WO2012166021A2 - PROCÉDÉ DE PRODUCTION D'UNE SOLUTION DE DIOXYDE DE CHLORE ET DE CHLORE DANS L'EAU ET APPAREIL DE SA MISE EN œUVRE - Google Patents

PROCÉDÉ DE PRODUCTION D'UNE SOLUTION DE DIOXYDE DE CHLORE ET DE CHLORE DANS L'EAU ET APPAREIL DE SA MISE EN œUVRE Download PDF

Info

Publication number
WO2012166021A2
WO2012166021A2 PCT/RU2012/000435 RU2012000435W WO2012166021A2 WO 2012166021 A2 WO2012166021 A2 WO 2012166021A2 RU 2012000435 W RU2012000435 W RU 2012000435W WO 2012166021 A2 WO2012166021 A2 WO 2012166021A2
Authority
WO
WIPO (PCT)
Prior art keywords
chlorine
housing
solution
chlorine dioxide
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/RU2012/000435
Other languages
English (en)
Russian (ru)
Other versions
WO2012166021A3 (fr
Inventor
Сергей Юрьевич КИРИЛЛОВ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JOINT STOCK Co "URALS SCIENTIFIC - RESEARSH INSTITUTE OF CHEMISTRY WITH EXPERIMENT PLANT"
Original Assignee
JOINT STOCK Co "URALS SCIENTIFIC - RESEARSH INSTITUTE OF CHEMISTRY WITH EXPERIMENT PLANT"
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JOINT STOCK Co "URALS SCIENTIFIC - RESEARSH INSTITUTE OF CHEMISTRY WITH EXPERIMENT PLANT" filed Critical JOINT STOCK Co "URALS SCIENTIFIC - RESEARSH INSTITUTE OF CHEMISTRY WITH EXPERIMENT PLANT"
Publication of WO2012166021A2 publication Critical patent/WO2012166021A2/fr
Publication of WO2012166021A3 publication Critical patent/WO2012166021A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C01B11/023—Preparation from chlorites or chlorates
    • C01B11/025—Preparation from chlorites or chlorates from chlorates without any other reaction reducing agent than chloride ions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/685—Devices for dosing the additives
    • C02F1/686—Devices for dosing liquid additives
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens

Definitions

  • the invention relates to the production of chlorine-containing oxidizing agents used as reagents in the disinfection and purification of drinking water, wastewater, recycled water, and in particular, to the production of an aqueous solution of a mixture of chlorine dioxide and chlorine.
  • An analogue of the present invention is a method and a reactor for producing a solution of chlorine dioxide (see RF patent for the invention N ° 2188791 "Method and reactor for producing a solution of chlorine dioxide", IPC ⁇ 01 ⁇ 11 / 02, application date 08.02.2001, published on 09/10/2002).
  • the process of producing chlorine dioxide and chlorine is carried out by reacting a solution of chlorate and sodium chloride with sulfuric acid in a multi-chamber reactor. Reagents are fed into the upper chamber of the reactor.
  • Chlorine dioxide and chlorine are emitted from the reaction solution in the form of bubbles, enter the gas-air space of the reactor and are removed from there by air, which is pumped through the reaction solution and the reactor using an ejector due to a vacuum of 75-150 mm Hg.
  • the chambers in the reactor are cascaded.
  • the reaction solution is poured through the wall of the upstream chamber into the underlying chamber.
  • the spent reaction solution, together with chlorine dioxide, chlorine and air entering the reactor is sucked out by a water-jet ejector.
  • additional water is supplied to the lower chamber.
  • Mixing of the reagents in the upper chamber is carried out by bubbling air supplied to the reactor.
  • the absorption of gaseous chlorine dioxide and chlorine by water and the preparation of a solution of chlorine dioxide and chlorine occurs in a water-jet ejector connected to the reactor.
  • This invention provides a high degree of conversion of chlorate to chlorine dioxide, but its significant drawback is the need to purge the reactor with air to sparge and remove gaseous chlorine dioxide and chlorine since the circulation in the solution is negligible. This leads to high power consumption and unstable hydrodynamics of the device.
  • the disadvantages of the analogue include: the inability to supply the solution from the installation directly to the suction line of a centrifugal pump; the impossibility of dividing the flow of the solution from the installation; at high capacities - the need for an absorption tower for air purification from chlorine-containing gases.
  • the closest analogue is the prototype of the invention is the European patent EP 3 ° 0106503, filing date 08.09.1983, publ. 06/11/1986
  • the interaction of the reactants in the reactor is carried out by the reduction of chlorate ions with chloride ions in a reaction medium containing sulfuric acid with a total acidity of 8.5-12 normal by supplying a solution of chlorate and sodium chloride and sulfuric acid to the reaction zone and removing the spent reaction solution from reaction zones.
  • a rarefied atmosphere is used to remove the gas mixture from water vapor.
  • the residence time of the reaction solution in the reaction zone is controlled.
  • the process is carried out at a temperature of 40-70 ° C under boiling conditions of the reaction mixture, which is ensured by maintaining a high vacuum (absolute pressure from 60 to 160 mm Hg or 8 21 kPa) without air purging.
  • a hollow cylindrical apparatus As a reactor for the production of chlorine dioxide and chlorine, a hollow cylindrical apparatus is used with separate inlets of a solution of chlorate and sodium chloride and sulfuric acid through the walls of the housing near the bottom, vertical rod-shaped heating elements of the reaction solution, brought through the bottom of the housing and placed in exhaust pipes, as well as one common a hole at the top cover to withdraw the resulting gas mixture diluted with water vapor and the spent reaction solution into the ejector.
  • the description due to strict automatic control of the regime and overflow of the spent reaction solution from the apparatus, crystallization of sodium sulfate from the solution in the reaction zone is prevented.
  • Boil mode on the one hand, to maintain a sufficiently high rate of vapor to the surface area of reaction medium (more than 0.5 g / m "cm2 in terms of chlorine dioxide) and have a small reactor volume (the size of the reactor in the installation arrangement, not all is of decisive importance).
  • the presence of a heating surface in addition to increasing energy consumption, imposes rather stringent conditions on the stationarity of the process, and hence its safety: the description indicates the possibility of localized zones of solution overheating, the formation of large gas bubbles and the breakdown of chlorine dioxide - “panting”.
  • the possibility of partial losses of chlorine dioxide due to its spontaneous decomposition near heating elements, as well as crystallization of sodium hydrogen sulfate from the reaction solution is not ruled out.
  • the stationarity of the process directly depends on the circulation of the solution in the apparatus.
  • the circulation in the reaction zone is carried out by heating, and without heating, the apparatus with the design characteristics given in the description, as it turned out during experimental reproduction, can work for no more than 2 hours. After that, the unevenness of temperature and concentration by volume begins to affect, "pant” and "pops" appear. This must be accompanied by an automatic shutdown of the installation.
  • the technical task is to reduce energy consumption for obtaining a solution of chlorine dioxide and chlorine and increase the stability of the hydrodynamic regime of the apparatus.
  • the technical problem is solved in that the method of producing a solution of chlorine dioxide and chlorine by the interaction of a solution of chlorate and sodium chloride with high sulfuric acid involves the use of a rarefied atmosphere to remove the resulting vapor-gas mixture of chlorine dioxide, chlorine and water, maintaining the concentration of sodium sulfate less saturation level of the reaction medium. At the same time, a rarefaction is maintained in the reaction zone (absolute pressure 22-100 kPa).
  • the absolute pressure scale i.e. absolute vacuum - 0 kPa, normal atmospheric pressure 760 mm Hg. Art. - 103.3 kPa, etc.
  • vacuum the "pressure"
  • an apparatus for producing a solution of chlorine dioxide and chlorine comprising a housing with nozzles for introducing reagents located in the lower part of the housing, an outlet for outputting gaseous products and spent aqueous solution located in the upper part of the housing and connected to an ejector connected to apparatus.
  • a circulation device in the form of a shell is fixed coaxially to the housing, and nozzles for introducing reagents are located in the end part of the housing, are inserted inside the circulation device and are located coaxially to the axis of the housing.
  • the casing of the apparatus can be made in the form of a shell with a section increasing towards the top.
  • the circulation device, made in the lower part of the body in the form of a shell can also have a cross section that increases towards the top.
  • the housing and the circulation device can be made in the form of a truncated cone.
  • the main difference between the proposed technical solution and the prototype of the method is the lack of heating and a lower vacuum (i.e., greater absolute pressure) in the apparatus.
  • a lower vacuum i.e., greater absolute pressure
  • the entire flow of treated water is supplied to the ejector of the installation, according to the claimed solution, only its smaller part (less than 5%), and the resulting technological solution is further connected to the general flow of disinfected water. Therefore, the specific energy consumption for obtaining a solution of chlorine dioxide and chlorine is significantly reduced.
  • the working pressure in the reactor according to the prototype is 60 160 mm Hg or 8 + 21 kPa. According to the claimed solution, it is proposed to conduct the process at a pressure of 22 + 100 kPa.
  • the stability of the hydrodynamic regime of the apparatus largely depends on the constancy of the pressure of the water supplied to the ejector. For example, at a nominal water pressure of 250 kPa, a short-term change in this pressure by 30 kPa (which is quite possible under real conditions) for an apparatus operating at a pressure of 40 kPa will only lead to its violation hydrodynamic regime while maintaining operability, but for an apparatus operating at a pressure below 22 kPa, this can cause the circulation of the solution in it to cease and, as a result, "pant” and "pops", leading to the termination of the apparatus.
  • the working temperature of the solution in the apparatus takes on higher values and the probability of spontaneous decomposition of chlorine dioxide increases significantly - the appearance of "panting” and "pops" leading to the termination of the apparatus.
  • the claimed apparatus due to the presence of a circulation device and an optimal design is characterized by a stationary mode and can operate in continuous installations with the possibility of changing its chlorine dioxide productivity over a wide range.
  • Table 1 shows the comparative specific energy consumption for the production of a solution of chlorine dioxide and chlorine.
  • the figure 1 presents a variant of the apparatus for implementing the method.
  • the apparatus comprises a housing (1) with an integrated circulation device (2).
  • the housing consists of two coaxial cylinders, with the cross section of the upper cylinder being larger than the cross section of the lower cylinder.
  • pipes for supplying sulfuric acid (3) and chlorate-chloride solution (4) are brought in inside the circulation device (2) parallel to its axis.
  • In the upper part of the housing (1) there is a pipe for the removal of vapor-gas-liquid mixture (5), connected to the ejector (6).
  • In the housing (1) of the apparatus there are openings for measuring the temperature of the solution (7) and pressure (8).
  • the device operates as follows. Water is supplied to the ejector (6), and a reduced pressure immediately forms in the apparatus, which is measured by the device through the pipe (8). When the pressure reaches 10 kPa, the water supply is stopped, and the housing (1) through the pipe (5) and the ejector (6) is automatically filled with water from the process solution pipeline due to the residual reduced pressure in the apparatus. After that, the water supply to the ejector (6) is resumed and its nominal pressure is set, while excess water from the casing (1) of the apparatus is sucked off by the ejector (6) through the pipe (5). Thus, the water level (and subsequently the level of the working solution) in the apparatus is determined by the position of the nozzle (5). Sulfuric acid is fed into the apparatus through a pipe (3), brought into the circulation device (2).
  • the circulating fluid circuit is formed in the apparatus, marked in figure 1: the inner part of the circulating device (2) - the upper part of the apparatus - the gap between the circulating device (2) and the lower part of the casing (1) of the apparatus - the lower part of the casing (1) - the inner part of the circulation device (2).
  • the gaseous chlorine dioxide and chlorine resulting from the chemical reaction, as well as the liquid phase from the housing (1), are sucked off by an ejector (6) through a pipe (5), where from mixing with water supplied to the ejector (6), the resulting aqueous solution is then sent to water treatment.
  • the apparatus allows you to vary the performance of a solution of chlorine dioxide and chlorine over a wide range without disturbing the hydrodynamics by changing the flow rate of the reagents supplied to it.
  • the shutdown of the apparatus is reduced to stopping the supply of acid and solution, as a result of which the pressure in the apparatus rapidly decreases and the apparatus is filled with water through the pipe (5), thereby terminating the chemical reaction in it.
  • Monitoring the operation of the apparatus is carried out by the pressure and temperature of the working solution in it, for which, through the nozzles (7) and (8), the sensors of the corresponding devices are introduced inside.
  • Example 1 Obtaining an aqueous solution of chlorine dioxide and chlorine lead in a cylindrical vertically arranged apparatus of continuous operation. Case inner diameter 46 mm, height 250 mm, cylindrical diameter circulation device 20 mm, height 150 mm.
  • Example 2 The method of carrying out the process is similar to that described in example 1. Obtaining an aqueous solution of chlorine dioxide and chlorine is carried out in a cylindrical vertically arranged apparatus of continuous action.
  • the inner diameter of the upper part of the apparatus is 150 mm, the height is 140 mm; inner diameter of the lower part of the apparatus - 70 mm, height - 210 mm; the diameter of the circulation pipe is 32 mm, the height is 220 mm, a disk with an outer diameter of 130 mm is attached to the upper end of the pipe.
  • the feed rate of the acid into the reactor is maintained at 1.5 l / h, the feed rate of the chlorate and sodium chloride solution is 2.75 l / h.
  • the water flow through the ejector is 1.56 m3 / h, the pressure (absolute) at the inlet to the ejector is 0.29 MPa, the discharge from the ejector is free.
  • the pressure (absolute) in the reactor is 26 kPa, and the temperature is 56 ° C.
  • the chlorine dioxide productivity in this case is 0.5 kg / h.
  • Example 3 The method of carrying out the process is similar to that described in example 1.
  • the preparation of an aqueous solution of chlorine dioxide and chlorine is carried out in a continuous apparatus, the apparatus body and the circulating device are truncated cones with diameters in the lower part of 70 and 35 mm, respectively, with diameters in the upper part of 180 and 100 mm, respectively, and heights of 300 and 210 mm, respectively.
  • the acid feed rate to the reactor was maintained at 2.03 l / h, the feed rate of the chlorate and sodium chloride solution was 3.85 l / h.
  • the water flow through the ejector is 2.22 m3 / h, the pressure (absolute) of the water at the inlet to the ejector is 0.16 MPa, the discharge from the ejector is free.
  • the pressure (absolute) in the reactor is 70 kPa, and the temperature is 65 ° C.
  • the chlorine dioxide productivity is 0.7 kg / h.
  • Example 4 The method of carrying out the process is similar to that described in example 1.
  • the preparation of an aqueous solution of chlorine dioxide and chlorine is carried out in a continuous apparatus, the apparatus body and the circulation device are truncated cones with diameters in the lower part of 45 and 25 mm, respectively, with diameters in the upper part of 130 and 55 mm, respectively, and a height of 210 and 130 mm, respectively.
  • Speed the acid supply to the reactor is maintained at 3.0 l / h, the feed rate of the chlorate and sodium chloride solution is 5.5 l / h.
  • the water flow through the ejector is 0.40 m3 / h, the pressure (absolute) of the water at the inlet to the ejector is 3.0 MPa, the discharge from the ejector is free.
  • the pressure (absolute) in the reactor is 100 kPa, the temperature is 63 ° C.
  • the chlorine dioxide productivity in this case is 0.8 kg / h).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

L'invention concerne la production d'oxydants chlorés utilisés en tant que réactifs pour décontaminer et purifier l'eau potable et notamment d'un mélange aqueux de dioxyde de chlore et de chlore. L'objectif technique visé est de réduire la consommation d'énergie et d'améliorer la stabilité du régime hydrodynamique de l'appareil. Cet objectif est réalisé grâce au fait que le procédé de production de mélange de dioxyde de chlore et de chlore est mis en œuvre par l'interaction du chlorate et du chlorure de sodium avec de l'acide sulfurique hautement concentré en utilisant une atmosphère très ténue pour évacuer de la zone de réaction du mélange vapeur /liquide en formation de dioxyde de chlore, de chlore et de solution de sulfate de sodium. La concentration de sulfate de sodium est maintenue à un niveau inférieur de saturation du milieu de réaction, et on crée dans la zone de réaction une pression absolue de 22-100 kPa. Pour mettre en œuvre le procédé on utilise un appareil comprenant un corps avec des tubulures d'admission de réactifs disposées dan la partie inférieur du corps et une tubulure d'évacuation des produits gazeux et de la solution aqueuse épuisée, ladite tubulure se situant dan la partie supérieure du corps et étant raccordée à un éjecteur raccordé à l'appareil. Coaxialement au corps on a monté un dispositif de recirculation se présentant comme une virole, et les tubulures d'admission et d'évacuation sont disposées dans la partie d'extrémité du corps, pénètrent à l'intérieur du dispositif de recirculation et se situent coaxialement à l'axe du corps.
PCT/RU2012/000435 2011-05-31 2012-06-04 PROCÉDÉ DE PRODUCTION D'UNE SOLUTION DE DIOXYDE DE CHLORE ET DE CHLORE DANS L'EAU ET APPAREIL DE SA MISE EN œUVRE Ceased WO2012166021A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2011122125 2011-05-31
RU2011122125/05A RU2503614C2 (ru) 2011-05-31 2011-05-31 Аппарат для осуществления способа получения раствора диоксида хлора и хлора в воде

Publications (2)

Publication Number Publication Date
WO2012166021A2 true WO2012166021A2 (fr) 2012-12-06
WO2012166021A3 WO2012166021A3 (fr) 2013-01-31

Family

ID=47260144

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2012/000435 Ceased WO2012166021A2 (fr) 2011-05-31 2012-06-04 PROCÉDÉ DE PRODUCTION D'UNE SOLUTION DE DIOXYDE DE CHLORE ET DE CHLORE DANS L'EAU ET APPAREIL DE SA MISE EN œUVRE

Country Status (2)

Country Link
RU (1) RU2503614C2 (fr)
WO (1) WO2012166021A2 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4079123A (en) * 1976-12-30 1978-03-14 Hooker Chemicals & Plastics Corporation Process for the production of chlorine dioxide
CA1163420A (fr) * 1982-09-09 1984-03-13 Erco Industries Limited Fabrication de bioxyde de chlore a petite echelle
RU2028867C1 (ru) * 1991-10-22 1995-02-20 Александр Владимирович Дворянинов Способ изготовления корпуса в форме усеченного конуса
RU2064450C1 (ru) * 1992-04-01 1996-07-27 Леонид Григорьевич Корниевский Биореактор
RU45378U1 (ru) * 2004-12-20 2005-05-10 Федеральное Государственное унитарное предприятие "Уральский научно-исследовательский химический институт с опытным заводом" /ФГУП "УНИХИМ с ОЗ"/ Установка для получения диоксида хлора

Also Published As

Publication number Publication date
RU2011122125A (ru) 2012-12-10
WO2012166021A3 (fr) 2013-01-31
RU2503614C2 (ru) 2014-01-10

Similar Documents

Publication Publication Date Title
EP0106503B1 (fr) Production de péroxyde de chlore
KR101697526B1 (ko) 고효율 마이크로오존버블반응기를 포함하는 오존수처리 시스템
CN1134140A (zh) 制造环氧烷类的方法
JP2015071141A5 (fr)
CN112456450B (zh) 一种含有机物废硫酸资源化利用的系统和方法
JP5392836B2 (ja) 一酸化炭素ガスの製造方法および製造装置
RU2503614C2 (ru) Аппарат для осуществления способа получения раствора диоксида хлора и хлора в воде
JP2017209615A (ja) 尿素水溶液の処理方法および装置
TW200624375A (en) Chemical process and apparatus
JP6197913B1 (ja) 有機物含有排水の処理方法及び装置
RU2307067C2 (ru) Способ получения раствора диоксида хлора и хлора в воде и реактор для его осуществления
JPH0671594B2 (ja) 水中の溶存酸素の除去方法および装置
RU2188791C1 (ru) Способ и реактор получения раствора диоксида хлора
JP5388199B2 (ja) 一酸化炭素ガスの製造方法および製造装置
AU2015298397A1 (en) Sequencing batch facility and method for reducing the nitrogen content in waste water
JP5012638B2 (ja) オゾン溶液の処理方法
RU156915U1 (ru) Устройство для очистки и обеззараживания воды
JP2004243280A (ja) 汚泥の好気性消化処理方法および装置
KR20220144121A (ko) 가스 용해장치
KR20070076437A (ko) 수처리 장치 및 발전 장치
KR101136023B1 (ko) 오존재활용 기능을 갖는 오존산화장치
KR101844955B1 (ko) 오존수 제조장치를 이용한 용수공급 시스템 및 이를 이용한 폐수처리 방법
EP4448973B1 (fr) Agencement d'éjecteur de jet, système et utilisation associés et son procédé de fonctionnement
CN103402622B (zh) 改进的氧化方法和反应器
CN211864583U (zh) 一种高浓度臭氧水制备装置

Legal Events

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

Ref document number: 12793338

Country of ref document: EP

Kind code of ref document: A2

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12793338

Country of ref document: EP

Kind code of ref document: A2