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US20130180887A1 - Process and agents to remove metals from high-boiling hydrocarbon fractions - Google Patents

Process and agents to remove metals from high-boiling hydrocarbon fractions Download PDF

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Publication number
US20130180887A1
US20130180887A1 US13/811,510 US201113811510A US2013180887A1 US 20130180887 A1 US20130180887 A1 US 20130180887A1 US 201113811510 A US201113811510 A US 201113811510A US 2013180887 A1 US2013180887 A1 US 2013180887A1
Authority
US
United States
Prior art keywords
sulfur
hydrocarbon
hydrocarbon fraction
demetallizing agent
sulfur source
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.)
Abandoned
Application number
US13/811,510
Other languages
English (en)
Inventor
Ingo Bauer
Rudolf Bonsch
Ute Raab-Brill
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.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
LAir Liquide SA pour lEtude et lExploitation des Procedes 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 LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Assigned to L'AIR LIQUIDE, SOCIETE ANONYME POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE reassignment L'AIR LIQUIDE, SOCIETE ANONYME POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RAAB-BRILL, UTE, BAUER, INGO, BOENSCH, RUDOLF
Publication of US20130180887A1 publication Critical patent/US20130180887A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20Organic compounds not containing metal atoms
    • C10G29/28Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G19/00Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20Organic compounds not containing metal atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1022Fischer-Tropsch products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/205Metal content

Definitions

  • This invention relates to a process for the removal of metals from high-boiling hydrocarbon fractions as well as agents to their removal.
  • the invention relates to a process and agents to separate nickel, cobalt and aluminum contaminants originating from catalysts and contained in the primary products of a hydrocarbon synthesis, e.g. pursuant to the Fischer-Tropsch process.
  • Hydrocarbons can be generated as synthesis products from chemical-catalytic processes like for example the Fischer-Tropsch process, the basics of which have been described in great detail in specialist literature, e.g. in Ullmann's Encyclopedia of Industrial Chemistry, sixth Edition, 1998 Electronic Release, key word “Coal Liquefaction”, chapter 2.2 “Fischer-Tropsch Synthesis”.
  • a modern process variant is the conversion of synthesis gas in a suspension of solid, fine-grain catalyst in the liquid product hydrocarbons (so-called slurry process).
  • slurry process high-activity catalysts are used whose active components contain metals such as cobalt and a support material such as alumina, as described in U.S. Pat. No. 4,801,573.
  • heavy metal contamination In addition to the heavy metal contamination also contamination with the metal of the catalyst support matrix (e.g. aluminum) is observed.
  • the metal contamination described may be disruptive for a further chemical-catalytic conversion of the product hydrocarbons since it may act as catalyst poison.
  • heavy metal contamination irrespective in which substance it is contained, represents a potential environmental and health hazard.
  • nickel and cobalt have to be mentioned here which are classified as carcinogenic.
  • both heavy metals represent valuable catalyst elements that should be recycled in order to prevent losses.
  • German patent publication DE 1212662 describes a process for the treatment of hydrocarbon oils for the purpose of removing metallic contaminants that are detrimental for the catalysts used for their conversion.
  • a solution of hydrogen fluoride in an organic solvent whereby the metals are converted into a hardly soluble precipitate that can be separated in a downstream step by means of a mechanical separation process.
  • the use of a highly reactive, gaseous hydrogen fluoride for the preparation of the treatment solution represents a downside for reasons of occupational safety and handling.
  • the DE patent application 2346058 shows a process for the removal of metal-containing impurities from a hydrocarbon material by contacting this material with a catalyst under hydrogenation conditions whereby the metal-containing contaminants are reduced to an elementary metal that is separated from the hydrocarbon phase as a precipitate.
  • the downside of this process is the complex process control to ensure a largely complete hydrogenation of the metallic contaminants while at the same time avoiding the hydrogenating cracking of the hydrocarbons.
  • the U.S. Pat. No. 4,518,484 describes a process for the treatment of metal-containing hydrocarbon feed streams that involves the following steps: (a) contacting the hydrocarbon feed streams in an extraction zone with at least one hydrocarbon solvent containing from 2 to 10 carbon atoms per molecule under supercritical conditions in the presence of a demetallizing agent based on an organophosphorus chemical, (b) recovering an overhead stream from the extraction zone that contains hydrocarbons substantially reduced in contaminating metals content and a bottoms product that contains the metal-laden solvent.
  • a demetallizing agent based on an organophosphorus chemical e.g., a demetallizing agent based on an organophosphorus chemical
  • the underlying task of the present invention therefore is to present a simple technology for the removal of metal contaminants from high-boiling hydrocarbon fractions and adequate means for performing such removal characterized by a simple process—in particular one without the use of aqueous media—that can be applied without the use of substances involving a high risk potential.
  • the solution as per this invention mainly results from the features of the characterising portion claim 1 in conjunction with the features of the precharacterising portion of the claim in that—in a process to obtain a hydrocarbon fraction with a low metals content, whereby the metals in the hydrocarbon fraction are chemically bonded or dispersed in colloidal or finely dispersed form in the hydrocarbon fraction, a demetallizing agent is added to the liquid hydrocarbon fraction that comprises the following components:
  • the invention also relates to a demetallizing agent as per claims 2 through 6 .
  • the feed hydrocarbon fraction to be treated must be liquid.
  • Wax-like hydrocarbons like for example those obtained as a product of the Fischer-Tropsch process, must be molten prior to the treatment, where necessary.
  • the process as per the present invention is conducted using a demetallizing agent comprising sulfur-impregnated activated carbon as its sulfur source.
  • a demetallizing agent comprising sulfur-impregnated activated carbon as its sulfur source.
  • the separation of the metal-containing, hardly soluble precipitate as per the present invention is done by means of a mechanical separation process, preferably by filtration, sedimentation, decantation or centrifugation, or combinations thereof.
  • the clouding could then be very easily separated from the reaction mixture using a folded filter.
  • the analysis of the filtrate did not produce a detectable concentration of nickel and aluminum (detection limit in each case: 5 ppm).
  • the cobalt concentration amounted to 5 ppm
  • the sulfur content in the filtrate amounted to approx. 50 ppm.
  • Leaving the filtrate in a drying cabinet for one hour resulted in slight clouding.
  • a repeated filtering of this sample showed that no more cobalt can be detected in the filtrate.
  • the sulfur content remained unchanged.
  • the analyses of the metal and sulfur contents were again performed by means of x-ray fluorescence analysis (XRF) using the UNIQUANT 2 method.

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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US13/811,510 2010-07-26 2011-07-21 Process and agents to remove metals from high-boiling hydrocarbon fractions Abandoned US20130180887A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE102010032263 2010-07-26
DE102010032263 2010-07-26
DE102011013470A DE102011013470A1 (de) 2010-07-26 2011-03-09 Verfahren und Mittel zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen
DE102011013470.0 2011-03-09
PCT/EP2011/062587 WO2012013581A2 (fr) 2010-07-26 2011-07-21 Processus et agents pour élimination de métaux contenus dans des fractions d'hydrocarbures à point d'ébullition élevé

Publications (1)

Publication Number Publication Date
US20130180887A1 true US20130180887A1 (en) 2013-07-18

Family

ID=44629994

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/811,510 Abandoned US20130180887A1 (en) 2010-07-26 2011-07-21 Process and agents to remove metals from high-boiling hydrocarbon fractions

Country Status (5)

Country Link
US (1) US20130180887A1 (fr)
EP (1) EP2598607A2 (fr)
CN (1) CN103025850A (fr)
DE (1) DE102011013470A1 (fr)
WO (1) WO2012013581A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210388462A1 (en) * 2018-12-11 2021-12-16 Eni S.P.A. Process for the selective recovery of transition metals from organic residues

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013104696A1 (de) 2013-05-07 2014-11-13 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen
DE102013106439A1 (de) 2013-06-20 2014-12-24 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen
DE102013106441A1 (de) 2013-06-20 2014-12-24 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen
DE102014107375A1 (de) 2014-05-26 2015-11-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Metallentfernung aus hochsiedenden Kohlenwasserstofffraktionen
DE102014107374A1 (de) 2014-05-26 2015-11-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen
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
JP6817656B2 (ja) * 2016-10-04 2021-01-20 エンライテン イノベーションズ インコーポレイテッド 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

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210388462A1 (en) * 2018-12-11 2021-12-16 Eni S.P.A. Process for the selective recovery of transition metals from organic residues
US12392011B2 (en) * 2018-12-11 2025-08-19 Eni S.P.A. Process for the selective recovery of transition metals from organic residues

Also Published As

Publication number Publication date
DE102011013470A1 (de) 2012-01-26
CN103025850A (zh) 2013-04-03
EP2598607A2 (fr) 2013-06-05
WO2012013581A2 (fr) 2012-02-02
WO2012013581A3 (fr) 2012-05-24

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Owner name: L'AIR LIQUIDE, SOCIETE ANONYME POUR L'ETUDE ET L'E

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BAUER, INGO;BOENSCH, RUDOLF;RAAB-BRILL, UTE;SIGNING DATES FROM 20130304 TO 20130321;REEL/FRAME:030075/0118

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