WO2009115888A1 - Procédé permettant la récupération d'eau et de matière organique de valeur à partir d'eaux usées au cours de la production d'acides carboxyliques organiques - Google Patents

Procédé permettant la récupération d'eau et de matière organique de valeur à partir d'eaux usées au cours de la production d'acides carboxyliques organiques Download PDF

Info

Publication number
WO2009115888A1
WO2009115888A1 PCT/IB2009/000522 IB2009000522W WO2009115888A1 WO 2009115888 A1 WO2009115888 A1 WO 2009115888A1 IB 2009000522 W IB2009000522 W IB 2009000522W WO 2009115888 A1 WO2009115888 A1 WO 2009115888A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
process according
organics
polymeric adsorbent
water
Prior art date
Application number
PCT/IB2009/000522
Other languages
English (en)
Inventor
Marzio Monagheddu
Luciano Piras
Giovani Cocco
Original Assignee
Dow Italia S.R.L.
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 Dow Italia S.R.L. filed Critical Dow Italia S.R.L.
Priority to CN2009801100269A priority Critical patent/CN102149642A/zh
Priority to JP2011500304A priority patent/JP2011515386A/ja
Publication of WO2009115888A1 publication Critical patent/WO2009115888A1/fr

Links

Classifications

    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

Definitions

  • the present invention relates to a process for recovery of water and valuable organics from wastewater during the production of aromatic carboxylic acids using polymeric absorbent resins.
  • Aromatic poly carboxylic acids such as terephthalic acid, isophthalic acid and trimellitic acid, are often produced by oxidation of alkyl aromatics with oxygen containing gas, to form crude product.
  • the crude product is mixed with a solvent to form a slurry, dissolved at high temperature, and subjected to hydrogenation to increase product purity.
  • the effluent of the hydrogenation reactor is crystallized and then sent to two stages of solid liquid separation.
  • the mother liquor from the first stage solid liquid separation contains water, metals, valuable organics, and other impurities, but cannot be recycled due to the high content of impurities.
  • the first stage mother liquor is generally sent to disposal. There is an opportunity to recover valuable organics present in the first stage mother liquor (sometimes referred to as a purge stream), and re use at least part of the purified water in the manufacturing process, thereby reducing plant environmental impact, water consumption and production losses.
  • JP2000070934A, and JP58135834 all describe processes utilizing ion exchange resins to purity wastewater, while the process reported in US5236594 describes using a non-ionic macroreticular polymeric resin.
  • Other efforts for purification of wastewater using various adsorbent materials include, for example, those described in US4079001, US4097376, JP55105636, and EP0966405.
  • US4670155 also describes a process utilizing a sorbent material. This reference recites removal of water from an organic compound by first co-sorbing an organic compound and water directly onto a particulate bed, and flowing a volatilized compound through the bed, wherein the volatilized compound preferentially volatizes water.
  • the present invention is a process for the removal of organics and recovery of water and organics from a liquid stream in a terephthalic acid production process, an isophthalic acid process, a trimellitic acid process, or a naphthalene dicarboxylic acid process, comprising the step of contacting the liquid stream with a polymeric adsorbent to form purified water.
  • Subsequent steps include regenerating the polymeric adsorbent resin by contacting the polymeric adsorbent resin with polymeric adsorbent resin regeneration solution to form recovered organics, washing the polymeric adsorbent resin with a washing solution comprising substantially water, and removing remaining regeneration solution adsorbed on the polymeric adsorbent resin by contacting the resin with a fluid comprising hot water, steam, or a hot inert gas.
  • the present invention provides a method for the recovery of water and organics without the need for pretreatment of the liquid stream or extra processing steps.
  • the use of a polymeric adsorbent resin provides an alternative to activated carbon that is significantly easier to regenerate on site resulting in smaller systems and lower costs.
  • the polymeric adsorbent resins also have high surface area and are free of salts, metals, and minerals that can leach back into product streams or catalyze undesirable reactions.
  • Polymeric adsorbents are engineered for regeneration under milder conditions than activated carbon, making on-site regeneration possible and allowing the organics to be returned to the process eliminating waste and cost.
  • the present invention involves the removal of organics from water, and the recovery of water and organics from a liquid stream in a chemical process.
  • Chemical processes suitable for employing the present invention include terephthalic acid production processes, isophthalic acid production processes, trimellitic acid processes, and naphthalene dicarboxylic acid production processes.
  • the liquid stream to be treated using the present invention is typically a wastewater stream in the chemical process, such wastewater stream comprising water, metals and organics.
  • the organics in the liquid stream include mono and poly alkyl substituted aromatic mono and poly carboxylic acids; mono and poly formil substituted aromatic mono and poly carboxylic acids; aromatic alkyl aldehydes, mono and poly alkyl substituted aromatic mono and poly aldehydes; aromatic carboxylic acid, aromatic poly carboxylic acid, where the aromatic part can include one or more condensate aromatic ring; and combinations thereof.
  • organic compounds to be removed are: toluic acid, terephthalic acid, isophthalic, carboxybenzaldehyde, benzoic acid, benzene tricarboxylic acid, trimellitic acid, dimethyl benzoic acid; methyl naphthalene-carboxylic acid; methyl benzoic acid; formyl benzene-dicarboxylic acid; diformyl benzoic acid; formyl naphthalene-carboxylic acid; formyl benzoic acid; dimethyl benzaldehyde; methylbenzene-dicarbaldehyde; naphthalene-dicarbaldehyde; benzene-dicarbaldehyde; methyl naphthalene-carbaldehyde; methyl benzaldehyde; naphthalene-dicarboxylic acid; benzene-tricarboxylic acid; benzene- dicarboxylic acid; and any combination
  • the first step of the present invention comprises contacting the liquid stream with a polymeric absorbent resin.
  • the result is purified water, with the organics remaining adsorbed to the polymeric adsorbent resin at this stage.
  • This first step may be performed in one or more beds in series as necessary to sufficiently separate the organics from the liquid stream.
  • the purified water can then be, at least partially, recycled back into the chemical process.
  • the first contacting step described above is conducted at a temperature of from 40 to 100 degrees C, and more preferably from 60 to 80 degrees C.
  • the first contacting step is conducted in any conventional particulate resin bed apparatus. Those skilled in the art will know the typical resin beds that may be used, including for example, fluidized beds, and more preferably, fixed beds.
  • the polymeric adsorbent resin After a period of time, as with most adsorbents, the polymeric adsorbent resin will become fully loaded with organics and therefore must be regenerated.
  • a resin bed is typically sized to last for a specified period of time before regeneration is required, or that the concentration levels of organics in the effluent stream from the resin bed will change, signaling a need for regeneration.
  • the organics are recovered and optimally may be used in the production process for the aromatic carboxylic acids.
  • the resin is contacted with a polymeric adsorbent resin regeneration solution.
  • the polymeric adsorbent resin regeneration solution comprises an aliphatic carboxylic acid solution having a concentration of from 70 to 100% acid in solution.
  • the polymeric adsorbent resin regeneration solution is an acetic acid solution with a concentration of from 80-100% acetic acid in solution, and more preferably from 90-100% acetic acid.
  • the recovered organics can then be recycled back into the chemical process.
  • the regenerating step is conducted at a temperature of from 40 to 100 degrees C, and more preferably from 60 to 80 degrees C.
  • the regeneration step is performed using any conventional pumping apparatus useful for pumping acetic acid through the resin bed.
  • the polymeric adsorbent resin is washed with a washing solution.
  • the washing solution is comprised of 90% or greater water. If any of the polymeric adsorbent resin regeneration solution remains adsorbed on the polymeric adsorbent resin after the washing step, it is removed by contacting the resin with a fluid comprising hot water, steam, or a hot inert gas.
  • Suitable polymeric adsorbent resins for use in the present invention include any high surface area highly cross-linked resin.
  • polymeric adsorbent resins include styrene polymer resins, and more preferably, styrene/divinylbenzene macroporous resins, such as those sold under the OPTIPORE trademark.
  • OPTIPORE L-493 is a particularly preferred polymeric adsorbent resin.
  • the polymeric adsorbent resins used in the present invention interact with a non-charged side of a molecule and therefore can be used with any organic compound, whether acidic, basic or neutral.
  • Polymeric adsorbent resins utilize a combination of mechanisms in the adsorption process, including Van der Waals forces, steric interaction, hydrogen bonding, hydrophobicity, and polarity, and the presence of charged ions is not critical.
  • one jacketed column is packed with 390 ml of settled highly cross- linked styrenic polymer (OPTIPORE L-493, The Dow Chemical Company).
  • the bed diameter is 2.54 cm and the bed height is 77 cm, for a resin bed volume of 390 ml.
  • the process fluid is collected from the plant in the reservoir, and allowed to cool down to ambient temperature. It is then connected to the lab apparatus, heated at 75 0 C, and then pumped through the resin.
  • the column is kept at 70 0 C by feeding hot water to the column jacket.
  • Chemical Oxygen Demand (“COD”), a test used to measure the amount of organic compounds in water, is measured in the reservoir.
  • COD is expressed in parts per million (ppm), which indicates the mass of oxygen consumed per liter of solution.
  • Samples are collected on the discharge side of the column and analyzed for COD.
  • the liquid not sampled is collected in known volume tanks and analyzed for COD.
  • Regeneration is performed by pumping through the loaded resin 96% acetic acid 4% water solution.
  • the column is kept at 70 0 C by feeding hot water to the column jacket.
  • the whole effluent is collected in a tank and analyzed for the organic content (excluding acetic acid.)
  • the amount of organics present in the wastewater stream is quantified in terms of COD according to ASTM D1252.
  • the recovered organics can not be evaluated by ASTM D 1252 because the regenerating agent is an organic acid, and therefore they are analyzed by HPLC according to the following operating conditions:
  • This example describes the results of adsorption.
  • the jacketed column is fed from the top to the bottom with 95,000 ml of mother liquor from a terephthalic acid production process at a flow rate of 140 ml/min, keeping the temperature at 70 0 C.
  • Table A shows the results.
  • bed volume means 50 x 390, or 19500 ml of sample pumped once through the column. ** 100 bed volume means 100 x 390, or 39000 ml of sample pumped once through the column. *** 200 bed volume means 200 x 390, or 78000 ml of sample pumped once through the column.
  • This example describes regeneration of the resin and recovery of organic compounds.
  • the jacketed column is drained and then fed, from the bottom to the top, with 4208 ml of regenerating fluid comprising 93% acetic acid and 7% water, at a flow rate of 48 ml/min, keeping the temperature at 70 0 C.
  • the amount of COD adsorbed onto the resin prior to this example is 136 g.
  • the composition of the effluent resulting from the regeneration is listed in Table B.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé d'élimination et de récupération d'eau et de matière organique à partir d'un flux liquide dans un procédé chimique. Le procédé comprend l'étape consistant à mettre en contact le flux liquide avec un adsorbant polymère pour former de l'eau purifiée. Les étapes suivantes comprennent la régénération de la résine adsorbante polymère en mettant en contact la résine adsorbante polymère avec une solution de régénération de la résine adsorbante polymère pour former de la matière organique récupérée ; le lavage de la résine adsorbante polymère avec une solution de lavage comprenant essentiellement de l'eau ; et l'élimination de la solution de régénération restante adsorbée sur la résine adsorbante polymère en mettant en contact la résine avec un fluide comprenant de l'eau chaude, de la vapeur, ou un gaz inerte chaud.
PCT/IB2009/000522 2008-03-20 2009-03-16 Procédé permettant la récupération d'eau et de matière organique de valeur à partir d'eaux usées au cours de la production d'acides carboxyliques organiques WO2009115888A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2009801100269A CN102149642A (zh) 2008-03-20 2009-03-16 从生产芳族羧酸的废水中回收水和有价值的有机物的方法
JP2011500304A JP2011515386A (ja) 2008-03-20 2009-03-16 芳香族カルボン酸の生産における廃水からの水および価値のある有機物の回収の方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7018408P 2008-03-20 2008-03-20
US61/070,184 2008-03-20

Publications (1)

Publication Number Publication Date
WO2009115888A1 true WO2009115888A1 (fr) 2009-09-24

Family

ID=40823508

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2009/000522 WO2009115888A1 (fr) 2008-03-20 2009-03-16 Procédé permettant la récupération d'eau et de matière organique de valeur à partir d'eaux usées au cours de la production d'acides carboxyliques organiques

Country Status (4)

Country Link
JP (1) JP2011515386A (fr)
KR (1) KR20100133441A (fr)
CN (1) CN102149642A (fr)
WO (1) WO2009115888A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102139976A (zh) * 2011-02-22 2011-08-03 上海化学工业区中法水务发展有限公司 Mdi生产过程中含盐废水的处理方法
EP2602240A1 (fr) * 2011-12-08 2013-06-12 Solvay Sa Procédé d'extraction d'acides dicarboxyliques aromatiques
US9315739B2 (en) 2011-08-18 2016-04-19 Kior, Llc Process for upgrading biomass derived products
US9382489B2 (en) 2010-10-29 2016-07-05 Inaeris Technologies, Llc Renewable heating fuel oil
US9387415B2 (en) 2011-08-18 2016-07-12 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
US9447350B2 (en) 2010-10-29 2016-09-20 Inaeris Technologies, Llc Production of renewable bio-distillate
US10427069B2 (en) 2011-08-18 2019-10-01 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
US10919787B2 (en) 2015-11-13 2021-02-16 Sabic Global Technologies B.V. Process using ion exchange resins for the treatment of wastewater emanating from purified terephthalic acid production

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104512943B (zh) * 2013-09-29 2016-05-11 中国石油化工股份有限公司 一种芳香族羧酸生产过程中氧化废水回用工艺
KR102526479B1 (ko) 2018-11-29 2023-04-26 롯데케미칼 주식회사 산화반응 모액으로부터의 유기산의 분리방법
CN110252269A (zh) * 2019-06-13 2019-09-20 江苏南大环保科技有限公司 一种用于处理含有高沸物废水的树脂再生方法
CN110252268A (zh) * 2019-06-13 2019-09-20 江苏南大环保科技有限公司 一种氯苯生产废水吸附树脂的再生方法
CN110975851B (zh) * 2019-12-26 2022-06-03 江苏南大环保科技有限公司 一种吸附有机物的树脂脱附再生方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207184A (en) * 1975-06-17 1980-06-10 Ciba-Geigy Ag Process for the purification of industrial effluents
US4675108A (en) * 1983-11-30 1987-06-23 Ecolochem, Inc. Apparatus for treating wash water from the manufacture of terephthalic acid
CN1680195A (zh) * 2005-01-13 2005-10-12 南京大学 对苯二甲酸生产废水的治理及其资源的回收方法
CN1935776A (zh) * 2006-10-24 2007-03-28 南京大学 一种治理邻苯二甲酸二乙酯废水并从中回收邻苯二甲酸二乙酯的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0556329A (ja) * 1991-08-23 1993-03-05 Mitsubishi Heavy Ind Ltd 画像ぶれ量検出装置
JP3952429B2 (ja) * 1998-08-27 2007-08-01 月島機械株式会社 テレフタル酸廃液の処理方法およびその処理装置
JP5028707B2 (ja) * 2000-09-22 2012-09-19 三菱瓦斯化学株式会社 芳香族カルボン酸の製造方法
JP2006298905A (ja) * 2005-03-22 2006-11-02 Mitsubishi Chemicals Corp 高純度テレフタル酸の製造方法
US20100048943A1 (en) * 2006-12-20 2010-02-25 Mitsubishi Gas Chemical Company Inc. Process for production of isophthalic acid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207184A (en) * 1975-06-17 1980-06-10 Ciba-Geigy Ag Process for the purification of industrial effluents
US4675108A (en) * 1983-11-30 1987-06-23 Ecolochem, Inc. Apparatus for treating wash water from the manufacture of terephthalic acid
CN1680195A (zh) * 2005-01-13 2005-10-12 南京大学 对苯二甲酸生产废水的治理及其资源的回收方法
CN1935776A (zh) * 2006-10-24 2007-03-28 南京大学 一种治理邻苯二甲酸二乙酯废水并从中回收邻苯二甲酸二乙酯的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PAN B; ZHANG W; LV L; ZHANG Q; ZHENG S: "Development of polymeric and polymer-based hybrid adsorbents for pollutants removal from waters", CHEMICAL ENGINEERING JOURNAL, vol. 151, no. 1-3, 11 March 2009 (2009-03-11), pages 19 - 29, XP002536738 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9382489B2 (en) 2010-10-29 2016-07-05 Inaeris Technologies, Llc Renewable heating fuel oil
US9447350B2 (en) 2010-10-29 2016-09-20 Inaeris Technologies, Llc Production of renewable bio-distillate
CN102139976A (zh) * 2011-02-22 2011-08-03 上海化学工业区中法水务发展有限公司 Mdi生产过程中含盐废水的处理方法
US9315739B2 (en) 2011-08-18 2016-04-19 Kior, Llc Process for upgrading biomass derived products
US9387415B2 (en) 2011-08-18 2016-07-12 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
US10427069B2 (en) 2011-08-18 2019-10-01 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
EP2602240A1 (fr) * 2011-12-08 2013-06-12 Solvay Sa Procédé d'extraction d'acides dicarboxyliques aromatiques
US10919787B2 (en) 2015-11-13 2021-02-16 Sabic Global Technologies B.V. Process using ion exchange resins for the treatment of wastewater emanating from purified terephthalic acid production

Also Published As

Publication number Publication date
CN102149642A (zh) 2011-08-10
JP2011515386A (ja) 2011-05-19
KR20100133441A (ko) 2010-12-21

Similar Documents

Publication Publication Date Title
WO2009115888A1 (fr) Procédé permettant la récupération d'eau et de matière organique de valeur à partir d'eaux usées au cours de la production d'acides carboxyliques organiques
EP2301893B1 (fr) Procédé pour traiter des eaux usées
WO2010071599A1 (fr) Procédé de traitement d’eaux usées produites dans un procédé de production d’acide aromatique
EP3003985B1 (fr) Procédé de réduction de la teneur totale en carbone organique dans des eaux usées
JP2005536326A5 (fr)
CN101058467B (zh) 一种精对苯二甲酸生产废水的处理方法
CA2908789A1 (fr) Procede et installation de traitement des eaux provenant des industries petrolieres et gazieres, notamment des eaux de production des champs petroliers et/ou gaziers
WO2016139626A1 (fr) Procédé de séparation de polluant à partir d'eaux usées et son système
EP2291330B1 (fr) Procédé pour le traitement du courant aqueux provenant de la réaction de fischer-tropsch au moyen de résines échangeuses d'ions
CN111995152B (zh) 利用甲基硫酸钠废渣合成苯甲醚时所产生的高浓度废水的处理方法
JP2006298905A (ja) 高純度テレフタル酸の製造方法
EP2234924A1 (fr) Procédé pour le traitement du courant aqueux provenant de la réaction de fischer-tropsch
JPH08229413A (ja) トリメリット酸製造用酸化触媒の分離方法
EP3374318B1 (fr) Procédé utilisant des résines d'échange d'ions pour le traitement d'eaux usées émanant de production d'acide téréphtalique purifié
CN101745410B (zh) 从芳香酸纯化过程产生的废水中回收催化剂的方法
RU2394017C2 (ru) Способ получения высокочистой терефталевой кислоты
WO2014189786A1 (fr) Épuration et recyclage d'eaux usées d'usine pure
JP7169241B2 (ja) 芳香族カルボン酸と脂肪族有機酸との混合物の製造方法
AU2009254215B2 (en) Process for the treatment of the aqueous stream coming from the Fischer-Tropsch reaction by means of ion exchange resins
WO2015157009A1 (fr) Épuration et recyclage d'eaux usées d'usines pures
KR20170009797A (ko) 폐수로부터 오염물질을 분리하기 위한 방법 및 그 시스템
JP2008150313A (ja) 高純度テレフタル酸の製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980110026.9

Country of ref document: CN

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

Ref document number: 09722623

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011500304

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 5875/CHENP/2010

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20107023372

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 09722623

Country of ref document: EP

Kind code of ref document: A1