    METHOD FOR THE PURIFICATION OF HYDROGEN PEROXIDE SOLUTIONS [0002]
    [2] Extremely high purity requirements are placed on chemicals used in the manufacture of highly integrated electrical circuits. Chemical quality with a low ppm area impurity is acceptable in the manufacture of a 1 megabit chip, but chemical quality is required with a maximum impurity level of less than 10 ppb in the manufacture of 4 to 16 megabit chips.
    [3] Hydrogen peroxide is one of the key chemicals in chip manufacturing that must meet these purity requirements. It is produced exclusively by the anthraquinone process and is refined and concentrated by rectification, usually on an aluminum or stainless steel-steel column, so that it has no purity of requirements. The distillate is contaminated, in particular with aluminum or other metals, due to contact with the installation part. In addition, it includes organic carbon compounds such as solvents (alcohols, ketones, aliphatic hydrocarbons and acids) ("organic C") and residues of anthraquinone derivatives as a result of the process. Therefore, in order to be used in microelectronics, hydrogen peroxide must be subjected to effective post-treatment to reduce the cation, anion and carbon content to the requisite purity level.
    [4] Purification of hydrogen peroxide solution by distillation alone does not achieve the required purity with respect to metal impurities and carbon. For example, this solution immediately contains volatile or vapor-volatile organic carbon compounds from the anthraquinone process, which can not be separated off in a simple manner by distillation. The content of organic carbon dissolved in the hydrogen peroxide may have a value of 150 mg / liter or less. However, metal ions and carbon impurities in hydrogen peroxide are particularly interfering in the manufacture of microchips, and these impurities have a more negative effect as the chips being manufactured become more highly integrated. Therefore, attempts have been made in the art to remove impurities from hydrogen peroxide by post treatment with a cation and / or an anion exchanger.
    [5] For this purpose, the proposed ion-exchange materials include a ring-substituted aromatic hydrocarbon cation exchange resin in the case of cation removal and an aromatic hydrocarbon anion exchange resin containing a tertiary amino or ammonium group or pyridine ring in the case of anion removal. The functional groups present in these ion exchange resins often make ion exchange resins very sensitive to oxidation, which requires purification of hydrogen peroxide using these ion exchange resins to be performed at relatively low temperatures of about 0 ° C and in particular carefully.
    [6] In order to avoid the problem of reaction with the oxidation-sensitive group, US Pat. No. 5,268,160 proposes further purification using a cross-linked polystyrene resin-based nonionic organic hydrophobic adsorbent resin. However, this method provides a hydrogen peroxide solution containing only a multiplicity of acceptable impurities and is therefore unsuitable for use in chip manufacture according to recent standards.
    [7] The high degree of oxidation sensitivity of the ion exchange resins can form hydroxy free radicals for the hydrogen peroxide in the presence of heavy metals such as Fe or Cu, which oxidatively attack the carbon- ≪ / RTI > can form epoxides or hydroperoxides that can be easily degraded with the < RTI ID = 0.0 > The formed epoxide or hydroperoxide not only explodes explosively but also decomposes in an explosive manner under certain circumstances. Therefore, the use of a cation exchanger or an anion exchanger in the purification of hydrogen peroxide solution is problematic and requires special care.
    [8] In order to avoid this problem, EP 0 502 466 A1 and DE 38 22 348 A1 disclose that metal ions present after distillation purification are removed using a chelating agent and a styrene-divinylbenzene copolymerization system nonionic Describes a further purification method of a hydrogen peroxide solution that separates and removes from a corresponding solution using an exchange polymer adsorbent. However, this method has the disadvantage that an undesirable chemical substance is added again to the pre-purified solution and subsequently separated again.
    [9] DE 42 14 075 A1 discloses a method of treating a hydrogen peroxide solution which is purified to separate and remove organic impurities with an anion exchanger and a nonionic adsorbent resin. In this method, the hydrogen peroxide solution to be purified is treated with a cationic resin in the form of an acid in the form of an acid and then with an intermediate-strength anionic resin in the form of a base at 0 ° C. And then treated with an adsorbent resin having a macroreticular structure, that is, a nonionic resin. The hydrogen peroxide solution treated in this manner no longer meets the recent requirements of the semiconductor industry because the concentration of organic impurities still present in the solution is too high.
    [10] In addition, U.S. Patent No. 4,879,048 discloses a method for further purification of hydrogen peroxide solution by reverse osmosis. However, the lifetime of the semi-permeable membrane becomes a problem. In addition, it does not attract recent purity requirements.
    [1] The present invention is directed to a method for further purification of a novel hydrogen peroxide solution which provides a high purity solution that can be used in semiconductor technology under recent high purity requirements.
    [11] It is therefore an object of the present invention to provide a process for the further purification of hydrogen peroxide solutions which is simple in process and capable of reducing the concentration of organic impurities (TOC) to less than 5 ppm and at the same time separating and removing interfering metal ions.
    [12] It is an object of the present invention to provide a process for the preparation of a purified hydrogen peroxide solution having a concentration ranging from 5 to 59%
    [13] a) anion exchange resin;
    [14] b) a nonionic adsorbent resin in the form of a hydrophobic aromatic crosslinked polymer having a macroporous structure; And
    [15] c) a neutral adsorbent resin selected from the group consisting of styrene-divinylbenzene resin having a high macroporous structure and formed by pyrolysis treatment
    [16] With the exception that the treatment of the adsorbent or the exchange resin is carried out in any desired order provided that the treatment of the neutral adsorbent resin is carried out in the final step.
    [17] The anion exchange resin selected in accordance with the present invention comprises a strong or weakly basic styrene-divinylbenzene resin containing a quaternary ammonium group as a functional group and a strong or weakly basic styrene-divinylbenzene resin containing a tertiary amino group as a functional group Lt; / RTI >
    [18] The nonionic adsorbent resin used in accordance with the present invention is selected from the group consisting of styrene-divinylbenzene resins having a macroporous structure and in particular a macroporous structure and a large surface area.
    [19] The neutral adsorbent resin used in the further purification step of the process according to the invention is a resin selected from the group consisting of styrene-divinylbenzene resins having a high macroporous structure and an intermediate surface area.
    [20] The hydrogen peroxide solution to be treated in order to carry out the process is passed according to the invention through successive connected columns at a flow density of 0.2 to 1.0 l / h · cm 2 , in particular 0.5 to 0.7 l / h · cm 2 .
    [21] When the additional purification step is carried out in a continuous connected stream, a residence time of from 0.008 to 20.0 minutes is advantageous.
    [22] Further purification of the hydrogen peroxide solution is carried out at 15 to 25 캜, preferably 20 캜.
    [23] This method is particularly advantageous and economical in continuous conditions. However, it can also be carried out batchwise.
    [24] Further, according to the present invention, this object is achieved by a process for preparing a hydrogen peroxide solution,
    [25] a) anion exchange resin;
    [26] b) nonionic adsorbent resin; And
    [27] c) Neutral adsorption resin
    [28] With a retention time of 0.0008 to 20.0 minutes, wherein the hydrogen peroxide solution, which is further purified, is separated and removed from the exchange or adsorption resin by filtration in each case, Lt; / RTI >
    [29] According to the invention, further purification of the continuously connected fluidized bed may be carried out at 0 to 20 ° C, in particular at 0 to 10 ° C, and may be carried out batchwise or continuously. As in the case of further purification in the column, 5 to 59% hydrogen peroxide solution can be used in the process according to the invention.
    [30] The hydrogen peroxide solution used in the process according to the invention is a solution which is preliminarily purified by distillation and contains very small amounts of impurities such as, for example, metal cations Al, Fe, Zn etc., or anions such as NO 3 - , PO 4 2- Positive ionic inorganic impurities, and organic impurities as a result of the production.
    [31] Experimental results show that continuous chromatographic treatment with anion exchange resin, nonionic adsorbent resin and neutral adsorbent resin can remove up to 95% of undesirable organic impurities present from 5 to 59% hydrogen peroxide solution without difficulty . For example, the TOC content of a 50% hydrogen peroxide solution can be reduced from 40 ppm to less than 5 ppm by the method according to the present invention, and the resulting solution has absolutely necessary purity for use in the semiconductor industry under current requirements.
    [32] It has been found that the reduction of the TOC content is achieved only by treating in the preferred manner with the three resins mentioned above. The reduction of the content in the solution by the treatment of the neutral adsorbent resin according to the present invention does not achieve the necessary purification in a process carried out on an industrial scale and the adsorption capacity of these resins on the organic constituents is limited and economically It is impossible to carry out the purification. In contrast, a combination consisting of a tablet, preferably a strong base anion exchange resin, a nonionic adsorbent resin and a special neutral adsorbent resin, provides excellent purification results.
    [33] The hydrogen peroxide solution preliminarily purified by distillation can be further purified by contacting the exchange resin and the various adsorbent resins by separate fluidized bed mixing, preferably by contacting the resin in a packed column have. The flow rate of the hydrogen peroxide solution should be set so that the content of carbon and ionogenic impurities in the effluent does not exceed the maximum amount that can be tolerated. Advantageously, it is set at a flow density of 0.2 to 1.0 l / h · cm 2 , especially 0.5 to 0.7 l / h · cm 2 .
    [34] The purified hydrogen peroxide exiting the adsorption column is collected in a suitable vessel. If further purification is carried out in a suitable flow, the hydrogen peroxide solution is separated off by filtration and collected in a suitable vessel. However, the residence time should be set so that the reaction with the resin does not occur even if adsorption of undesirable impurities occurs. Excellent purification results can be obtained under suitable conditions, i.e. at a temperature of 0 to 20 DEG C, preferably 0 to 5 DEG C, atmospheric pressure and a residence time of the hydrogen peroxide solution of 0.008 to 20.0 minutes, while at the same time the oxygen content of the hydrogen peroxide solution And no reaction with the exchange resin was observed on the basis of the change of the temperature or the warming.
    [35] Continuous treatment with various resins can be processed in any desired order. Particularly excellent results are obtained due to the adsorption capacity when the neutral adsorbent resin is used in the final purification step. Very particularly good results are obtained, however, when the order is an anion exchange resin, a nonionic adsorbent resin and then a neutral adsorbent resin. This procedure is particularly important since the adsorption capacity of the neutral adsorbent is a limiting factor in this process and complex optimization of the volume flow rate and the ratio of volume to volume in the various purification steps is essential. However, if the columns are connected in turn in the preferred manner, this operation will not be necessary. This process parameter is not a problem especially if the treatment of the neutral adsorbent resin is performed last.
    [36] The strongly basic anion exchange resin that can be used is a styrene-divinylbenzene resin. For example, a corresponding resin is commercially available under the trade name Amberlyst A-26 (manufacturer: Rohm & Hass). Active groups of the resin is a -N (CH 3) 2 · Cl . Additional resins comprising the same active groups are AMBERLYSTM A-15, AMBERLIST TM A-21 and AMBERLIST TM A-27. Other suitable resins include Amberjet TM 4200 Cl, Amberjette TM 4400 Cl, Amberlite TM IRA 402 Cl, Amberlite TM IRA 404 Cl, Such as Amberlite® IRA 900 Cl, Amberlite® IRA 904 Cl, Amberlite® IRA 400 Cl, Amberlite® IRA 410 Cl, Amberlite® IRA 420 Cl, (Registered trademark) IRA 440 Cl, Amberlite (registered trademark) IRA 458, and Amberlite (registered trademark) 16766. The weakly basic anion exchange resins IRA-35, IRA-93, IRA-94 and IRA-68 available under the tradename AMBERLITE (R) are likewise suitable. It is also possible to use anion exchange resins sold under the trade names Dowex, Diaion Type I and Type II, and Duolite, which are strong or weakly basic.
    [37] According to a strong point of view, functional groups of anion exchangers can be oxidatively attacked by hydrogen peroxide solution, but experiments have shown that by setting appropriate operating parameters, they can be completely or substantially completely prevented. Depending on the solution being treated, this can be achieved by setting a high volume flow rate and / or by corresponding cooling. If necessary, this reaction can be carried out by cooling to about 0 캜. However, this was usually found to be necessary only when a solution having a relatively high content was to be further purified. In the case of further purification of the lower concentration range of solutions this is unnecessary because the reaction is first kept at a relatively low level or by setting a suitable volume flow rate and secondly the local temperature change can be suppressed.
    [38] The nonionic adsorbent resin that can be used in the process according to the present invention is a styrene-divinylbenzene resin having a macroporous structure and a large surface area. The corresponding resins do not have components which can be cleaned off, for example monomers or polymerization auxiliaries. This adsorbent is a completely nonionic hydrophobic polymer that does not have an ionic functional group and therefore the adsorption properties are solely based on the macroporous structure, the broad pore dimensions, the significantly large surface area and the aromatic nature of the surface. Therefore, this adsorbent is clearly distinguished from cations and anion exchangers which are very sensitive to oxidation due to the functional groups present on the surface. Nonionic adsorbent resins adsorb and liberate ionic species through hydrophobic and polar interactions, that is, they have high affinity for hydrophobic organic materials but low affinity for hydrophilic materials such as water or hydrogen peroxide.
    [39] Corresponding resins are commercially available, for example, under the trade names of Amberlite® XAD-4, hydrophobic polyaromatic resins, Amberlite® XAD-2 and Amberlite® XAD-16, Intermediate polar acrylic resin Diaion (TM) HP2MG and Diaion (TM) HP22SS, HP20, a variant of finer segmented specification. The adsorbent resin has a continuous polymer phase and especially regular pores. They are stable in the pH range of 0 to 14 and at temperatures of 250 DEG C or less. Under process conditions, the resin is all active at ambient temperature, i.e., at a temperature of 20 to 30 占 폚, and at a low temperature, e.g., below 0 占 폚.
    [40] Continuous treatment with a basic anion exchange resin and a nonionic adsorbent resin allows substantially complete removal of polarity and any ionic impurities from the hydrogen peroxide solution while protecting the used resin to the greatest extent possible.
    [41] Suitable neutral adsorbent resins are, for example, carbonized styrene-divinylbenzene resins having a high macroporous structure and a medium surface area. This resin is commercially available, for example, under the trade name Ambersorb (R). AmberSorb® 573, AmberSorb® 563, AmberSorb® 564, AmberSorb® 572, AmberSorb® 575, AmberSorb® 600 and AmberSorb® (registered trademark) RTI ID = 0.0 > 1500) < / RTI > can be used in the process according to the invention. The various resins listed are carbonized adsorbents made from highly sulphonated macroporous styrene-divinylbenzene ion exchange resins which have been pyrolyzed in a special way. As a result of the manufacturing process, the corresponding adsorbents have uniform porosity, constant hydrophobic properties and excellent mechanical stability.
    [42] As a result of the experiment, only the combination of the purification steps of the above-mentioned treatment method, which comprises treatment of the neutral adsorbent resin in the final stage and treatment of the anion exchange resin in each case and treatment of the nonionic adsorbent resin, (TOC) to a level that meets the high quality requirements of the semiconductor industry, i.e., less than 5 ppm, and more preferably less than 1 ppm.
    [43] In this regard, it has also been found that this is a unique characteristic of neutral adsorbent resins which precisely leads to a reduction in the content of organic impurities.
    [44] The difference between the non-ionic and neutral adsorbent resins will be apparent in the example of Table 1 below using the nonionic adsorbent resin, Amberlite XAD-4, and the neutral adsorbent resin, Amber Sorb 563,
    [45] designation Nonionic adsorbent resin Special Neutral Adsorption Resin Yes Amberlite XAD-4 (registered trademark) AmberSorb TM 563 matrix Styrene-DVB Styrene-DVB; Pyrolysis furnace post-treatment Surface area (m 2 / g) 750 550 Porosity (g / ml) 0.5 0.6 Minor Pore / Big Pole Ratio Greater than 1 One
    [46] The special neutral adsorbent resin used in the process according to the invention has the following product characteristics distinguished from conventional nonionic adsorbent resins:
    [47] Microporous: macroporous ratio can be adopted to a value of less than 1, porosity is high macroporosity, greater than 0.55 g / ml in surface area / weight unit ratio of less than 600 m2 / g;
    [48] Excellent mechanical stability and chemical resistance; And
    [49] Adsorbent resins are more accessible (more effective) to relatively high molecular weight organic components due to the relatively high ratio of macropores.
    [50] It is desirable to remove impurities resulting from the preparation by means of a suitable pure solvent known to a person skilled in the art prior to the use of the exchange and adsorption resins in the process according to the invention, Because it decomposes hydrogen peroxide. In order to preliminarily wash the nonionic adsorbent resin, it is preferable to use, for example, a lower alcohol, preferably methanol. Anion exchange resins which can be used according to the invention can be prewashed with, for example, 2-propanol and subsequently with ultrapure water while the neutral adsorption resin can be prewashed with steam and then with ultrapure water.
    [51] The process according to the invention can be carried out batchwise and the exchanges and adsorption resins used in this case are regenerated each time a given amount of hydrogen peroxide solution is further purified. However, it is also possible to carry out this process continuously, for example by means of a column of the same charge, which can be converted by changing the direction of the volumetric flow when saturated with impurities which are present parallel to the column currently being used It is possible.
    [52] In this way, each column can be individually regenerated, volume flow does not need to be discontinued, and discarded run time does not occur. The adsorption capacity of the resin used is no longer a limiting factor.
    [53] The combination of anion exchange resin and adsorbent resin provided in Table 2 below is highly suitable for carrying out the process according to the invention. The combinations shown are provided by way of example and are not to be construed as limiting the invention.
    [54] fair Step 1: Anion exchange resin Step 2: Nonionic adsorbent resin Step 3: Neutral adsorption resin Rohm and Haas Product Name AMBERLIST (R) A-26 Amberlite 占 XAD-2 AmberSorb TM 563 AMBERLIST (R) A-27 Amberlite 占 XAD-4 AmberSorb® 564 AmberJet (R) 4200 Cl Amberlite 占 XAD-16 Amber sorb (R) 572 Amp; num; 4400 Cl < RTI ID = 0.0 > AmberSorb TM 575 Amberlite (R) IRA 402 Cl AmberSorb TM 600 Amberlite (R) IRA 404 Cl AmberSorb 占 1500
    [55] The method according to the present invention is carried out using conditions and methods known per se to those skilled in the art. A column having a ratio between column height and column diameter of from 7.5: 1 to 2.5: 1, preferably from 6: 1 to 4: 1, particularly preferably 5: 1, is used, Good purification results are achieved using a column that flows the bed volume of the hydrogen peroxide solution. However, the method can also be carried out in a column having a height of 10 to 200 cm and a diameter of 1 to 2 cm. However, columns with a height of 2.5 to 4 m and a diameter of 0.50 to 0.8 m are particularly suitable in the case of relatively large amounts of tablets.
    [56] An important factor in the success of the purification process according to the present invention is that all devices and vessels used in the purification are made of a suitable material which prevents highly pure hydrogen peroxide from being subsequently re-contaminated, for example by metal ions, . Suitable materials have been found, in particular, as borosilicate glass, polytetrafluoroethylene, polyvinylidene fluoride and high pressure polyethylene.
    [57] The present invention provides a particularly simple and beneficial purification method of hydrogen peroxide for use in microelectronics applications. The method according to the invention is particularly advantageous in that very low levels of organic impurities, especially in hydrogen peroxide solutions, can also be removed very effectively and in particular the interference cations such as Na, K, Mg, Al, Ca, Fe, It is distinguished by the fact that it is completely removed.
    [58] The hydrogen peroxide solution further purified by the method according to the present invention has increased stability and meets the recent purity requirements for the manufacture of highly integrated chips.
    [59] It will be readily apparent to those skilled in the art from the description of the invention provided herein that it is possible to produce highly pure hydrogen peroxide solutions that meet the high requirements for use in modern chip manufacturing methods. The examples provided below serve to provide a better understanding of the present invention and are not intended to limit the invention thereto.
    [60] EXAMPLES, METHODS AND RESULTS:
    [61] In order to demonstrate the efficiency of the process according to the invention, the following aqueous solutions of hydrogen peroxide and exchange and adsorption resins were used and the following analytical methods were used:
    [62] Hydrogen peroxide solution:
    [63] Source: Merck KGaA (Merck KGaA), anthraquinone process ("autoxidation process")
    [64] Product number: Batch KD09971042
    [65] Concentration: 50% ± 1% or 30% ± 1%
    [66] Quantity: 2.5ℓ
    [67] Adsorption resin:
    [68] Anionic exchange resin: Amberly < RTI ID = 0.0 > A <
    [69] Nonionic adsorbent resin: Amberlite 占 XAD-4
    [70] Neutral adsorption resin: Amber sorb (R) 563
    [71] Pretreatment: All resins were rinsed with ultra pure water for 8 hours before use.
    [72] Analysis method:
    [73] Determination of TOC using Shimadzu TOC 5000 (measurement method based on complete decomposition of sample on platinum catalyst at elevated temperature). The total amount of carbon dioxide formed was measured with an infrared spectrometer.
    [74] Cations and anions were not specifically determined.
    [75] Example 1
    [76] Flow rate: 1.0 l / h
    [77] Flow Density: 0.3 l / h · cm 2
    [78] Step: adsorbentTOC (ppm) Step 1 (standard H 2 O 2 50%)38.0 Step 1: AMBERLIST (R) A-2623.7 Step 2: Amberlite 占 XAD-44.7 Step 3: AmberSorb TM 5632.4
    [79] Pressure: atmospheric pressure
    [80] Temperature: Room temperature
    [81] Column material: Polyethylene
    [82] This experiment confirmed the excellent mechanical stability and chemical resistance of the three steps for relatively high concentrations of hydrogen peroxide solutions and showed that the third step achieved significant additional purification in the TOC range of less than 5 ppm.
    [83] Example 2
    [84] Flow rate: 1.0 l / h
    [85] Flow Density: 0.3 l / h · cm 2
    [86] Step: adsorbentTOC (ppm) After the first step (reference H 2 O 2 30%)11.5 AMBERLITE (R) XAD-4 alone1.6 Amber Sorb (registered trademark) 563 alone1.1 First, Amberlite XAD-4, followed by AmberSorb (R) 5630.4
    [87] This experiment showed that the nonionic adsorbent resin and the special neutral adsorbent resin had different selectivities in the reduction of the relatively high molecular weight organic component concentration. Only when the two adsorbent resins were used in combination, the content of organic components (TOC) in the hydrogen peroxide solution was reduced to less than 1 ppm.
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] A purified hydrogen peroxide solution having a concentration ranging from 5 to 59%
    a) anion exchange resin;
    b) a nonionic adsorbent resin in the form of a hydrophobic aromatic crosslinked polymer having a macroporous structure; And
    c) a neutral adsorbent resin selected from the group consisting of styrene-divinylbenzene resin having a high macroporous structure and formed by pyrolysis treatment
    Wherein the treatment of the adsorbent or exchange resin is carried out in any desired order, provided that the treatment of the neutral adsorbent resin is carried out in the final step.
    [2" claim-type="Currently amended] The method according to claim 1,
    The anion exchange resin used is a resin selected from the group consisting of a weak or strong basic styrene-divinylbenzene resin containing a quaternary ammonium group as a functional group and a weak or strong basic styrene-divinylbenzene containing a tertiary amino group as a functional group Lt; / RTI >
    [3" claim-type="Currently amended] The method according to claim 1,
    Wherein the nonionic adsorbent resin used is a polymer selected from the group consisting of hydrophobic aromatic crosslinked polymers having a macroporous structure, especially styrene-divinylbenzene resins having a macroporous structure and a large surface area.
    [4" claim-type="Currently amended] 4. The method according to any one of claims 1 to 3,
    Characterized in that the hydrogen peroxide solution to be treated is passed through successive connected columns at a flow density of 0.2 to 1.0 l / h · cm 2 , in particular 0.5 to 0.7 l / h · cm 2 .
    [5" claim-type="Currently amended] 4. The method according to any one of claims 1 to 3,
    Characterized in that the hydrogen peroxide solution to be purified is passed through a continuously connected fluidized bed at a retention time of from 0.008 to 20.0 minutes.
    [6" claim-type="Currently amended] 6. The method according to any one of claims 1 to 5,
    15 < 0 > C to 25 < 0 > C, preferably 20 < 0 > C.
    [7" claim-type="Currently amended] 7. The method according to any one of claims 1 to 6,
    ≪ / RTI > is carried out continuously.
    [8" claim-type="Currently amended] 7. The method according to any one of claims 1 to 6,
    Characterized in that it is carried out batchwise.
    [9" claim-type="Currently amended] The method according to any one of claims 1 to 3 and 5,
    0 > C to 20 < 0 > C, especially 0 to 10 < 0 > C.
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    同族专利:
    公开号 | 公开日
    US6939527B2|2005-09-06|
    TW574136B|2004-02-01|
    JP2003535007A|2003-11-25|
    US20030165420A1|2003-09-04|
    DE10026363A1|2001-11-29|
    AU6382601A|2001-12-11|
    KR100742479B1|2007-07-25|
    EP1284925A1|2003-02-26|
    WO2001092149A1|2001-12-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-05-27|Priority to DE10026363A
    2000-05-27|Priority to DE10026363.1
    2001-03-29|Application filed by 메르크 파텐트 게엠베하
    2001-03-29|Priority to PCT/EP2001/003584
    2003-05-09|Publication of KR20030036198A
    2007-07-25|Application granted
    2007-07-25|Publication of KR100742479B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE10026363A|DE10026363A1|2000-05-27|2000-05-27|Process for the purification of hydrogen peroxide solutions|
    DE10026363.1|2000-05-27|
    PCT/EP2001/003584|WO2001092149A1|2000-05-27|2001-03-29|Method for the purification of hydrogen peroxide solutions|
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