• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention firstly relates to a method for purifying hydrogen peroxide, comprising: - providing a starting stream containing hydrogen peroxide at a content greater than 50% by weight, as well as at least one stabilizer; a single step of purification of the starting stream, said single stage consisting of reverse osmosis purification; the collection of a purified stream at the end of said single purification step. The invention also relates to a solution obtainable by this method.
    公开号:FR3022899A1
    申请号:FR1456165
    申请日:2014-06-30
    公开日:2016-01-01
    发明作者:Philippe Zydowicz；Benoit Requieme；Michel Jauffret
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to a process for the purification of hydrogen peroxide and a solution of hydrogen peroxide. BACKGROUND OF THE INVENTION Hydrogen peroxide is a product used in various industrial applications, particularly in electronics and in the food industry. Existing processes for producing hydrogen peroxide result in the presence of impurities or low concentration organic or inorganic contaminants in the product. In addition, because of the corrosive nature of hydrogen peroxide vis-à-vis many metallic materials, the transport or storage of hydrogen peroxide can be accompanied by enrichment of contaminants such as Fe, Cu, Mn or Cr.
    [0002] In general, the contaminants present in a solution of hydrogen peroxide can be catalysts for the decomposition of hydrogen peroxide. It is known to use stabilizers to limit the decomposition of hydrogen peroxide. It is also known to purify hydrogen peroxide in order to reduce the content of contaminants, for example by distillation or filtration on resins or membranes. Thus, US 4,879,043 describes the use of reverse osmosis to purify a stream of hydrogen peroxide having a titer of 5 to 50% by weight.
    [0003] US 6,333,018 describes the use of reverse osmosis to purify a stream of hydrogen peroxide having a titer of 60 to 70% by weight, in the absence of stabilizers. The document WO 2005/033005 describes a purification of hydrogen peroxide in at least two stages, for example a reverse osmosis step and then a step of contacting with an adsorption resin. In fact, the desired specifications for hydrogen peroxide vary according to industrial applications. Thus, for the regulated applications, in the cosmetics, the pharmacy or the agrifood, a very high purity is necessary. On the other hand, for mass-use applications (in chemistry, or in the production of paper pulp), the hydrogen peroxide produced commonly has a much higher amount of contaminants. However, there is a need for an intermediate grade, for example in the field of the production of peracids, including peracetic acid. In other words, it is desired to improve to a certain extent the purity of the hydrogen peroxide of the type used for mass-use applications, with a relatively low cost and using a simple process, without implementing the complex techniques in use for regulated applications. SUMMARY OF THE INVENTION The invention firstly relates to a process for purifying hydrogen peroxide, comprising: providing a hydrogen peroxide-containing starting stream at a content of greater than 50% by weight, as well as at least one stabilizer; a single step of purification of the starting stream, said single stage consisting of reverse osmosis purification; the collection of a purified stream at the end of said single purification step. According to one embodiment, the starting stream is prepared by a process comprising a passage over an adsorption resin. According to one embodiment, the starting stream contains at least 55% by weight, preferably at least 60% by weight, of hydrogen peroxide. According to one embodiment, the stabilizer is chosen from phosphate or pyrophosphate salts, tin salts, organophosphorus compounds and in particular phosphonates, carboxylic acids, borates, nitrates and combinations thereof. the stabilizer 30 preferably being a mixture of sodium pyrophosphate and sodium stannate. In one embodiment, the reverse osmosis purification comprises: passing the starting stream over a single membrane; - The collection of a permeate and a retentate from the membrane, the purified stream being constituted by the permeate. According to one embodiment, reverse osmosis purification comprises: passing the starting stream over a first membrane; collecting a permeate and a retentate from the first membrane; - The permeate passage from the first membrane on a second membrane; Collecting a permeate and a retentate derived from the second membrane, the purified stream being constituted by the permeate issuing from the second membrane. According to one embodiment, the reverse osmosis purification is carried out on a membrane of polyamide, polypiperazine, polyacrylonitrile or polysulfone type, and preferably on a polyamide membrane on a polysulfone support. According to one embodiment, the purified stream contains: less than 100 mg / kg of total organic carbon; - less than 5 mg / kg of phosphorus; Less than 0.04 mg / kg iron; and less than 0.1 mg / kg of the sum of chromium and nickel. According to one embodiment, the purification of the starting stream uses one or more membranes, said membranes being used for a duration greater than or equal to 1 week, preferably greater than or equal to 2 weeks, or greater than or equal to 3 weeks, or greater than or equal to 4 weeks. The invention also relates to a solution containing more than 50% by weight of hydrogen peroxide, also containing at least one stabilizer, and containing: less than 100 mg / kg of total organic carbon; - less than 5 mg / kg of phosphorus; - less than 0.04 mg / kg of iron; and less than 0.1 mg / kg of the sum of chromium and nickel.
    [0004] According to one embodiment, the solution contains at least 55% by weight, preferably at least 60% by weight, of hydrogen peroxide. According to one embodiment, the stabilizer is chosen from phosphate or pyrophosphate salts, tin salts, organophosphorus compounds and especially phosphonates, carboxylic acids, borates, nitrates and combinations thereof the stabilizer is preferably a mixture of sodium pyrophosphate and sodium stannate. According to one embodiment, the stabilizer content is between 5 and 50 mg per kg of solution. The present invention overcomes the disadvantages of the state of the art. In particular, it makes it possible to produce hydrogen peroxide having intermediate specifications between those of the mass-use applications and those of the regulated applications, and this at low cost and with a relatively simple process. DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows. Unless stated otherwise, all the concentrations or contents mentioned are mass values. The invention provides for the supply of a starting stream containing hydrogen peroxide at a content greater than 50% by weight. This starting stream is preferably directly from a hydrogen peroxide production unit, and has not undergone any prior purification other than possibly a passage on adsorption resin during its production. It is an aqueous solution of hydrogen peroxide. The invention is advantageously applied to feed streams containing at least 52%, at least 55%, at least 58%, at least 60%, at least 62% or at least 65% hydrogen peroxide. The starting stream contains at least one stabilizer. This stabilizer is usually added directly at the output of the production unit. The stabilizer content ranges from 1 to 400 mg / kg, preferably from 5 to 300 mg / kg. As the stabilizer, it is possible to use, for example, phosphate or pyrophosphate salts, tin salts, organophosphorus compounds and in particular phosphonates, carboxylic acids, borates, nitrates or combinations thereof. The preferred stabilizer is a mixture of sodium pyrophosphate and sodium stannate containing 1 to 150 mg of each stabilizer per kg of product, preferably 15 to 100 mg of each stabilizer per kg of product, preferably 20 to 110 mg each stabilizer per kg of product, preferably 25 to 120 mg of each stabilizer per kg of product. The invention provides a single step of purifying the starting stream, which is a reverse osmosis purification step. Thus, the invention excludes the presence of purification steps by another technique, such as distillation steps, ion exchange, exposure to ozone or ultraviolet radiation, ultrafiltration or nanofiltration, etc. The reverse osmosis purification step can comprise a single passage on a reverse osmosis membrane, or a succession of several passages on reverse osmosis membranes, in particular a succession of two or three passages on osmosis membranes. reverse. The succession of several passes on reverse osmosis membranes can be implemented by having reverse osmosis units in series. Of course, it is also possible to have reverse osmosis units in parallel depending on the desired flow rate.
    [0005] The reverse osmosis membranes used in the context of the invention are semi-permeable membranes of polyamide, polypiperazine, polyacrylonitrile or polysulfone type, and preferably are polyamide membranes on polysulfone support. Each step of passage over a reverse osmosis membrane makes it possible to collect a permeate and a retentate, the permeate being the fraction depleted in contaminants. The passage on the membrane is forced by application of adequate pressure. The retentate, enriched with contaminants, can also be recovered, for example in the form of a hydrogen peroxide with lower specifications. If only a part of the starting stream is purified, it is possible to mix the retentate with the other part (not subject to purification) of the starting stream. The permeation flux may be, for example, between 10 and 200 L / h.m2, preferably between 20 and 180 L / h.m2, preferably between 50 and 150 L / h.m2. The pressure may for example be between 10 and 80 bar, preferably between 15 and 70 bar, preferably between 25 and 40 bar. The FCV (Voluminal Concentration Factor calculated as the ratio of the feed rate to the retentate flow rate) can be, for example, between 1 and 10, preferably between 1.2 and 8, preferably between 1.5 and 5, of preferably between 2 and 4. A problem with reverse osmosis purification of hydrogen peroxide streams is that hydrogen peroxide has a tendency to chemically attack the membranes, especially when present at a high concentration. Thus, US 4,879,043 teaches the use of reverse osmosis only for streams containing less than 50% hydrogen peroxide. The present inventors have found that the life of certain membranes in the presence of a stream containing more than 50% hydrogen peroxide does not exceed a few hours or days. On the other hand, certain membranes have an increased resistance to hydrogen peroxide and can be used continuously for a period of at least 1, 2, 3 or even 4 weeks.
    [0006] EXAMPLES The following example illustrates the invention without limiting it. In this example, the content of different contaminants is compared in a solution S containing 60% of stabilized hydrogen peroxide with 110 mg of sodium pyrophosphate and 30 mg of sodium stannate (expressed as Na 2 SnO 3, 3H 2 O) per kg of solution. before and after purification by reverse osmosis (in one step or in two steps, notation "01") using a KOCH TFC-XR reverse osmosis membrane, under the following operating conditions: pressure: 35 bar, temperature: 22 ° C, FCV: 2.5, permeation flow: 70 L / h.m2. The starting solution S tested has typical specifications of a hydrogen peroxide of high diffusion. Solution S was prepared by a process comprising a passage on adsorption resin. Specifications commonly used for the production of peracetic acid are also indicated. The results are shown in the table below ("TOC" means: total organic carbon). The metal contents were determined according to the methods described in standards NF EN ISO 17294-2 and NF EN ISO 11885; the TOC content was determined according to the method described in standard NF EN 1484.
    [0007] 3022 899 7 S S + 1 step S + 2 steps Example 01 01 specifications TOC (mg / kg) 240 100 40 <100 P (mg / kg) 45 9 2 <5 Fe (mg / kg) 0.3 0.05 0 , 03 <0.04 Sn (mg / kg) 13.5 0.7 0.03 - Cr + Ni 0.15 <0.1 <0.1 <0.1 (mg / kg)
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. A method of purifying hydrogen peroxide, comprising: - providing a hydrogen peroxide containing starting stream of greater than 50% by weight, and at least one stabilizer; a single step of purification of the starting stream, said single stage consisting of reverse osmosis purification; the collection of a purified stream at the end of said single purification step.
    [0002]
    The process of claim 1, wherein the starting stream is prepared by a process comprising a passage over an adsorption resin.
    [0003]
    3. Process according to claim 1 or 2, wherein the starting stream contains at least 55% by weight, preferably at least 60% by weight, of hydrogen peroxide.
    [0004]
    4. Method according to one of claims 1 to 3, wherein the stabilizer is selected from phosphate or pyrophosphate salts, tin salts, organophosphorus compounds and in particular phosphonates, carboxylic acids, borates, nitrates and combinations thereof, the stabilizer preferably being a mixture of sodium pyrophosphate and sodium stannate.
    [0005]
    5. Method according to one of claims 1 to 4, wherein the reverse osmosis purification comprises: - the passage of the starting stream on a single membrane; - The collection of a permeate and a retentate from the membrane, the purified stream being constituted by the permeate.
    [0006]
    6. Method according to one of claims 1 to 5, wherein the reverse osmosis purification comprises: - the passage of the starting stream on a first membrane; Collecting a permeate and a retentate derived from the first membrane; - The permeate passage from the first membrane on a second membrane; Collecting a permeate and a retentate derived from the second membrane, the purified stream being constituted by the permeate issuing from the second membrane.
    [0007]
    7. Method according to one of claims 1 to 6, wherein the reverse osmosis purification is performed on a membrane of polyamide type, polypiperazine, polyacrylonitrile or polysulfone, and preferably on a polyamide membrane on a polysulfone support. 15
    [0008]
    8. Process according to one of claims 1 to 7, wherein the purified stream contains: less than 100 mg / kg of total organic carbon; - less than 5 mg / kg of phosphorus; - less than 0.04 mg / kg of iron; and less than 0.1 mg / kg of the sum of chromium and nickel.
    [0009]
    9. Method according to one of claims 1 to 8, wherein the purification of the starting stream uses one or more membranes, said membranes being used for a duration greater than or equal to 1 week, preferably greater than or equal to 2 weeks, or greater than or equal to 3 weeks, or greater than or equal to 4 weeks.
    [0010]
    10. A solution containing more than 50% by weight of hydrogen peroxide, also containing at least one stabilizer, and containing: - less than 100 mg / kg of total organic carbon; - less than 5 mg / kg of phosphorus; - less than 0.04 mg / kg of iron; and less than 0.1 mg / kg of the sum of chromium and nickel.
    [0011]
    11. The solution of claim 10, containing at least 55% by weight, preferably at least 60% by weight, of hydrogen peroxide.
    [0012]
    12. The solution of claim 10 or 11, wherein the stabilizer is selected from phosphate or pyrophosphate salts, tin salts, organophosphorus compounds and in particular phosphonates, carboxylic acids, borates, nitrates and phosphonates. combinations thereof, the stabilizer preferably being a mixture of sodium pyrophosphate and sodium stannate.
    [0013]
    13. The solution according to one of claims 10 to 12, wherein the stabilizer content is between 5 and 50 mg per kg of solution.
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    FR3022899B1|2014-06-30|2020-10-02|Arkema France|PROCESS FOR PURIFYING HYDROGEN PEROXIDE AND HYDROGEN PEROXIDE SOLUTION|FR3022899B1|2014-06-30|2020-10-02|Arkema France|PROCESS FOR PURIFYING HYDROGEN PEROXIDE AND HYDROGEN PEROXIDE SOLUTION|
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    CN109772168A|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|
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    法律状态:
    2015-06-08| PLFP| Fee payment|Year of fee payment: 2 |
    2016-01-01| PLSC| Search report ready|Effective date: 20160101 |
    2016-05-16| PLFP| Fee payment|Year of fee payment: 3 |
    2017-05-11| PLFP| Fee payment|Year of fee payment: 4 |
    2018-05-14| PLFP| Fee payment|Year of fee payment: 5 |
    2020-05-12| PLFP| Fee payment|Year of fee payment: 7 |
    2021-05-13| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1456165A|FR3022899B1|2014-06-30|2014-06-30|PROCESS FOR PURIFYING HYDROGEN PEROXIDE AND HYDROGEN PEROXIDE SOLUTION|FR1456165A| FR3022899B1|2014-06-30|2014-06-30|PROCESS FOR PURIFYING HYDROGEN PEROXIDE AND HYDROGEN PEROXIDE SOLUTION|
    CN202110842246.3A| CN113387331A|2014-06-30|2015-06-26|Method for purifying hydrogen peroxide and hydrogen peroxide solution|
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    CN202110850723.0A| CN113353891A|2014-06-30|2015-06-26|Method for purifying hydrogen peroxide and hydrogen peroxide solution|
    PCT/FR2015/051732| WO2016001539A1|2014-06-30|2015-06-26|Hydrogen peroxide purification process and hyrodgen peroxide solution|
    US15/318,313| US10822235B2|2014-06-30|2015-06-26|Hydrogen peroxide purification process and hydrogen peroxide|
    CA2953471A| CA2953471A1|2014-06-30|2015-06-26|Hydrogen peroxide purification process and hyrodgen peroxide solution|
    EP15753713.5A| EP3160900A1|2014-06-30|2015-06-26|Hydrogen peroxide purification process and hyrodgen peroxide solution|
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