EP0611182A1 - Verfahren zur Entfernung von Quecksilber aus Kohlenwasserstoffen mittels einem vorgeschwefeltem Absorbens - Google Patents

Verfahren zur Entfernung von Quecksilber aus Kohlenwasserstoffen mittels einem vorgeschwefeltem Absorbens Download PDF

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Publication number
EP0611182A1
EP0611182A1 EP94400193A EP94400193A EP0611182A1 EP 0611182 A1 EP0611182 A1 EP 0611182A1 EP 94400193 A EP94400193 A EP 94400193A EP 94400193 A EP94400193 A EP 94400193A EP 0611182 A1 EP0611182 A1 EP 0611182A1
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EP
European Patent Office
Prior art keywords
sulfur
metal
mass
organic
precursor
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EP94400193A
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English (en)
French (fr)
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EP0611182B1 (de
Inventor
Charles Cameron
Jean Cosyns
Partick Sarrazin
Jean-Paul Boitiaux
Philippe Courty
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03

Definitions

  • the present invention relates to the removal of arsenic from hydrocarbons. More particularly, the invention relates to the pretreatment of an arsenic capture mass allowing its capture with very high efficiency from the initial start-up period of the process.
  • liquid condensates byproducts of gas production
  • certain crude oils can contain many metallic compounds in trace amounts and often in the form of organometallic complexes. These metal compounds are very often poisons from the catalysts used during the transformation of these cuts into commercial products.
  • the applicant's processes have good performances for the demercurization and the de-arsenification of liquid hydrocarbons serving as feedstocks of various treatment processes.
  • the patent US Pat. No. 4,911,825 clearly shows the advantage of carrying out a capture of mercury and possibly arsenic in a two-step process where the first step consists in bringing the charge in contact in the presence of hydrogen with a catalyst containing at least one metal from the group consisting of nickel, cobalt, iron and palladium.
  • the mercury is not (or very little) captured by the catalyst but is captured, in a second step, by a mass containing sulfur or sulfur-containing compounds.
  • US Pat. No. 4,046,674 describes a process for removing arsenic (in an amount greater than 2 ppm) with a capture mass containing at least one nickel compound (which is at least a sulfide) in an amount of 30-70% by weight NiO , and at least one molybdenum compound (which is at least one sulfide) in an amount 2-20% by weight Mo O3.
  • This mixed absorbent sulfide requires, in order not to desulfurize, the presence of large amounts of sulfur (greater than 0.1%) in the feed and high operating temperatures (of the order of 288 and 343 ° C. in the examples ).
  • the present invention overcomes these drawbacks.
  • the object of the present invention is a method for removing arsenic in which the capture mass is pretreated before being brought into contact with the charge to be purified.
  • a mixture of the charge with hydrogen is brought into contact with a presulfurized capture mass containing at least one metal from the group formed by iron, nickel, cobalt, molybdenum, tungsten, chromium and palladium where at least 5% of the metal is in the sulphide state, and in general at most 50%.
  • the capture mass used in the composition of the present invention consists of at least one metal M chosen from the group formed by iron, nickel, cobalt, molybdenum, tungsten and palladium and a support.
  • the metal M must be in sulphide form for at least 5% of its totality and for at most, in general, 50%.
  • nickel or the combination of nickel with palladium is used.
  • the solid mineral dispersant (support) can be chosen from the group formed by alumina, silica-aluminas, silica, zeolites, activated carbon, clays and aluminous cements. It will preferably have a large surface, a sufficient pore volume and an adequate average pore diameter.
  • the BET surface should be greater than 50 m2 / g and preferably between approximately 100 and 350 m2 / g.
  • the preparation of a solid (or precursor of the capture mass) containing at least one metal M in metallic form or in the form of supported metal oxide is sufficiently known to those skilled in the art not to be described in the context of the present invention.
  • the content of metal M in the mass (calculated in oxide form) is preferably at least 5% by weight and at most 60% by weight, and even more advantageously at most 30%.
  • the case of palladium is particular, we can have at most 0.2% by weight of palladium (calculated as metal).
  • the addition of sulfur can be done, off-site, by impregnating the precursor of the capture mass either with ammonium sulphide and / or a colloidal suspension of sulfur in water or with a sulfur-containing agent. say sulfur and / or one or more sulfur compounds, in an organic solution.
  • a reducing agent is for example, formaldehyde, acetaldehyde, hydrazine, methyl formate, formic acid, etc.
  • the collection mass Before being brought into contact with the load to be treated, the collection mass is, if necessary, reduced by hydrogen or by a gas containing hydrogen at a temperature of 120 to 600 ° C. and preferably of 140 to 400 ° C.
  • the solid thus prepared, presulfurized then reduced constitutes the capture mass, in its active form, of the present invention.
  • the capture mass can be used in a temperature range which can range from 120 to 250 ° C, more advantageously from 130 to 220 ° C or even 130-200 ° C, preferably 140-190 ° C and even more preferred from 140 to 180 ° C.
  • the operating pressures will preferably be chosen from 1 to 40 bars and more advantageously from 5 to 35 bars.
  • the spatial velocities calculated with respect to the capture mass can be from 1 to 50 h -1 and more particularly from 1 to 30 h -1 (volume of liquid per volume of mass per hour).
  • the hydrogen flow rate relative to the capture mass is for example between 1 and 500 volumes (gas under normal conditions) per volume of the mass per hour.
  • the charges to which the invention applies more particularly contain from 0 to 1000 milligrams of sulfur per kilogram of charge and from 10 ⁇ 3 to 5 milligrams of arsenic per kilogram of charge.
  • Capture mass A Fifteen kilograms of a macroporous alumina support in the form of beads 1.5-3 mm in diameter and having a specific surface of 160 m2 / g, a total pore volume of 1.05 cm3 / g and a macroporous volume (diameter> 0.1 ⁇ m) of 0.4 cm3 / g are impregnated with 20% by weight of nickel in the form of an aqueous nitrate solution. After drying at 120 ° C for 5 h and thermal activation at 450 ° C for 2 h under air sweep, beads containing 25.4% by weight of nickel oxide are obtained.
  • Capture mass B Five kilograms of mass A are dry impregnated with a solution containing 175 g of DEODS diethanoldisulfide (including 74 g of sulfur) in 5150 cm3 of a 15% methyl formate solution in a white spirit. The catalyst thus prepared is activated at 150 ° C for 1 h.
  • the capture mass A was reduced to 400 ° C. under a flow rate of 20 l / h of hydrogen at 2 bar of pressure for 4 h. Then, the reactor was cooled to the reaction temperature 180 ° C. A heavy condensate of liquefied gas with hydrogen is then passed over the collection mass. The charge flow rate is 400 cm3 / h and that of hydrogen is 3.5 l / h. The test is carried out under a pressure of 35 bars.
  • the condensate used during this test (condensate A) has the following characteristics: initial boiling point: 21 ° C final boiling point: 470 ° C arsenic content: 65 ⁇ g / kg sulfur content: 237 mg / kg
  • a second arsenic uptake test was carried out using a condensate (condensate B) having the following characteristics: initial boiling point: 21 ° C final boiling point: 491 ° C arsenic content 80: ⁇ g / kg sulfur content: 117 mg / kg
  • Example 1 The pre-reduction and operating conditions are identical to those of the test of Example 1. It is noted, as in Example 1, of arsenic contents in the effluents, from 5 to 10 ⁇ g / kg, during the 240 first hours of warm-up.
  • the reactor was loaded with 50 cm3 of capture mass B, presulfurized as described above. All the other test conditions are identical to those indicated in Example 1 including the charge (condensate A). The arsenic content remains below the detection limit ( ⁇ 5 ⁇ g / kg) throughout the test.
  • the capture mass B was reduced to 300 ° C under a flow rate of 20 l / h of hydrogen at 2 bar of pressure for 6 h before cooling it to the reaction temperature 180 ° C. It is also noted that the content of arsenic in the effluent is below the detection limit ( ⁇ 5 ⁇ g / kg) throughout the test.

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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)
  • Catalysts (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP94400193A 1993-02-08 1994-01-28 Verfahren zur Entfernung von Arsen aus Kohlenwasserstoffen mittels einem vorgeschwefeltem Absorbens Expired - Lifetime EP0611182B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9301442A FR2701269B1 (fr) 1993-02-08 1993-02-08 Procédé d'élimination d'arsenic dans des hydrocarbures par passage sur une masse de captation présulfurée.
FR9301442 1993-02-08

Publications (2)

Publication Number Publication Date
EP0611182A1 true EP0611182A1 (de) 1994-08-17
EP0611182B1 EP0611182B1 (de) 1999-06-09

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ID=9443891

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EP94400193A Expired - Lifetime EP0611182B1 (de) 1993-02-08 1994-01-28 Verfahren zur Entfernung von Arsen aus Kohlenwasserstoffen mittels einem vorgeschwefeltem Absorbens

Country Status (7)

Country Link
US (1) US5531886A (de)
EP (1) EP0611182B1 (de)
JP (1) JP3486756B2 (de)
KR (1) KR100285674B1 (de)
CN (1) CN1048036C (de)
DE (1) DE69418911T2 (de)
FR (1) FR2701269B1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006037884A1 (fr) * 2004-10-06 2006-04-13 Institut Francais Du Petrole Procede de captation selective de l'arsenic dans les essences riches en soufre et en olefines
WO2019197351A1 (fr) 2018-04-11 2019-10-17 IFP Energies Nouvelles Masse de captation de l'arsenic à base de nanoparticules de sulfure de nickel
WO2019197352A1 (fr) 2018-04-11 2019-10-17 IFP Energies Nouvelles Procédé de captation de l'arsenic mettant en œuvre une masse de captation à base de particules d'oxyde de nickel
FR3116828A1 (fr) 2020-11-27 2022-06-03 IFP Energies Nouvelles Procédé de captation d'impuretés organométalliques mettant en œuvre une masse de captation à base de cobalt et de molybdène et contenant du carbone

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1091796C (zh) * 1999-07-17 2002-10-02 巴陵石化鹰山石油化工厂 一种硫化镍-钼系加氢脱硫脱砷催化剂的方法
CN100392046C (zh) * 2003-08-07 2008-06-04 上海化工研究院 低温或常温脱除液态石油烃中高沸点砷化物的脱砷剂
GB0611316D0 (en) * 2006-06-09 2006-07-19 Johnson Matthey Plc Improvements in the removal of metals from fluid streams
US20140291246A1 (en) 2013-03-16 2014-10-02 Chemica Technologies, Inc. Selective Adsorbent Fabric for Water Purification
FR3104460A1 (fr) 2019-12-17 2021-06-18 IFP Energies Nouvelles Masse de captation d'impuretés organométalliques préparée par la voie sels fondus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4046674A (en) * 1976-06-25 1977-09-06 Union Oil Company Of California Process for removing arsenic from hydrocarbons
US4069140A (en) * 1975-02-10 1978-01-17 Atlantic Richfield Company Removing contaminant from hydrocarbonaceous fluid
EP0332526A1 (de) * 1988-03-10 1989-09-13 Institut Français du Pétrole Verfahren zur Entfernung von Quecksilber und möglichem Arsen aus Kohlenwasserstoffen
WO1990010684A1 (fr) * 1989-03-16 1990-09-20 Institut Français Du Petrole Procede pour l'elimination du mercure et eventuellement d'arsenic dans les hydrocarbures
EP0466568A1 (de) * 1990-07-13 1992-01-15 EUROPEENNE DE RETRAITEMENT DE CATALYSEURS (en abrégé EURECAT) Verfahren zur Vorbehandlung eines Katalysators durch eine Mischung aus einem schwefelenthaltenden Mittel und einem organischen Reduktionsmittel

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804750A (en) * 1972-12-22 1974-04-16 Atlantic Richfield Co Shale oil treatment
US4853110A (en) * 1986-10-31 1989-08-01 Exxon Research And Engineering Company Method for separating arsenic and/or selenium from shale oil
DZ1209A1 (fr) * 1987-05-26 2004-09-13 Inst Francais Du Petrole Procédé de préparation et de régeneration d'une masse solide de captation du mercure renfermant du cuivre.
DE3822132C2 (de) * 1987-07-02 1997-11-20 Inst Francais Du Petrole Verwendung eines Katalysators zur Entfernung von Arsen und/oder Phosphor aus diese enthaltenden flüssigen Kohlenwasserstoffen
EP0357873B1 (de) * 1988-08-10 1992-08-26 Jgc Corporation Verfahren zum Entfernen von Quecksilber aus Kohlenwasserstoffen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069140A (en) * 1975-02-10 1978-01-17 Atlantic Richfield Company Removing contaminant from hydrocarbonaceous fluid
US4046674A (en) * 1976-06-25 1977-09-06 Union Oil Company Of California Process for removing arsenic from hydrocarbons
EP0332526A1 (de) * 1988-03-10 1989-09-13 Institut Français du Pétrole Verfahren zur Entfernung von Quecksilber und möglichem Arsen aus Kohlenwasserstoffen
WO1990010684A1 (fr) * 1989-03-16 1990-09-20 Institut Français Du Petrole Procede pour l'elimination du mercure et eventuellement d'arsenic dans les hydrocarbures
EP0466568A1 (de) * 1990-07-13 1992-01-15 EUROPEENNE DE RETRAITEMENT DE CATALYSEURS (en abrégé EURECAT) Verfahren zur Vorbehandlung eines Katalysators durch eine Mischung aus einem schwefelenthaltenden Mittel und einem organischen Reduktionsmittel

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006037884A1 (fr) * 2004-10-06 2006-04-13 Institut Francais Du Petrole Procede de captation selective de l'arsenic dans les essences riches en soufre et en olefines
US7901567B2 (en) 2004-10-06 2011-03-08 IFP Energies Nouvelles Process for selective capture of arsenic in gasolines rich in sulphur and olefins
WO2019197351A1 (fr) 2018-04-11 2019-10-17 IFP Energies Nouvelles Masse de captation de l'arsenic à base de nanoparticules de sulfure de nickel
WO2019197352A1 (fr) 2018-04-11 2019-10-17 IFP Energies Nouvelles Procédé de captation de l'arsenic mettant en œuvre une masse de captation à base de particules d'oxyde de nickel
FR3116828A1 (fr) 2020-11-27 2022-06-03 IFP Energies Nouvelles Procédé de captation d'impuretés organométalliques mettant en œuvre une masse de captation à base de cobalt et de molybdène et contenant du carbone

Also Published As

Publication number Publication date
KR940019837A (ko) 1994-09-15
DE69418911D1 (de) 1999-07-15
FR2701269B1 (fr) 1995-04-14
FR2701269A1 (fr) 1994-08-12
US5531886A (en) 1996-07-02
CN1091767A (zh) 1994-09-07
JP3486756B2 (ja) 2004-01-13
KR100285674B1 (ko) 2001-05-02
JPH06256772A (ja) 1994-09-13
DE69418911T2 (de) 1999-09-30
EP0611182B1 (de) 1999-06-09
CN1048036C (zh) 2000-01-05

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