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 PDFInfo
- 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
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.
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102013106441.8 | 2013-06-20 | ||
DE201310106441 DE102013106441A1 (de) | 2013-06-20 | 2013-06-20 | Verfahren zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen |
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)
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)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8685233B2 (en) * | 2006-08-22 | 2014-04-01 | Dork Ketal Chemicals (I) Private Limited | Method of removal of calcium from hydrocarbon feedstock |
-
2013
- 2013-06-20 DE DE201310106441 patent/DE102013106441A1/de not_active Ceased
-
2014
- 2014-06-17 WO PCT/EP2014/062704 patent/WO2014202594A1/fr active Application Filing
Patent Citations (10)
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)
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 |
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