WO2014202594A1 - Procédé pour éliminer des métaux de fractions hydrocarbonées à haut point d'ébullition - Google Patents

Procédé pour éliminer des métaux de fractions hydrocarbonées à haut point d'ébullition Download PDF

Info

Publication number
WO2014202594A1
WO2014202594A1 PCT/EP2014/062704 EP2014062704W WO2014202594A1 WO 2014202594 A1 WO2014202594 A1 WO 2014202594A1 EP 2014062704 W EP2014062704 W EP 2014062704W WO 2014202594 A1 WO2014202594 A1 WO 2014202594A1
Authority
WO
WIPO (PCT)
Prior art keywords
metals
water
liquid phase
phase
hydrocarbon
Prior art date
Application number
PCT/EP2014/062704
Other languages
English (en)
Inventor
Giuseppe CUSATI
Roberta Olindo
Gerhard Birke
Original Assignee
L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude
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 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude filed Critical L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude
Publication of WO2014202594A1 publication Critical patent/WO2014202594A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/10—Recovery of used refining agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
    • C10G17/04—Liquid-liquid treatment forming two immiscible phases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only

Definitions

  • This invention relates to a process for removing metals from high-boiling hydrocarbon fractions, in particular for separating catalyst-induced nickel, cobalt and aluminum impurities from the primary products of a hydrocarbon synthesis, for example by the Fischer- Tropsch process.
  • Hydrocarbons can be obtained as synthesis products from chemico-catalytical processes, such as for example the Fischer-Tropsch process, the fundamentals of which have been described in detail in the literature, e.g. in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 1998 Electronic Release, keyword “Coal Liquefaction", chapter 2.2 “Fischer-Tropsch Synthesis”.
  • a modern process variant is the conversion of synthesis gas in a suspension of the solid, fine-grained catalyst into the liquid product hydrocarbons (so-called slurry process).
  • highly active catalysts which as active components contain metals, for example cobalt, on a carrier material, for example alumina, as it is described in the US patent specification US 4,801 ,573.
  • German patent specification DE 1212662 describes a method for the treatment of hydrocarbon oils for the purpose of removing metallic impurities, which are detrimental for the catalysts used in their conversions. It is proposed to treat the contaminated hydrocarbon oils with a solution of hydrogen fluoride in an organic solvent, whereby the metals are transferred into a hardly soluble precipitate which subsequently can be separated with a mechanical separation method.
  • the above-described problems in the treatment of a two-phase mixture of hydrocarbon phase and aqueous phase thereby are avoided.
  • What is disadvantageous, however, is the use of the highly reactive, gaseous hydrogen fluoride for preparing the treatment solution for reasons of occupational safety and handling.
  • the US patent specification US 4,518,484 indicates a method for the treatment of metal- containing hydrocarbon feed streams, which comprises the following steps: (a) contacting the hydrocarbon feed streams in an extraction zone with at least one hydrocarbon solvent with 2 to 10 carbon atoms per molecule under supercritical conditions in the presence of an organophosphorus-based demetalizing agent, (b) discharging a top product from the extraction zone, which contains the hydrocarbons largely liberated from metals, and a bottom product which contains the solvent loaded with the metals.
  • What is to be regarded as disadvantageous is the expensive procedure, in particular the adjust- ment of supercritical conditions.
  • Subject-matter of the patent application DE 10201 1013470 A1 is a process and means for removing metal impurities from hydrocarbon fractions, as they are obtained for example as product of the Fischer-Tropsch synthesis by using a suspended catalyst.
  • the treatment of the feed hydrocarbon fractions is effected with a demetalizing agent, comprising at least one sulfur source and at least one basic compound, under anhydrous conditions.
  • the metals to be removed are obtained as precipitate which can easily be separated with a mechanical separation method, for example the filtration.
  • the International Patent Application WO 2006/053350 A1 discloses a method for separating metal impurities such as aluminum or cobalt from hydrocarbon fractions, in which the hydrocarbon fraction is treated with an aqueous phase at temperatures of at least 160 °C, typically about 170 °C, wherein the aqueous phase optionally can comprise an acid, for example an organic acid such as maleic acid.
  • aqueous phase optionally can comprise an acid, for example an organic acid such as maleic acid.
  • Detailed conditions of this meth- od, such as the set pH value are not disclosed there.
  • the solution of the object according to the invention substantially results from the features of claim 1 by a process for producing a hydrocarbon fraction poor in metals, wherein the metals are chemically bound in the hydrocarbon fraction or are dispersed in the hydrocarbon fraction in colloidal or finely dispersed form, comprising the following steps: (a) providing the metal-containing hydrocarbon fraction in liquid form,
  • the feed hydrocarbon fraction must be present in liquid form.
  • Wax-like hydrocarbons as they are obtained for example as products of the Fischer-Tropsch process, possibly must be molten before the treatment.
  • the optimum pH range therefore lies between 3 and 5, particularly preferably at pH 3. Even smaller pH values are not preferred, since then the corrosiveness of the aqueous phase will rise and thus more corrosion-resistant and therefore more expensive materials will have to be used for the respective plant sections.
  • the temperature also is an important influencing variable for the effectiveness of the method according to the invention. At a temperature of 150 °C a complete removal of the metal impurities within the measurement accuracy has been achieved already after 10 minutes, and in addition a smaller amount of EDTA was used. By further increasing the temperature, the required EDTA quantities could be reduced even further. There was each formed a third phase in which the metals are accumulated and which optically is distinctly visible. This third phase was removed by mechanical separation, preferably by filtration. The hydrocarbon fraction liberated from metal impurities then can be separated from the water by a simple phase separation. Further preferred aspects of the invention
  • the filtration is used in the process step according to claim 1 , item (d).
  • the use of the centrifugation or decantation also is possible; however, the filtration offers an optimum with regard to expenditure and separation efficiency achieved.
  • the water-containing liquid phase is recirculated after an optional treatment by the process step according to claim 1 , item (b).
  • water can be obtained as reaction product of a preceding or downstream stage and thus already is present in the process, for example during the production of synthesis gas or the subsequent Fischer-Tropsch synthesis, so that here only a minimum or possibly even no fresh-water feed stream at all is required. It appears to be possible in principle to again and again circulate the used water, possibly after treatment.
  • the complexing agent forms complexes of the chelate type with the metals to be removed.
  • particularly stable metal complexes are formed and the metals are removed from the hydrocarbon fraction in a particularly efficient way.
  • ethylenediaminetetraacetic acid and/or ethylenediaminetetraace- tate (EDTA) are used as complexing agents.
  • Example 1 Invention
  • a hydrocarbon mixture (wax fraction from the Fischer-Tropsch synthesis with a metal content of about 351 wt-ppm (aluminum 220 wt-ppm, nickel 109 wt-ppm, cobalt 22 wt-ppm)) were molten at 85 °C and presented in a glass flask under reflux cooling.
  • the determination of the metal content was effected by X-ray fluorescence analysis (RFA) with the method Uniquant 2.
  • RFA X-ray fluorescence analysis
  • To the molten wax 100 g of an aqueous EDTA solution with a pH value of 5 were added. The amount of EDTA in the water corresponded to 5 g.
  • the mixture was heated to 100 °C under vigorous stirring.
  • the experimental arrangement was under atmospheric pressure. This temperature was maintained for 4 hours.
  • a hydrocarbon mixture (wax fraction from the Fischer-Tropsch synthesis with a metal content of about 351 wt-ppm (aluminum 220 wt-ppm, nickel 109 wt-ppm, cobalt 22 wt-ppm)) were molten at 85 °C and presented in a glass flask under reflux cooling.
  • the determination of the metal content was effected by X-ray fluorescence analysis (RFA) with the method Uniquant 2.
  • RFA X-ray fluorescence analysis
  • To the molten wax 100 g of an aqueous EDTA solution with a pH value of 3 were added. The amount of EDTA in the water corresponded to 5 g.
  • the mixture was heated to 100 °C under vigorous stirring.
  • the experimental arrangement was under atmospheric pressure. This temperature was maintained for 4 hours. After terminating stirring, a grey-green phase was formed, which contained most of the metals and could be separated by a fluted filter.
  • the filtrate was
  • a hydrocarbon mixture (wax fraction from the Fischer-Tropsch synthesis with a metal content of about 351 wt-ppm (aluminum 220 wt-ppm, nickel 109 wt-ppm, cobalt 22 wt-ppm)) were molten at 85 °C and presented in an autoclave.
  • the determination of the metal content was effected by X-ray fluorescence analysis (RFA) with the method Uniquant 2.
  • RFA X-ray fluorescence analysis
  • To the molten wax 100 g of an aqueous EDTA solution with a pH value of 3 were added. The amount of EDTA in the water corresponded to 0.25 g.
  • the mixture was heated to 150 °C under vigorous stirring.
  • the autoclave was under a pressure of 4.7 bar, absolute. This temperature was maintained for 10 minutes.
  • a hydrocarbon mixture (wax fraction from the Fischer-Tropsch synthesis with a metal content of about 351 wt-ppm (aluminum 220 wt-ppm, nickel 109 wt-ppm, cobalt 22 wt-ppm)) were molten at 85 °C and presented in an autoclave.
  • the determination of the metal content was effected by X-ray fluorescence analysis (RFA) with the method Uniquant 2.
  • RFA X-ray fluorescence analysis
  • To the molten wax 100 g of an aqueous EDTA solution with a pH value of 3 were added. The amount of EDTA in the water corresponded to 0.10 g.
  • the mixture was heated to 200 °C under vigorous stirring.
  • the autoclave was under a pressure of 16 bar, absolute. This temperature was maintained for 10 minutes.
  • a hydrocarbon mixture (wax fraction from the Fischer-Tropsch synthesis with a metal content of about 351 wt-ppm (aluminum 220 wt-ppm, nickel 109 wt-ppm, cobalt 22 wt-ppm)) were molten at 85 °C and presented in an autoclave.
  • the determination of the metal content was effected by X-ray fluorescence analysis (RFA) with the method Uniquant 2.
  • RFA X-ray fluorescence analysis
  • To the molten wax 100 g of water were added and the mixture was heated to 150 °C under vigorous stirring. The autoclave was under a pressure of 4.7 bar, absolute. This temperature was maintained for one hour and the mixture was then cooled to 90 °C.
  • the invention provides a process for removing metal impurities from hydrocarbon fractions, which as compared to the processes known from the prior art is characterized by its technical simplicity and by the absence of additional extracting agents, in particular those foreign to the process. Furthermore, it is advantageous that only substances with low to medium hazard potential are used, and the use of substances with high hazard potential, such as hydrogen fluoride, is avoided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Procédé pour éliminer des métaux de fractions hydrocarbonées à haut point d'ébullition. L'invention porte sur un procédé pour éliminer des impuretés métalliques de fractions hydrocarbonées, au fur et à mesure qu'elles sont obtenues par exemple en tant que produit de la synthèse Fischer-Tropsch par utilisation d'un catalyseur en suspension. Selon l'invention, la fraction hydrocarbonée à traiter est donc mélangée à l'état fondu à une phase aqueuse sous agitation à une température d'au moins 100°C, la phase aqueuse ayant un pH non supérieur à 5 et contenant en outre un agent complexant. Les métaux à éliminer sont séparés dans une phase distincte et peuvent être éliminés par le procédé, par exemple au moyen d'une filtration.
PCT/EP2014/062704 2013-06-20 2014-06-17 Procédé pour éliminer des métaux de fractions hydrocarbonées à haut point d'ébullition WO2014202594A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201310106441 DE102013106441A1 (de) 2013-06-20 2013-06-20 Verfahren zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen
DE102013106441.8 2013-06-20

Publications (1)

Publication Number Publication Date
WO2014202594A1 true WO2014202594A1 (fr) 2014-12-24

Family

ID=51134021

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/062704 WO2014202594A1 (fr) 2013-06-20 2014-06-17 Procédé pour éliminer des métaux de fractions hydrocarbonées à haut point d'ébullition

Country Status (2)

Country Link
DE (1) DE102013106441A1 (fr)
WO (1) WO2014202594A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3103858A1 (fr) * 2015-06-08 2016-12-14 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Procede de lavage de liquides organiques avec une solution comprenant des composés fluorohydrocarbonés

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1212662B (de) 1962-05-09 1966-03-17 Universal Oil Prod Co Verfahren zum Entfernen metallischer und stickstoffhaltiger Verunreinigungen aus Kohlenwasserstoffoelen
US4518484A (en) 1984-02-16 1985-05-21 Phillips Petroleum Company Metals removal with a light hydrocarbon and an organophosphorous compound
US4801573A (en) 1987-10-23 1989-01-31 501 Den Norske Stats Oljeslenskap A.S. Catalyst for production of hydrocarbons
US4988433A (en) * 1988-08-31 1991-01-29 Chevron Research Company Demetalation of hydrocarbonaceous feedstocks using monobasic carboxylic acids and salts thereof
WO1998027181A1 (fr) 1996-12-16 1998-06-25 Rentech, Inc. Dispositif separateur catalyseur/cire pour reacteur de fischer-tropsch a combustible en suspension
US6476086B1 (en) * 2001-04-04 2002-11-05 Hydrocarbon Technologies, Inc. Coalescence enhanced gravity separation of iron catalyst from Fischer-Tropsch catalyst/wax slurry
US20050004239A1 (en) * 2003-07-02 2005-01-06 Chevron U.S.A. Inc. Acid treatment of a fischer-tropsch derived hydrocarbon stream
US20060006102A1 (en) * 2004-07-07 2006-01-12 Chevron U.S.A. Inc. Process for removing aluminum contaminants from fischer-tropsch feed streams using dicarboxylic acid
WO2006053350A1 (fr) 2004-11-10 2006-05-18 Sasol Technology (Pty) Ltd Traitement de courants d'hydrocarbures de masse molaire elevee
DE102011013470A1 (de) 2010-07-26 2012-01-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren und Mittel zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA200901193B (en) * 2006-08-22 2010-06-30 Dorf Ketal Chemicals I Private Method of removal of calcium from hydrocarbon feedstock

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1212662B (de) 1962-05-09 1966-03-17 Universal Oil Prod Co Verfahren zum Entfernen metallischer und stickstoffhaltiger Verunreinigungen aus Kohlenwasserstoffoelen
US4518484A (en) 1984-02-16 1985-05-21 Phillips Petroleum Company Metals removal with a light hydrocarbon and an organophosphorous compound
US4801573A (en) 1987-10-23 1989-01-31 501 Den Norske Stats Oljeslenskap A.S. Catalyst for production of hydrocarbons
US4988433A (en) * 1988-08-31 1991-01-29 Chevron Research Company Demetalation of hydrocarbonaceous feedstocks using monobasic carboxylic acids and salts thereof
WO1998027181A1 (fr) 1996-12-16 1998-06-25 Rentech, Inc. Dispositif separateur catalyseur/cire pour reacteur de fischer-tropsch a combustible en suspension
US6476086B1 (en) * 2001-04-04 2002-11-05 Hydrocarbon Technologies, Inc. Coalescence enhanced gravity separation of iron catalyst from Fischer-Tropsch catalyst/wax slurry
US20050004239A1 (en) * 2003-07-02 2005-01-06 Chevron U.S.A. Inc. Acid treatment of a fischer-tropsch derived hydrocarbon stream
US20060006102A1 (en) * 2004-07-07 2006-01-12 Chevron U.S.A. Inc. Process for removing aluminum contaminants from fischer-tropsch feed streams using dicarboxylic acid
WO2006053350A1 (fr) 2004-11-10 2006-05-18 Sasol Technology (Pty) Ltd Traitement de courants d'hydrocarbures de masse molaire elevee
DE102011013470A1 (de) 2010-07-26 2012-01-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren und Mittel zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Ullmann's Encyclopedia of Industrial Chemistry", 1998, article "Electronic Release, keyword ''Coal Liquefaction"

Also Published As

Publication number Publication date
DE102013106441A1 (de) 2014-12-24

Similar Documents

Publication Publication Date Title
CN109563436B (zh) 通过热处理纯化原料
KR102049003B1 (ko) 황 함량이 감소된 카본 블랙 분말을 얻기 위한 방법
EA016272B1 (ru) Способ извлечения ультратонких твердых частиц из углеводородной жидкости
WO2012013581A2 (fr) Processus et agents pour élimination de métaux contenus dans des fractions d'hydrocarbures à point d'ébullition élevé
AU2004253963B2 (en) Acid treatment of a Fischer-Tropsch derived hydrocarbon stream
JP6817656B2 (ja) 液体炭化水素からアルカリ金属塩を含む粒子を分離するための方法
WO2020121220A1 (fr) Processus de récupération sélective de métaux de transition à partir de résidus organiques
AU2005260789B2 (en) Method of treatment of Fischer-Tropsch derived hydrocarbons
WO2014202594A1 (fr) Procédé pour éliminer des métaux de fractions hydrocarbonées à haut point d'ébullition
WO2008155730A8 (fr) Élimination de particules ultra-fines d'un courant de fischer tropsch
WO2010096400A1 (fr) Procédé d'élimination du mercure d'hydrocarbures
WO2014202596A1 (fr) Procédé pour éliminer des métaux à partir de fractions d'hydrocarbures à point d'ébullition élevé
US20180094198A1 (en) Process for separating particles containing alkali metal salts from liquid hydrocarbons
WO2014180759A1 (fr) Procédé pour éliminer des métaux de fractions d'hydrocarbures à point d'ébullition élevé
WO2015180845A1 (fr) Procédé d'élimination d'impuretés métalliques de fractions lourdes d'hydrocarbures
DE102014107374A1 (de) Verfahren zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen
RU2683283C1 (ru) Способ регенерации молибденсодержащего катализатора гидроконверсии тяжелого углеводородного сырья
WO1996005271A1 (fr) Procede d'extraction des mercaptans a bas poids moleculaire presents dans le petrole et les condensats de gaz
JP2017019762A (ja) ジメチルスルホキシドの精製方法
HU225697B1 (en) Method for purifying of used oils
Kadiev et al. Extraction of Molybdenum Compounds from Solid Carbon-Containing Hydroconversion Residue of Heavy Oil Raw Materials
FR2548206A1 (fr) Procede de formation de melanges de sels metalliques solubles, principalement du vanadium et du nickel, et utilisation des melanges formes comme catalyseurs d'hydrotraitement d'hydrocarbures lourds, en phase liquide
US20150322353A1 (en) Contaminant removal from hydrocarbon streams with lactamium based ionic liquids
JPS6011954B2 (ja) 石油系鉱油中の鉄分を除去する方法
GB2448253A (en) Acid treatment of a fischer-tropsch derived hydrocarbon stream

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: 14735871

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14735871

Country of ref document: EP

Kind code of ref document: A1