• 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 process is used to remove TOC and AOX from brine by high-pressure wet oxidation with iron II salts as catalyst and oxygen as oxidant at 260 ° C. The oxidation leads only to acetic acid, which is adsorbed in a second process step from the brine to synthetic activated carbon, while the catalyst salts are redeposited in a final process stage.
    公开号:AT511354A4
    申请号:T8392011
    申请日:2011-06-07
    公开日:2012-11-15
    发明作者:Walter Dipl Ing Kanzler
    申请人:Kanzler Walter；
    IPC主号:
    专利说明:

    Process for the treatment of contaminated brine solutions for chlor-alkali electrolysis
    In saponification processes, such as e.g. in the production of epichlorohydrin, i.a. fall more or less concentrated saline solutions - brine - whose introduction into receiving waters is not allowed because in addition to the salt cargo contaminants with hydrocarbons or halogenated hydrocarbons, mostly chlorinated hydrocarbons are included. On the other hand, the brine solutions are often free of inorganic impurities, making them an interesting raw material for chlor-alkali electrolysis.
    The invention is therefore based on the object to clean such brine so that it can serve as a raw material for the electrolysis.
    In the case of the production of epichlorohydrin, a brine containing about 20 wt.% NaCl and containing about 8000 mg / l TOC, caused by glycerol, epichlorohydrin and dichlorohydrin, is charged. Due to the high salt content, the brine can only be introduced into a conventional biological sewage treatment plant in about 20 -100 times diluted form. Similar brine solutions are also formed in the production of epoxy resins, which is also cleaved with sodium hydroxide, a chlorine atom from the epichlorohydrin.
    Conventional methods of wet oxidation, such as peroxide, hypochlorite, UV, ozone, electrooxidation, are eliminated because of inefficiency. Namely, in these methods, chlorine gas is preferably produced when applied to these sols, and only a small amount of TOC and AOX is decomposed.
    Pressure oxidation process as known in the art, e.g. DE 102006001955, which work with solid catalysts, have no required conversion in salt solutions, since the catalysts do not achieve a lifetime because of the hydrochloric acid formed. Also, those methods which use hydrogen peroxide as the oxidizing agent, e.g. EP 0680931, achieve no significant sales in brine solutions. No. 6,139,755 deals with municipal wastewater with a free-radical initiator, a catalyst and oxygen at 80 to 140 ° C., using metal salts as catalyst and hydrogen peroxide as radical initiator. It is obviously a kind of "Fenton reaction". For brine, this procedure does not work. Surprisingly, it has been found, according to the invention, that iron II can oxidize salts at higher temperatures (> 220 ° C) with oxygen also into brine TOC and AOX, in particular glycerol, epichlorohydrin and dichlorohydrin.
    The object is achieved according to the invention in that the pH of the brine is adjusted to a pH of <2 by acids, preferably hydrochloric acid, the brine 40-400 mg / l, preferably 80-100 mg / l, iron Il chloride is added, the brine is brought to a pressure of 30-60 bar, over one or more heat exchangers (W1, W2) preheated to 170-260'C and in a reactor (RI) with the oxygen-containing gas, preferably oxygen, in cocurrent flows from bottom to top, heated by the reaction at 240 to 275 ° C, preferably 260 "C, and the resulting reaction products in the oxidation, preferably acetic acid, after cooling (Wl), preferably by the untreated brine, relaxation (VI) and degassing (Bl) on one
    Adsorbent (All, A12), preferably synthetic activated carbon, in particular Lewatit AF5, is adsorbed and then after raising the pH to 5-10, preferably pH 7.5, by alkali, preferably NaOH, the iron II and iron III salts are separated ,
    Tests in the supercritical area with the addition of strong oxidizing agents have shown that it is also possible to break down TOC in brine without producing Chforgas. However, the method has the disadvantage that the salts in the supercritical region are insoluble and clog the reactor and also no material is available for these conditions.
    It was therefore searched for effective catalysts that are available inexpensively and can be deposited again after the reaction. Iron II in the form of chloride has proved to be the best solution. By the end of the reaction, the catalyst itself is largely reacted to form iron III. In any case, it is possible to reduce the reaction end temperature in the reactor to 240 to 275 C depending on the component by addition of iron II chloride. Since the heat of reaction in the decomposition of the TOC and AOX increases the temperature in the reactor between 10 and 100 ° C. (depending on the load of the brine), the inlet temperature into the reactor must be only 170 to 250 ° C. For the brine from epichlorohydrin production, the optimum temperature conditions are 200 ° C at the reactor inlet and 260 ° C at the reactor outlet. The concentration of catalyst was optimal with 100 mg / l ferric chloride. Higher concentrations do not bring significantly higher sales.
    It is not possible to increase the temperature in the reactor above 270 ° C, since even the best titanium alloys fail at temperatures above it.
    The conversion of AOX was practically 100% in these experiments, while TOC is degraded by only 90%. This is because the oxidation process proceeds via various intermediates and pathways mostly via acetic acid and acetic acid is only partially oxidized under the given conditions because of the stability of the molecule. The starting components, e.g. Glycerol, epichlorohydrin and dichlorohydrin are only detectable in traces after the reaction.
    None of the known wet oxidation processes were able to oxidize the acetic acid in the brine.
    By separating the acetic acid with liquid-liquid extraction, it is possible to further separate 90% of the acetic acid. The deposition of 99% TOC is still too little, since today's membranes of chlorine alkali electrolysis tolerate a maximum of 5-10 mg / l TOC.
    Therefore, various commercially available adsorbents were tested which could not handle the problem economically (it was therefore surprising that the synthetic "activated carbon" Lewatit AF5 can adsorb acetic acid up to 3% by weight, because of its synthetic production, its uniform pore structure The adsorption must be carried out in the acidic range and the regeneration is carried out with dilute sodium hydroxide solution by customary adsorption processes, such as 2-bed interchange processes or 3-bed processes with adsorber, polisher, regeneration, which are familiar to the person skilled in the art.
    The deposition of the iron is carried out according to the invention either by ion exchange or by filtration. In both cases, the pH must be increased to 7.5-8 for complete separation of iron II. • · · ♦ * · · · ft ft
    It is also advantageous in the method according to the invention that no foreign ions except iron are introduced into the system, so that the brine preparation in the chlor-alkali electrolysis can be greatly simplified. For applications where the brine needs only 90% cleaning - e.g. if the brine can not be used and e.g. discharged into the sea water - can be omitted the adsorption stage for the acetic acid.
    Application example: 1 mJ / h brine from a production of epoxy resins with a salt content of 21% by weight is loaded with a TOC of 4000 mg / l. Half of the TOC is glycerin and epichlorohydrin. The brine is added with 100 mg / l iron II chloride and adjusted to pH <2. The high pressure pump PI raises the pressure to 50 bar and before the countercurrent heat exchanger W1 5 Nm * / h of 98% oxygen at 55 bar are added. In the W1 the temperature of the brine is increased from 40eC to 210 ° C and in the heater W2 the temperature of the brine is raised to 215 "C with 40 bar of saturated steam. The heated brine now enters the reactor, where at the entrance another 15 Nm3 / h 98% oxygen are added. The reactor has a height of 9 meters and the residence time is 2.8 hours. Due to the heat of reaction, the brine heats up to 260 ° C. The TOC is thereby converted to 89% and the AOX to> 99.9%.
    The treated brine from the reactor releases its heat in the recuperator W1 to the raw brine and is thereby cooled to <90 ° C, the gases contained as the formed CO 2 and the oxygen excess are deposited in the flash tank Bl while the brine in the adsorber All that is filled with Lewatit AF5. The TOC {acetic acid) in front of the adsorber is 440 mg / l and after the adsorber 3 mg / l. While the adsorber All is in operation, the adsorber A12 is regenerated with 4 wt .-% sodium hydroxide solution. After 8 hours of operation, the adsorbers are switched. All is in regeneration, A12 in adsorption. After the adsorber, the pH to 7.5 with 4 wt. % sodium hydroxide solution and the iron ions are from the brine to a content of &lt; 0.3 mg / l deposited. The separation takes place on an ion exchanger of the type Lewatit TP207. The ion exchanger is operated as the adsorber in the 2-bed change process and the regeneration is carried out with 2% hydrochloric acid.
    权利要求:
    Claims (6)
    [1]
    1. A process for the oxidation of hydrocarbons and chlorinated hydrocarbons in brine by oxygen-containing gases, preferably oxygen, by high-pressure catalytic oxidation, characterized in that the pH of the brine is adjusted to a pH of <2 by acids, preferably hydrochloric acid , the brine 40-400 mg / l, preferably 80-100 mg / l, iron Il chloride is added, the brine is brought to a pressure of 30-60 bar, via one or more heat exchangers Wl, W2) to 170 - Preheated 260 ° C and in a reactor (RI) with the oxygen-containing gas, preferably oxygen, flows in cocurrent from bottom to top, heated by the reaction at 240 - 275 ° C, preferably 260 ° C, and at the oxidation resulting reaction products, preferably acetic acid, after cooling (Wl), preferably by the untreated brine, relaxation (VI) and degassing (Bl) of an adsorbent (All, A12), preferably synthe activated charcoal, in particular Lewatit AF5, and then after raising the pH to 5-10, preferably pH 7.5, by alkali, the iron II and iron III salts are separated.
    [2]
    2. The method according to claim 1, characterized in that the oxygen-containing gas, preferably oxygen, to a small part, preferably 20% of the total amount, the raw brine is added in front of the heat exchanger Wl.
    [3]
    3. The method according to claim 1, characterized in that the brine after Bl on &lt; 40 * C is cooled and the adsorber is alternately regenerated with dilute sodium hydroxide solution, preferably 4 wt.% Sodium hydroxide solution.
    [4]
    4. The method according to claim 1, daurch characterized in that the iron deposition is carried out by ion exchangers, which are regenerated alternately.
    [5]
    5. The method according to claim l., Characterized in that the iron deposition takes place after the neutralization of the sols by filtration.
    [6]
    6. The method according to claim 1, characterized in that the activated carbon stage can be omitted if the brine is delivered to your receiving water and the conversion achieved in the high-pressure oxidation is already sufficient.
    类似技术:
    公开号 | 公开日 | 专利标题
    AT511354B1|2012-11-15|METHOD FOR THE PREPARATION OF POLLUTED SOLUTIONS FOR CHLORINE ALKALI ELECTROLYSIS
    EP0696261B1|1997-07-30|Method of treating waste water containing organic and inorganic compounds arising from the manufacture of epichlorohydrin
    WO2000078682A1|2000-12-28|Method of decomposing organic compounds in water
    EP1483204A1|2004-12-08|Preparation of waste water containing sodium chloride for use in chlor-alkali electrolysis
    DE3032875A1|1981-03-19|METHOD FOR CHLORALKALI ELECTROLYSIS
    EP1947061A1|2008-07-23|Method for eliminating organic compounds containing nitrogen from water containing salt
    US20210101815A1|2021-04-08|Process for the work-up and reuse of salt-containing process water
    Verdickt et al.2012|Applicability of ion exchange for NOM removal from a sulfate-rich surface water incorporating full reuse of the brine
    EP3448815B1|2022-01-26|Method for oxidising hydrocarbons and similar in aqueous salt solutions
    DE112017001666B4|2020-08-13|Process for reducing the emission of pollutants in phenol and acetone production
    WO1995014639A1|1995-06-01|Process for the treatment of waste water containing organic and inorganic compounds
    CN104163526B|2016-07-06|A kind of pH that regulates strengthens the method for nitrosamine precursor in ion exchange removal water
    DE1939391A1|1970-02-12|Process for purifying crude ethylene dichloride
    DE102006050608A1|2007-05-03|Procedure for softening drinking water in an industrial reactor using a weakly acidic cation exchanger, comprises regenerating the cation exchanger by the water after taking up alkaline earth metal ions
    EP3867422B1|2022-03-09|Electrochemical system for the synthesis of aqueous oxidising agent solutions
    DE60006718T2|2004-10-28|METHOD FOR RECOVERING COPPER FROM AQUEOUS SOLUTIONS CONTAINING IODINE ORGANIC COMPOUNDS
    DE102017119566B4|2021-08-12|Device for obtaining products from the electrolysis of alkali metal chloride solution
    CH643754A5|1984-06-29|Process for converting a strongly basic ion exchanger resin into the bicarbonate form, and use of the ion exchanger resin regenerated according to this process
    WO2016026646A1|2016-02-25|Method and system for treating swimming pool water, and swimming pool with corresponding system
    WO2016023884A2|2016-02-18|Method for in-situ regeneration of activated carbon loaded with trihalomethanes using alkaline hydrolysis
    DE1163785B|1964-02-27|Process for the production of chlorine produced by the electrolysis of aqueous alkali chloride solutions
    WO2020089192A1|2020-05-07|Method for removing polyfluorinated organic compounds from water by means of an adsorbent and regeneration of the latter
    DE4229355A1|1994-03-10|Process and appts for the removal of chlorinated organic cpds from effluent - esp. from epichlorohydrin prodn
    WO2007048814A1|2007-05-03|Process for softening water using a cation exchanger, and regeneration thereof
    WO2004101147A1|2004-11-25|Regeneration method for cation exchangers
    同族专利:
    公开号 | 公开日
    CN103889906A|2014-06-25|
    WO2012167297A1|2012-12-13|
    EP2718236A1|2014-04-16|
    AT511354B1|2012-11-15|
    CN103889906B|2017-05-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR1578208A|1967-08-24|1969-08-14|
    DE102006001955A1|2006-01-16|2007-07-19|Dge Dr.-Ing. Günther Engineering Gmbh|Purification of wastewater contaminated with organic substances, by catalytic wet oxidation with hydrogen peroxide, comprises treating the wastewater at temperature and pressure in reactor and in catalytic reactor|
    WO2009026208A2|2007-08-23|2009-02-26|Dow Global Technologies Inc.|Brine purification|
    WO2011032311A1|2009-09-17|2011-03-24|宁波万华聚氨酯有限公司|Method for treating waste saline water produced in production process of diphenylmethane diisocyanate |
    DE2559374C2|1975-12-31|1982-10-21|Bayer Ag, 5090 Leverkusen|Process for the wet-oxidative degradation of organic compounds in waste water|
    JPS54129755A|1978-03-31|1979-10-08|Dainippon Ink & Chemicals|Treatment method of waste water|
    DE4415911A1|1994-05-05|1995-11-09|Linde Ag|Process for the treatment of a medium containing organic components|
    DE59806619D1|1997-06-14|2003-01-23|Walter Marte|OXIDATION PROCESS AND SYSTEM FOR TREATING WASTEWATER|
    CN101468843A|2008-08-26|2009-07-01|云南锡业集团（控股）有限责任公司|Processing method for organotin wastewater containing high concentration chloride|
    CN101601998A|2009-06-11|2009-12-16|浙江省环境保护科学设计研究院|A kind of Preparation of catalysts method that is used for treating high-concentration organic wastewater through catalytic oxidation|
    CN101798154B|2009-12-30|2011-04-20|宁波环洋化工有限公司|Method for processing wastewater produced in saponification cyclization step in epoxy chloropropane production method|CN105645624A|2014-11-13|2016-06-08|中国科学院大连化学物理研究所|Resource utilization method for high-salt wastewater from epichlorohydrin preparation through glycerol method|
    CN105621764B|2016-03-17|2018-05-15|浙江奇彩环境科技股份有限公司|A kind for the treatment of process of epoxychloropropane production waste water|
    AT518626A1|2016-04-27|2017-11-15|Kanzler Walter|Process for the oxidation of hydrocarbons in dilute aqueous solutions|
    US20210238071A1|2018-07-27|2021-08-05|Spolek Pro Chemickou A Hutni Vyrobu, Akciova Spolecnost|Process to treat waste brine|
    CN110316808B|2019-07-16|2021-05-07|北京理工大学|Method and apparatus for treating organic wastewater by catalytic wet oxidation|
    CN112159037B|2020-09-25|2021-08-24|南京大学|Dai serge high concentration organic wastewater pretreatment device|
    法律状态:
    2020-02-15| MM01| Lapse because of not paying annual fees|Effective date: 20190607 |
    优先权:
    申请号 | 申请日 | 专利标题
    AT8392011A|AT511354B1|2011-06-07|2011-06-07|METHOD FOR THE PREPARATION OF POLLUTED SOLUTIONS FOR CHLORINE ALKALI ELECTROLYSIS|AT8392011A| AT511354B1|2011-06-07|2011-06-07|METHOD FOR THE PREPARATION OF POLLUTED SOLUTIONS FOR CHLORINE ALKALI ELECTROLYSIS|
    CN201280028114.6A| CN103889906B|2011-06-07|2012-06-06|Method for processing contaminated brine solutions for chlor-alkali electrolysis|
    EP12729834.7A| EP2718236A1|2011-06-07|2012-06-06|Method for processing contaminated brine solutions for chlor-alkali electrolysis|
    PCT/AT2012/000163| WO2012167297A1|2011-06-07|2012-06-06|Method for processing contaminated brine solutions for chlor-alkali electrolysis|
    [返回顶部]