EP0463044B1 - Process for eliminating mercury and possibly arsenic in hydrocarbons - Google Patents

Process for eliminating mercury and possibly arsenic in hydrocarbons Download PDF

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Publication number
EP0463044B1
EP0463044B1 EP90904870A EP90904870A EP0463044B1 EP 0463044 B1 EP0463044 B1 EP 0463044B1 EP 90904870 A EP90904870 A EP 90904870A EP 90904870 A EP90904870 A EP 90904870A EP 0463044 B1 EP0463044 B1 EP 0463044B1
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EP
European Patent Office
Prior art keywords
charge
catalyst
metal
mercury
arsenic
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EP90904870A
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German (de)
French (fr)
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EP0463044A1 (en
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Philippe Courty
Pierre Dufresne
Jean-Paul Boitiaux
Germain Bâtiment Condé MARTINO
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • 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
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content

Definitions

  • liquid condensates by-products of gas production can contain many trace metal compounds, generally present in the form of organometallic complexes, in which the metal forms bonds with one or more carbon atoms of the organometallic radical.
  • metal compounds are poisonous catalysts used in petroleum transformation processes. In particular, they poison the hydrotreatment and hydrogenation catalysts by gradually depositing on the active surface.
  • Metallic compounds are found in particular in heavy cuts from the distillation of petroleum crude (nickel, vanadium, arsenic, mercury) or in natural gas condensates (mercury, arsenic).
  • the thermal or catalytic cracking treatments of the above hydrocarbon cuts can allow the elimination of certain metals (for example nickel, vanadium ...) ; on the other hand, certain other metals (for example mercury, arsenic ...) capable of forming volatile compounds and / or being volatile in the element state (mercury) are found at least in part in the cuts more light and can therefore poison the catalysts of subsequent transformation processes.
  • Certain metals for example nickel, vanadium ...)
  • certain other metals for example mercury, arsenic ...) capable of forming volatile compounds and / or being volatile in the element state (mercury) are found at least in part in the cuts more light and can therefore poison the catalysts of subsequent transformation processes.
  • Mercury also presents the risk of causing corrosion by the formation of amalgams, for example with aluminum-based alloys, in particular in the process sections operating at a temperature low enough to cause condensation of liquid mercury (cryogenic fractionations , exchangers).
  • Prior methods are known for removing mercury or arsenic from hydrocarbons in the gas phase; one operates in particular in the presence of solid masses, which can be called indifferently: adsorption, capture, trapping, extraction and metal transfer masses.
  • Patent FR 2534826 describes other masses consisting of elemental sulfur and an inorganic support.
  • Patent DE 2149993 teaches the use of Group VIII metals (nickel, platinum, palladium).
  • US Patent 4069140 describes the use of various absorbent masses.
  • the supported iron oxide is described, the use of lead oxide is described in US Pat. No. 3,782,076 and that of copper oxide in US Patent 3,812,653.
  • the object of the invention is a process for removing mercury and possibly arsenic contained in a hydrocarbon feedstock and which remedies the defects of the previous processes.
  • Another object of the invention is to be able to remove the mercury and possibly the arsenic even in hydrocarbon feedstocks further containing significant proportions of sulfur.
  • significant proportions is meant from 0.005 to 3% by weight and in particular from 0.02 to 2% by weight.
  • a sulfur compound for example an organic sulphide, or alternatively hydrogen sulphide, either in the raw charge (before de-arsenification) or in the charge treated in the presence of hydrogen and of the de-arsenification mass with catalytic properties, before demercurization in the presence of the second bed.
  • a sulfur compound for example an organic sulphide, or alternatively hydrogen sulphide
  • the charge also contains arsenic, it is also eliminated.
  • the operation is preferably carried out with the feed at least partly in the liquid phase.
  • the catalyst also allows hydrodesulfurization, hydrodenitrification and, at least in part, hydrogenation of the unsaturated compounds which may be present in the feed, which can turn out to be advantageous when said fillers are intended for steam cracking.
  • said mass allows effective demetallation if, in addition to arsenic and mercury, vanadium and / or nickel are present.
  • the arsenic capture mass with catalytic properties subsequently designated as "the catalyst" used in the composition of the assembly which is the subject of the present invention therefore consists of at least one metal M chosen from the group formed by iron, nickel, cobalt, palladium, platinum and at least one metal N chosen from the group formed by chromium, molybdenum, tungsten and uranium, these metals, in the form of oxides and / or oxysulfides and / or sulfides, which can be used as such or preferably be deposited on at least one support from the list which follows. Under conditions of use, it is imperative that the metal M and / or the metal N are present in sulfurized form for at least 50% of their totality.
  • the respective amounts of metal or metals M and of metal or metals N contained in the catalyst are usually such that the atomic ratio of metal or metals M to metal or metals N, M / N is approximately 0.3: 1 to 0, 7: 1 and preferably from about 0.3: 1 to about 0.45: 1.
  • the quantity by weight of metals contained in the finished catalyst expressed by weight of metal relative to the weight of the finished catalyst is usually, for the metal or metals N, from about 2 to 30% and preferably from about 5 to 25%, and for the metal or metals M of approximately 0.01 to 15%, more particularly of approximately 0.01 to 5% and preferably of approximately 0.05 to 3% for palladium and / or platinum; and approximately 0.5 to 15% and preferably approximately 1 to 10% in the case of non-noble metals M (Fe, Co, Ni).
  • metals N molybdenum and / or tungsten are preferably used, and among the metals M, the non-noble metals iron, cobalt and / or nickel are preferred.
  • the following combinations of metals are used: nickel-molybdenum, nickel-tungsten, cobalt-molybdenum, cobalt-tungsten, iron-molybdenum and iron-tungsten.
  • the most preferred combinations are nickel-molydene and cobalt-molybdenum. It is also possible to use combinations of three metals, for example nickel-cobalt-molybdenum.
  • the porous mineral matrix is chosen so that the final catalyst has the optimal pore volume characteristics.
  • This matrix usually comprises at least one of the elements of the group formed by alumina, silica, silica-alumina, magnesia, zirconia, titanium oxide, clays, aluminous cements, aluminates, for example magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, copper and zinc aluminates, mixed aluminates, for example those comprising at least two of the metals mentioned above.
  • matrices containing alumina for example alumina and silica-alumina or alternatively titanium oxide.
  • the matrix contains silica it is preferable that the quantity of silica is at most equal to 25% by weight relative to the total weight of the matrix.
  • the matrix can also contain, in addition to at least one of the compounds mentioned above, at least one crystalline or natural zeolitic alumino-silicate (zeolite).
  • zeolite crystalline or natural zeolitic alumino-silicate
  • the amount of zeolite usually represents from 0 to 95% by weight and preferably from 1 to 80% by weight relative to the weight of the matrix.
  • mixtures of alumina and zeolite or alternatively mixtures of silica-alumina and zeolite.
  • zeolites with an atomic ratio of framework, silicon to aluminum (Si / Al) greater than about 5: 1.
  • zeolites with faujasite structures are used, and in particular stabilized or ultra-stabilized Y zeolites.
  • the most commonly used matrix is alumina, and transition alumina, pure or mixed, such as ⁇ C ⁇ T , ⁇ , ⁇ , is usually preferred.
  • Said matrix will preferably have a large surface area and a sufficient pore volume, that is to say respectively at least 50 m2 / g and at least 0.5 cm3 / g, for example 50 to 350 m2 / g and 0, 5 to 1.2 cm3 / g.
  • the fraction of macroporous volume, consisting of all the pores with an average diameter at least equal to 0.1 ⁇ m, may represent from 10% to 30% of the total pore volume.
  • the catalyst Before use, the catalyst can, if necessary, be treated with a gas containing hydrogen at a temperature of 50 to 500 ° C. It can also, if necessary, be presulphurized at least in part, for example according to the French SULFICAT (R) process, or else by treatment in the presence of a gas containing hydrogen sulphide and / or any other sulphurized compound.
  • a gas containing hydrogen at a temperature of 50 to 500 ° C.
  • R French SULFICAT
  • the mass of mercury capture used in the composition of the assembly which is the subject of the present invention consists of sulfur or a sulfur compound deposited on a porous mineral support or matrix chosen, for example, from the group formed by l alumina, silica-alumina, silica, zeolites, clays, active carbon, aluminous cements, titanium oxides, zirconium oxide or among the other supports, consisting of a porous mineral matrix, cited for the catalyst.
  • Use will preferably be made of a compound containing sulfur and a metal P, where P is chosen from the group formed by copper, iron, silver and, preferably, by copper or the copper-silver association. At least 50% of the metal P is used in the form of sulphide.
  • This capture mass can be prepared according to the method recommended in US patent 4094777 of the applicant or by depositing copper oxide on an alumina then sulphurization by means of an organic polysulphide as described in the French patent application 87 / 07442 of the plaintiff.
  • the proportion of elementary sulfur combined or not in the capture mass is advantageously between 1 and 40% and preferably between 1 and 20% by weight.
  • the proportion of metal P combined or not in the form of sulphide will preferably be between 0.1 and 20% of the total weight of the capture mass.
  • the assembly consisting of the catalyst and the mercury capture mass can be used either in two reactors or in one.
  • reactors When two reactors are used, they can be arranged in series, the reactor containing the catalyst being advantageously placed before that containing the capture mass.
  • the catalyst and the capture mass can be arranged either in two separate beds or mixed intimately.
  • the volume ratio of the mass of desarsenification with catalytic properties to the mass of demercurization may vary between 1:10 and 5: 1.
  • the one containing the mass of desarsenification with catalytic properties may be operated in a temperature range which can range from 180 to 450 ° C., more advantageously from 230 to 420 ° C. and in a preferred manner, from 260 to 390 ° C.
  • the operating pressures will preferably be chosen from 1 to 50 bars absolute, more particularly from 5 to 40 bars and more advantageously from 10 to 30 bars.
  • the hydrogen flow rate expressed in liters of gaseous hydrogen (TPN) per liter of liquid charge will preferably be chosen between 1 and 1000, more particularly between 10 and 300 and more advantageously from 30 to 200.
  • the hourly volumetric speed calculated with respect to the mass of desarsenification with catalytic properties, may be from 0.1 to 30 hours ⁇ 1 more particularly from 0.5 to 20h ⁇ 1 and preferably from 1 to 10 hours ⁇ 1 (volumes of liquid, per volume of mass and per hour).
  • the demercurization mass will be operated in a temperature range which can range from 0 to 400 ° C, more advantageously from 20 to 350 ° C and, preferably, from 40 to 330 ° C.
  • the operating pressures and the flow rate of hydrogen D will be those defined with respect to the mass of desarsenification with catalytic properties.
  • the hourly volumetric speed, calculated with respect to the mass of demercurization may be that indicated for the mass of desarsenification with catalytic properties, it being understood as indicated above, that the volume ratio of the mass of desarsenification to the mass of demercurization may vary from 1:10 to 5: 1, depending in particular on the proportions of arsenic and mercury contained in the charge. It goes without saying that the relative proportions of the two masses and therefore the hourly volumetric speeds relative to the latter may then be very different (same liquid flow but different mass volumes).
  • the charge treated in the presence of the catalyst can optionally be cooled before passing over the demercurization mass.
  • the two capture masses being then placed in a single reactor, this can be operated in a temperature range which can range from 180 to 400 ° C, more advantageously 190 to 350 ° C and in a way preferred 200 to 330 ° C.
  • the hydrogen-rich gas recovered after separation of the purified liquid product it may prove to be advantageous to recycle at the top, at least in part, the hydrogen-rich gas recovered after separation of the purified liquid product.
  • the said recycling allows better control of the partial pressure ratio pH partiS / pH2 in the reaction medium.
  • the feed contains little sulfur (for example less than 20 ppm by weight) it may also prove to be advantageous to add to the feed and / or in the hydrogen at least one sulfur compound in order to increase the said pH2S / pH2 ratio.
  • the charges to which the invention more particularly applies contain from 10 ⁇ 3 to 2 milligrams of mercury per kilogram of charge and, optionally from 10 ⁇ 2 to 10 milligrams arsenic per kilogram of charge.
  • HR 306 catalyst 250 cm3 of HR 306 catalyst, produced by PROCATALYSE, are loaded into a steel reactor 3 cm in diameter.
  • Said HR 306 catalyst consisting of extrudates with a diameter of 1.2 mm and a length of 2 to 10 mm, contains 2.36% of cobalt and 9.33% of molybdenum by weight; the matrix consists of transition alumina.
  • the specific surface is 210 square meters per gram and the pore volume is 0.48 / cm3 / g.
  • the catalyst is then subjected to a presulfurization treatment.
  • a hydrogen sulfide-hydrogen mixture in the volume proportions 3:97 is injected at a rate of 10 l / h.
  • the temperature rise rate is 1 ° C / min and the final level (350 ° C) is 2 hours.
  • this catalyst has a very low efficiency in retaining mercury; on the other hand, it has good effectiveness in retaining arsenic.
  • a capture mass consisting of a copper sulphide is prepared, deposited on an alumina support as described in US Patent No. 4094777 of the Applicant.
  • the mass contains 12% by weight of copper and 6% by weight of sulfur in the form of sulphide.
  • the matrix consists of transition alumina.
  • the specific surface is 70 m2 / g and the pore volume of 0.4 cm3 / g.
  • the capture mass is not effective in retaining arsenic. On the other hand, it has transient effectiveness in retaining mercury, but it drops very quickly over time.
  • the condensate is allowed to pass for 1000 hours.
  • the results of analyzes of mercury in the product after 50, 100, 200, 500 and 1000 hours are summarized in Table III below.
  • Example 5 according to the invention.
  • the operating conditions remain identical, with the exception of the operating temperature of the HR 306 catalyst, brought to 340 ° C. and to the hydrogen flow rate, brought to 200 liters / liter of charge, ie 100 liters / hour.
  • Example 4 The experiment described in Example 4 is reproduced.
  • the reactor containing 100 cm3 of copper sulphide capture mass is now loaded with: 100 cm3 of said mass and 50 cm3 of demercurization mass composed of 13% by weight of sulfur on activated carbon, of the CALGON HGR type, prepared according to the teaching of patent USP3194629.
  • Example 7 according to the invention.
  • Example 3 The first reactor used in Example 3 is now loaded with 200 cm3 of the HMC 841 catalyst, sold by PROCATALYSE.
  • This catalyst consisting of beads of diameters 1.5 to 3 mm contains 1.96% nickel and 8% molybdenum by weight; the matrix consists of transition alumina. The specific surface is 140 m2 / g and the pore volume of 0.89 cm3 / g.
  • the HMC 841 catalyst was presulphurized before loading (ex-situ sulphurization) according to the SULFICAT (R) process sold by the company EURECAT; its sulfur content is 4.8% by weight.
  • the second reactor is loaded with 200 cm3 of a demercurization mass containing 8% of sulfur, 14.5% of copper and 0.2% by weight of silver, prepared according to the teaching of US Pat. No. 4,094,777, then presulphurized by contacting an organic polysulphide according to the teaching of French patent 87-07442 of the applicant.
  • the analysis of the purified liquid effluent shows that it contains only 60 ppm (weight) of sulfur and 33 ppm (weight) of nitrogen.
  • the hydrodesulfurization rate and the hydrodenitrogenation rate are therefore respectively 95.4 and 24%.
  • the effluent contains only 28% of aromatics (compared to 41% in the fresh feed), which demonstrates, in addition to the activity in desarsenification and in demercurization, the additional properties in hydrodesulfurization in hydrodenitrogenation and in hydrogenation of aromatics of the assembly (catalyst + demercurization mass) according to the invention.
  • the operating temperature is equal to 220 ° C.
  • the operating pressure equal to 50 bars (absolute)
  • the flow rate is 200 liters per liter of charge, or 120 liters per hour.
  • the charge rate is 0.6 liters per hour.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)

Abstract

Process for eliminating mercury and possibly arsenic from hydrocarbon fillers containing mercury and sulphur, characterized in that said filler is made to pass through in the presence of hydrogen and contact an arsenic-capturing body ('catalyst') having catalytic properties, said 'catalyst' containing at least one metal of the group consisting of nickel, cobalt, iron, palladium and platinum, at least one metal of the group consisting of chromium, molybdenum, tungsten and uranium and an active phase support, whereby said 'catalyst' is followed on the same filler path by, or is combined with, a mercury-capturing body containing a sulphide of at least one metal of the copper, iron and silver group or sulphur and an active phase support.

Description

Il est connu que les condensats liquides sous-produits de la production du gaz (gaz naturel, gaz associé) et les pétroles bruts peuvent contenir de nombreux composés métalliques à l'état de traces, généralement présents sous forme de complexes organométalliques, dans lesquels le métal forme des liaisons avec un ou plusieurs atomes de carbone du radical organométallique.It is known that the liquid condensates by-products of gas production (natural gas, associated gas) and crude oils can contain many trace metal compounds, generally present in the form of organometallic complexes, in which the metal forms bonds with one or more carbon atoms of the organometallic radical.

Ces composés métalliques sont des poisons des catalyseurs utilisés dans les procédés de transformation du pétrole. En particulier, ils empoisonnent les catalyseurs d'hydrotraitement et d'hydrogénation en se déposant progressivement sur la surface active. Des composés métalliques se trouvent notamment dans les coupes lourdes provenant de la distillation du brut pétrolier (nickel, vanadium, arsenic, mercure) ou encore dans les condensats de gaz naturel (mercure, arsenic).These metal compounds are poisonous catalysts used in petroleum transformation processes. In particular, they poison the hydrotreatment and hydrogenation catalysts by gradually depositing on the active surface. Metallic compounds are found in particular in heavy cuts from the distillation of petroleum crude (nickel, vanadium, arsenic, mercury) or in natural gas condensates (mercury, arsenic).

Les traitements de craquage thermique ou catalytique des coupes d'hydrocarbures ci-dessus, par exemple leur vapocraquage pour conversion en coupes d'hydrocarbures plus légers, peuvent permettre l'élimination de certains métaux (par exemple le nickel, le vanadium...); par contre, certains autres métaux (par exemple le mercure, l'arsenic...) susceptibles de former des composés volatils et/ou étant volatils à l'état d'élément (mercure) se retrouvent au moins en partie dans les coupes plus légères et peuvent, de ce fait, empoisonner les catalyseurs des procédés de transformation subséquents. Le mercure présente en outre le risque de provoquer des corrosions par formation d'amalgames, par exemple avec les alliages à base d'aluminium, notamment dans les sections des procédés opérant à une température suffisamment basse pour provoquer la condensation de mercure liquide (fractionnements cryogéniques, échangeurs).The thermal or catalytic cracking treatments of the above hydrocarbon cuts, for example their steam cracking for conversion into lighter hydrocarbon cuts, can allow the elimination of certain metals (for example nickel, vanadium ...) ; on the other hand, certain other metals (for example mercury, arsenic ...) capable of forming volatile compounds and / or being volatile in the element state (mercury) are found at least in part in the cuts more light and can therefore poison the catalysts of subsequent transformation processes. Mercury also presents the risk of causing corrosion by the formation of amalgams, for example with aluminum-based alloys, in particular in the process sections operating at a temperature low enough to cause condensation of liquid mercury (cryogenic fractionations , exchangers).

Des procédés antérieurs sont connus pour éliminer le mercure ou l'arsenic dans les hydrocarbures en phase gazeuse; on opère notamment en présence de masses solides, lesquelles peuvent être dénommées indifferemment : masses d'adsorption, de captation, de piégeage, d'extraction, de transfert de métaux.Prior methods are known for removing mercury or arsenic from hydrocarbons in the gas phase; one operates in particular in the presence of solid masses, which can be called indifferently: adsorption, capture, trapping, extraction and metal transfer masses.

Pour ce qui concerne les masses pour démercurisation : le brevet US 3194629 décrit des masses constituées de soufre ou encore d'iode déposé sur charbon actif.As regards the masses for demercurization: US Pat. No. 3,194,629 describes masses consisting of sulfur or of iodine deposited on activated carbon.

Le brevet US 4094777 de la demanderesse décrit d'autres masses comprenant du cuivre au moins en partie sous forme de sulfure et un support minéral. Ces masses peuvent également renfermer de l'argent.US patent 4094777 of the applicant describes other masses comprising copper at least partly in the form of sulphide and an inorganic support. These masses can also contain money.

La demande française 87-07442 de la demanderesse décrit un mode de préparation spécifique des dites masses.French application 87-07442 of the applicant describes a specific method of preparation of said masses.

Le brevet FR 2534826 décrit d'autres masses constituées de soufre élémentaire et d'un support minéral.Patent FR 2534826 describes other masses consisting of elemental sulfur and an inorganic support.

Pour ce qui concerne la désarsénification:Regarding the de-arsenification:

Le brevet DE 2149993 enseigne d'utiliser les métaux du groupe VIII (nickel, platine, palladium).Patent DE 2149993 teaches the use of Group VIII metals (nickel, platinum, palladium).

Le brevet US 4069140 décrit l'utilisation de diverses masses absorbantes. L'oxyde de fer supporté est décrit, l'emploi d'oxyde de plomb est décrit dans le brevet US 3782076 et celui d'oxyde de cuivre dans le brevet US 3812653.US Patent 4069140 describes the use of various absorbent masses. The supported iron oxide is described, the use of lead oxide is described in US Pat. No. 3,782,076 and that of copper oxide in US Patent 3,812,653.

Or, si certains des produits décrits dans l'art antérieur présentent de bonnes performances pour la démercurisation ou encore pour la désarsénification de gaz (par exemple l'hydrogène) ou de mélanges gazeux (par exemple le gaz naturel) et plus particulièrement lorsque le gaz naturel contient une quantité importante d'hydrocarbures renfermant trois ou plus de trois atomes de carbone, les essais effectués par la demanderesse montrent que les mêmes produits se révèlent peu efficaces dès que les charges contiennent des composés autres que les métaux élémentaires, par exemple pour l'arsenic, des arsines comprenant des chaînes hydrocarbonées renfermant deux ou plus de deux atomes de carbone ou bien, pour le mercure, le diméthylmercure et les autres composés du mercure comprenant des chaînes hydrocarbonées renfermant deux ou plus de deux atomes de carbone et, éventuellement d'autres éléments non métalliques (soufre, azote...).However, if some of the products described in the prior art exhibit good performance for demercurization or also for the de-arsenification of gas (for example hydrogen) or gaseous mixtures (for example natural gas) and more particularly when the gas natural contains a significant amount of hydrocarbons containing three or more than three carbon atoms, the tests carried out by the applicant show that the same products prove to be ineffective as soon as the fillers contain compounds other than elemental metals, for example for arsenic, arsines comprising hydrocarbon chains containing two or more carbon atoms or, for mercury, dimethylmercury and the other mercury compounds comprising hydrocarbon chains containing two or more of two carbon atoms and, possibly other non-metallic elements (sulfur, nitrogen ...).

En outre, d'autres essais menés à bien par la demanderesse, montrent que lorsque du soufre est présent dans la charge, il peut interagir avec les éléments métalliques actifs pour la désarsénification lesquels, alors transformés en sulfures au moins pour partie, peuvent alors présenter une perte d'activité significative.In addition, other tests carried out by the applicant, show that when sulfur is present in the feed, it can interact with the active metallic elements for the de-arsenification which, then transformed into sulfides at least in part, can then have significant loss of activity.

L'objet de l'invention est un procédé d'élimination du mercure et éventuellement d'arsenic contenus dans une charge hydrocarbonée et qui remédie aux défauts des procédés antérieurs.The object of the invention is a process for removing mercury and possibly arsenic contained in a hydrocarbon feedstock and which remedies the defects of the previous processes.

Un autre objet de l'invention est de pouvoir éliminer le mercure et éventuellement l'arsenic même dans des charges hydrocarbonées contenant en outre des proportions significatives de soufre. Par proportions significatives on entend de 0,005 à 3% poids et notamment de 0,02 à 2% poids.Another object of the invention is to be able to remove the mercury and possibly the arsenic even in hydrocarbon feedstocks further containing significant proportions of sulfur. By significant proportions is meant from 0.005 to 3% by weight and in particular from 0.02 to 2% by weight.

Selon le procédé de l'invention, on fait passer un mélange de la charge et d'hydrogène au contact d'un catalyseur que par la suite on appellera arbitrairement masse de captation d'arsenic, à propriétés catalytiques, renfermant :

  • au moins un métal M du groupe formé par le fer, le cobalt, le nickel, le palladium et le platine
  • au moins un métal N du groupe formé par le chrome, le molybdène, le tungstène et l'uranium
  • et éventuellement un support de phase active, à base d'au moins une matrice minérale poreuse, le dit catalyseur étant suivi sur le trajet de la charge de,,ou mélangé à, une masse de captation du mercure, renfermant du soufre et/ou au moins un sulfure métallique d'au moins un métal P choisi dans le groupe formé par le cuivre, le fer et l'argent, et un support de phase active.
According to the process of the invention, a mixture of the charge and of hydrogen is passed through in contact with a catalyst which will subsequently be called arbitrarily an arsenic capture mass, with catalytic properties, containing:
  • at least one metal M from the group formed by iron, cobalt, nickel, palladium and platinum
  • at least one metal N from the group formed by chromium, molybdenum, tungsten and uranium
  • and optionally an active phase support, based on at least one porous mineral matrix, the said catalyst being followed on the path of the charge of ,, or mixed with, a mass for capturing mercury, containing sulfur and / or at least one metal sulfide of at least one metal P chosen from the group formed by copper, iron and silver, and an active phase support.

Selon un autre mode de réalisation de l'invention, on peut également ajouter un composé du soufre; par exemple un sulfure organique, ou encore du sulfure d'hydrogène, soit dans la charge brute (avant désarsénification), soit dans la charge traitée en présence d'hydrogène et de la masse de désarsénéfication à propriétés catalytiques, avant démercurisation en présence du deuxième lit.According to another embodiment of the invention, it is also possible to add a sulfur compound; for example an organic sulphide, or alternatively hydrogen sulphide, either in the raw charge (before de-arsenification) or in the charge treated in the presence of hydrogen and of the de-arsenification mass with catalytic properties, before demercurization in the presence of the second bed.

Lorsque la charge renferme aussi de l'arsenic, celui-ci est également éliminé. On opère de préférence avec la charge au moins en partie en phase liquide.When the charge also contains arsenic, it is also eliminated. The operation is preferably carried out with the feed at least partly in the liquid phase.

Il a aussi été découvert, d'une façon surprenante, qu'en présence de concentrations élevées en arsenic ou encore en présence de vitesses volumétriques horaires "liquides" élevées pouvant provoquer une captation imparfaite de l'arsenic (par exemple moins de 90%) sur la masse de captation d'arsenic à propriétés catalytiques, la masse de captation du mercure fonctionne également de manière très satisfaisante pour la captation de l'arsenic.It has also been discovered, surprisingly, that in the presence of high arsenic concentrations or in the presence of high "liquid" hourly volumetric velocities which can cause an imperfect uptake of arsenic (for example less than 90%) on the mass of arsenic capture with catalytic properties, the mass of mercury capture also functions very satisfactorily for the capture of arsenic.

Il a enfin été découvert que, d'une manière surprenante, le catalyseur permet également une hydrodésulfuration, une hydrodenitrification et, au moins pour partie une hydrogénation des composés insaturés pouvant se trouver dans la charge, ce qui peut se révèler avantageux lorsque les dites charges sont destinées au vapocraquage. Enfin la dite masse permet une démétallation efficace si, outre l'arsenic et le mercure, du vanadium et/ou du nickel sont présents.Finally, it has been discovered that, surprisingly, the catalyst also allows hydrodesulfurization, hydrodenitrification and, at least in part, hydrogenation of the unsaturated compounds which may be present in the feed, which can turn out to be advantageous when said fillers are intended for steam cracking. Finally, said mass allows effective demetallation if, in addition to arsenic and mercury, vanadium and / or nickel are present.

D'une façon surprenante, les propriétés catalytiques de ladite masse de captation d'arsenic demeurent inchangées, même en cas d'absence stricte du dit métal dans la charge.Surprisingly, the catalytic properties of said arsenic capture mass remain unchanged, even in the event of the strict absence of said metal in the charge.

La dite masse de captation d'arsenic à propriétés catalytiques est donc un solide complexe, lequel, en présence d'hydrogène et sous les conditions opératoires décrites ci-après :

  • active par catalyse les composés de mercure et d'arsenic (si l'arsenic est présent) et les transforme en composés réactifs vis-à-vis des masses de captation objet de l'invention,
  • capte sélectivement l'arsenic (si de l'arsenic est présent)
  • active par catalyse les dits composés du mercure même en l'absence stricte de composés d'arsenic.
Said arsenic capture mass with catalytic properties is therefore a complex solid, which, in the presence of hydrogen and under the operating conditions described below:
  • activates the mercury and arsenic compounds by catalysis (if the arsenic is present) and transforms them into reactive compounds vis-à-vis the capture masses object of the invention,
  • selectively captures arsenic (if arsenic is present)
  • activates by catalysis the so-called mercury compounds even in the strict absence of arsenic compounds.

La masse de captation d'arsenic à propriétés catalytiques désignée par la suite comme "le catalyseur" entrant dans la composition de l'ensemble faisant l'objet de la présente invention est donc constituée d'au moins un métal M choisi dans le groupe formé par le fer, le nickel, le cobalt, le palladium, le platine et d'au moins un métal N choisi dans le groupe formé par le chrome le molybdène, le tungstène et l'uranium, ces métaux, sous forme d'oxydes et/ou d'oxysulfures et/ou de sulfures, pouvant être utilisés tels quels ou de préférence être déposé sur au moins un support de la liste qui fait suite. En conditions d'usage il est impératif que le métal M et/ou le métal N se trouvent sous forme sulfurée pour au moins 50% de leur totalité.The arsenic capture mass with catalytic properties subsequently designated as "the catalyst" used in the composition of the assembly which is the subject of the present invention therefore consists of at least one metal M chosen from the group formed by iron, nickel, cobalt, palladium, platinum and at least one metal N chosen from the group formed by chromium, molybdenum, tungsten and uranium, these metals, in the form of oxides and / or oxysulfides and / or sulfides, which can be used as such or preferably be deposited on at least one support from the list which follows. Under conditions of use, it is imperative that the metal M and / or the metal N are present in sulfurized form for at least 50% of their totality.

Il est connu de l'homme de métier que l'état d'équilibre entre les formes réduites et sulfurées dépend entre autres des conditions opératoires et notamment, outre la température, des pressions partielles en hydrogène, en sulfure d'hydrogène, et en vapeur d'eau dans le milieu réactionnel, e.g. :

Figure imgb0001
Figure imgb0002
 It is known to those skilled in the art that the state of equilibrium between the reduced and sulfurized forms depends inter alia on the operating conditions and in particular, in addition to the temperature, partial pressures of hydrogen, of hydrogen sulfide, and of vapor of water in the reaction medium, eg:
Figure imgb0001
Figure imgb0002

Les quantités respectives de métal ou métaux M et de métal ou métaux N contenues dans le catalyseur sont habituellement telles que le rapport atomique métal ou métaux M sur métal ou métaux N, M/N soit d'environ 0,3:1 à 0,7:1 et de préférence d'environ 0,3:1 à environ 0,45:1 .The respective amounts of metal or metals M and of metal or metals N contained in the catalyst are usually such that the atomic ratio of metal or metals M to metal or metals N, M / N is approximately 0.3: 1 to 0, 7: 1 and preferably from about 0.3: 1 to about 0.45: 1.

La quantité pondérale de métaux contenus dans le catalyseur fini exprimée en poids de métal par rapport au poids du catalyseur fini est habituellement, pour le métal ou les métaux N d'environ 2 à 30% et de préférence d'environ 5 à 25%, et pour le métal ou les métaux M d'environ 0,01 à 15%, plus particulièrement d'environ 0,01 à 5% et de préférence d'environ 0,05 à 3% pour le palladium et/ou le platine; et d'environ 0,5 à 15% et de préférence d'environ 1 à 10% dans le cas des métaux M non-nobles (Fe, Co, Ni).The quantity by weight of metals contained in the finished catalyst expressed by weight of metal relative to the weight of the finished catalyst is usually, for the metal or metals N, from about 2 to 30% and preferably from about 5 to 25%, and for the metal or metals M of approximately 0.01 to 15%, more particularly of approximately 0.01 to 5% and preferably of approximately 0.05 to 3% for palladium and / or platinum; and approximately 0.5 to 15% and preferably approximately 1 to 10% in the case of non-noble metals M (Fe, Co, Ni).

Parmi les métaux N on utilise de préférence le molybdène et/ou le tungstène et parmi les métaux M on préfère employer les métaux non nobles fer, cobalt et/ou nickel. D'une manière avantageuse on utilise les associations de métaux suivantes : nickel-molybdène, nickel-tungstène, cobalt-molybdène, cobalt-tungstène, fer-molybdène et fer-tungstène. Les associations les plus préférées sont nickel-molydène et cobalt-molybdène. Il est également possible d'utiliser des associations de trois métaux, par exemple nickel-cobalt-molybdène.Among the metals N, molybdenum and / or tungsten are preferably used, and among the metals M, the non-noble metals iron, cobalt and / or nickel are preferred. Advantageously, the following combinations of metals are used: nickel-molybdenum, nickel-tungsten, cobalt-molybdenum, cobalt-tungsten, iron-molybdenum and iron-tungsten. The most preferred combinations are nickel-molydene and cobalt-molybdenum. It is also possible to use combinations of three metals, for example nickel-cobalt-molybdenum.

La matrice minérale poreuse est choisie de manière à ce que le catalyseur final ait les caractéristiques de volume poreux optimales. Cette matrice comprend habituellement au moins un des éléments du groupe formé par l'alumine, la silice, la silice-alumine, la magnésie, la zircone, l'oxyde de titane, les argiles, les ciments alumineux, les aluminates, par exemple les aluminates de magnésium, de calcium , de strontium, de barium, de manganèse, de fer, de cobalt, de nickel, de cuivre et de zinc, les aluminates mixtes par exemple ceux comprenant au moins deux des métaux cités ci-avant.The porous mineral matrix is chosen so that the final catalyst has the optimal pore volume characteristics. This matrix usually comprises at least one of the elements of the group formed by alumina, silica, silica-alumina, magnesia, zirconia, titanium oxide, clays, aluminous cements, aluminates, for example magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, copper and zinc aluminates, mixed aluminates, for example those comprising at least two of the metals mentioned above.

On peut préférer utiliser des matrices contenant de l'alumine par exemple l'alumine et la silice-alumine ou encore de l'oxyde de titane. Lorsque la matrice contient de la silice il est préférable que la quantité de silice soit au plus égale à 25% en poids par rapport au poids total de la matrice.It is preferable to use matrices containing alumina, for example alumina and silica-alumina or alternatively titanium oxide. When the matrix contains silica it is preferable that the quantity of silica is at most equal to 25% by weight relative to the total weight of the matrix.

La matrice peut également renfermer outre au moins l'un des composés cités ci-avant, au moins un alumino-silicate zéolithique cristallin, (zéolithe) synthétique ou naturel. La quantité de zéolithe représente habituellement de 0 à 95% en poids et de préférence de 1 à 80% en poids par rapport au poids de la matrice.The matrix can also contain, in addition to at least one of the compounds mentioned above, at least one crystalline or natural zeolitic alumino-silicate (zeolite). The amount of zeolite usually represents from 0 to 95% by weight and preferably from 1 to 80% by weight relative to the weight of the matrix.

On peut aussi utiliser avantageusement des mélanges d'alumine et de zéolithe,ou encore des mélanges de silice-alumine et de zéolithe.It is also advantageous to use mixtures of alumina and zeolite, or alternatively mixtures of silica-alumina and zeolite.

Parmi les zéolithes on préfère habituellement employer des zéolithes dont le rapport atomique de charpente, silicium sur aluminium (Si/Al) est supérieur à environ 5:1. On emploie avantageusement des zéolithes de structures faujasite et en particulier les zéolithes Y stabilisées ou ultrastabilisées.Among the zeolites, it is usually preferred to use zeolites with an atomic ratio of framework, silicon to aluminum (Si / Al) greater than about 5: 1. Advantageously, zeolites with faujasite structures are used, and in particular stabilized or ultra-stabilized Y zeolites.

La matrice la plus couramment employée est l'alumine, et on préfère usuellement les alumines de transition, pures ou en mélange, telles que γC γT, δ, ϑ.The most commonly used matrix is alumina, and transition alumina, pure or mixed, such as γ C γ T , δ, ϑ, is usually preferred.

La dite matrice présentera de préférence une grande surface et un volume poreux suffisant, c'est-à-dire respectivement au moins 50 m2/g et au moins 0,5 cm3/g, par exemple 50 à 350 m2/g et 0,5 à 1,2 cm3/g. La fraction de volume macroporeux, constituée de l'ensemble des pores de diamètre moyen au moins égal à 0,1 µm pourra représenter de 10% à 30% du volume poreux total.Said matrix will preferably have a large surface area and a sufficient pore volume, that is to say respectively at least 50 m2 / g and at least 0.5 cm3 / g, for example 50 to 350 m2 / g and 0, 5 to 1.2 cm3 / g. The fraction of macroporous volume, consisting of all the pores with an average diameter at least equal to 0.1 μm, may represent from 10% to 30% of the total pore volume.

La préparation d'un tel catalyseur est suffisamment connue de l'homme de métier pour ne pas être répétée dans le cadre de la présente invention.The preparation of such a catalyst is sufficiently known to those skilled in the art not to be repeated in the context of the present invention.

Avant utilisation, le catalyseur peut, si nécessaire, être traité par un gaz contenant de l'hydrogène à une température de 50 à 500°C. Il peut également, si nécessaire, être présulfuré au moins pour partie, par exemple selon le procédé français SULFICAT (R), ou encore par traitement en présence d'un gaz contenant du sulfure d'hydrogène et/ou tout autre composé sulfuré.Before use, the catalyst can, if necessary, be treated with a gas containing hydrogen at a temperature of 50 to 500 ° C. It can also, if necessary, be presulphurized at least in part, for example according to the French SULFICAT (R) process, or else by treatment in the presence of a gas containing hydrogen sulphide and / or any other sulphurized compound.

La masse de captation du mercure entrant dans la composition de l'ensemble faisant l'objet de la présente invention est constituée par du soufre ou un composé soufré déposé sur un support ou matrice minérale poreuse choisie, par exemple, dans le groupe formé par l'alumine, les silice-alumines, la silice, les zéolithes, les argiles, les charbons actifs, les ciments alumineux, les oxydes de titane, l'oxyde de zirconium ou encore parmi les autres supports, constitués d'une matrice minérale poreuse, cités pour le catalyseur.The mass of mercury capture used in the composition of the assembly which is the subject of the present invention consists of sulfur or a sulfur compound deposited on a porous mineral support or matrix chosen, for example, from the group formed by l alumina, silica-alumina, silica, zeolites, clays, active carbon, aluminous cements, titanium oxides, zirconium oxide or among the other supports, consisting of a porous mineral matrix, cited for the catalyst.

On peut utiliser, comme masse de captation, du soufre déposé sur un support et par exemple un produit commercial tel le CALGON HGR, et plus généralement tout produit constitué par du soufre déposé sur un charbon actif ou sur une alumine macroporeuse tel que décrit dans le brevet français 2534826.It is possible to use, as capture mass, sulfur deposited on a support and for example a commercial product such as CALGON HGR, and more generally any product constituted by sulfur deposited on an activated carbon or on a macroporous alumina as described in French patent 2534826.

On utilisera de préférence un composé renfermant du soufre et un métal P, où P est choisi dans le groupe formé par le cuivre, le fer, l'argent et, de façon préférée, par le cuivre ou l'association cuivre-argent. Au moins 50% du métal P est employé sous forme de sulfure.Use will preferably be made of a compound containing sulfur and a metal P, where P is chosen from the group formed by copper, iron, silver and, preferably, by copper or the copper-silver association. At least 50% of the metal P is used in the form of sulphide.

Cette masse de captation peut être préparée selon la méthode préconisée dans le brevet US 4094777 de la demanderesse ou encore par dépôt d'oxyde de cuivre sur une alumine puis sulfuration au moyen d'un polysulfure organique tel que décrit dans la demande de brevet français 87/07442 de la demanderesse.This capture mass can be prepared according to the method recommended in US patent 4094777 of the applicant or by depositing copper oxide on an alumina then sulphurization by means of an organic polysulphide as described in the French patent application 87 / 07442 of the plaintiff.

La proportion de soufre élémentaire combiné ou non dans la masse de captation est avantageusement comprise entre 1 et 40% et de façon préférée entre 1 et 20% en poids.The proportion of elementary sulfur combined or not in the capture mass is advantageously between 1 and 40% and preferably between 1 and 20% by weight.

La proportion en métal P combiné ou non sous forme de sulfure sera de préférence comprise entre 0,1 et 20% du poids total de la masse de captation.The proportion of metal P combined or not in the form of sulphide will preferably be between 0.1 and 20% of the total weight of the capture mass.

L'ensemble constitué par le catalyseur et la masse de captation du mercure pourra être mis en oeuvre soit dans deux réacteurs soit en un seul.The assembly consisting of the catalyst and the mercury capture mass can be used either in two reactors or in one.

Lorsque deux réacteurs seront utilisés, ils pourront être disposés en série, le réacteur renfermant le catalyseur étant avantageusement placé avant celui renfermant la masse de captation.When two reactors are used, they can be arranged in series, the reactor containing the catalyst being advantageously placed before that containing the capture mass.

Lorsqu'un seul réacteur est utilisé, le catalyseur et la masse de captation pourront être disposés soit en deux lits séparés soit mélangés intimement.When only one reactor is used, the catalyst and the capture mass can be arranged either in two separate beds or mixed intimately.

Selon les quantités de mercure et/ou d'arsenic (calculées sous forme élémentaire) contenues dans la charge, le rapport volumique de la masse de désarsénification à propriétés catalytiques à la masse de démercurisation pourra varier entre 1:10 et 5:1.Depending on the quantities of mercury and / or arsenic (calculated in elementary form) contained in the charge, the volume ratio of the mass of desarsenification with catalytic properties to the mass of demercurization may vary between 1:10 and 5: 1.

Lorsque l'on opère en réacteur séparés, on pourra opérer celui contenant la masse de désarsénification à propriétés catalytiques dans un domaine de température pouvant aller de 180 à 450°C, plus avantageusement de 230 à 420°C et d'une façon préférée, de 260 à 390°C.When operating in separate reactors, the one containing the mass of desarsenification with catalytic properties may be operated in a temperature range which can range from 180 to 450 ° C., more advantageously from 230 to 420 ° C. and in a preferred manner, from 260 to 390 ° C.

Les pressions opératoires seront choisies de préférence de 1 à 50 bars absolus, plus particulièrement de 5 à 40 bars et de façon plus avantageuse de 10 à 30 bars.The operating pressures will preferably be chosen from 1 to 50 bars absolute, more particularly from 5 to 40 bars and more advantageously from 10 to 30 bars.

Le débit d'hydrogène, exprimé en litres d'hydrogène gazeux (TPN) par litre de charge liquide sera choisi de préférence entre 1 et 1000, plus particulièrement entre 10 et 300 et de façon plus avantageuse de 30 à 200.The hydrogen flow rate, expressed in liters of gaseous hydrogen (TPN) per liter of liquid charge will preferably be chosen between 1 and 1000, more particularly between 10 and 300 and more advantageously from 30 to 200.

La vitesse volumétrique horaire, calculée par rapport à la masse de désarsénification à propriétés catalytiques, pourra être de 0,1 à 30 heures⁻¹ plus particulièrement de 0,5 à 20h⁻¹ et d'une façon préférée, de 1 à 10 h⁻¹ (volumes de liquide, par volume de masse et par heure).The hourly volumetric speed, calculated with respect to the mass of desarsenification with catalytic properties, may be from 0.1 to 30 hours⁻¹ more particularly from 0.5 to 20h⁻¹ and preferably from 1 to 10 hours ⁻¹ (volumes of liquid, per volume of mass and per hour).

La masse de démercurisation sera opérée dans un domaine de température pouvant aller de 0 à 400°C, plus avantageusement de 20 à 350°C et, d'une façon préférée, de 40 à 330°C.The demercurization mass will be operated in a temperature range which can range from 0 to 400 ° C, more advantageously from 20 to 350 ° C and, preferably, from 40 to 330 ° C.

Les pressions opératoires et le débit d'hydrogène D seront ceux définis par rapport à la masse de désarsénification à propriétés catalytiques.The operating pressures and the flow rate of hydrogen D will be those defined with respect to the mass of desarsenification with catalytic properties.

La vitesse volumétrique horaire, calculée par rapport à la masse de démercurisation, pourra être celle indiquée pour la masse de désarsénification à propriétés catalytiques, étant bien entendu comme indiqué ci-avant, que le rapport volumique de la masse de désarsénification à la masse de démercurisation pourra varier de 1:10 à 5:1, en fonction notamment des'proportions en arsenic et en mercure contenues dans la charge. Il va'donc de soi que les proportions relatives des deux masses et donc les vitesses volumétriques horaires par rapport à ces dernières pourront alors être très différentes (même débit liquide mais volumes de masse différents).The hourly volumetric speed, calculated with respect to the mass of demercurization, may be that indicated for the mass of desarsenification with catalytic properties, it being understood as indicated above, that the volume ratio of the mass of desarsenification to the mass of demercurization may vary from 1:10 to 5: 1, depending in particular on the proportions of arsenic and mercury contained in the charge. It goes without saying that the relative proportions of the two masses and therefore the hourly volumetric speeds relative to the latter may then be very different (same liquid flow but different mass volumes).

Dans un mode de réalisation de l'invention, la charge traitée en présence du catalyseur peut éventuellement être refroidie avant passage sur la masse de démercurisation.In one embodiment of the invention, the charge treated in the presence of the catalyst can optionally be cooled before passing over the demercurization mass.

Dans un autre mode, les deux masses de captation étant alors disposées dans un réacteur unique, on pourra opérer celui-ci dans un domaine de température pouvant aller de 180 à 400°C, plus avantageusement 190 à 350°C et d'une façon préférée 200 à 330°C.In another mode, the two capture masses being then placed in a single reactor, this can be operated in a temperature range which can range from 180 to 400 ° C, more advantageously 190 to 350 ° C and in a way preferred 200 to 330 ° C.

Enfin, comme il est connu de l'homme de métier, il peut se révèler avantageux de recycler en tête, au moins pour partie, le gaz riche en hydrogène récupéré après séparation du produit liquide purifié. Outre une diminution importante de la consommation en hydrogène, le dit recyclage permet un meilleur contrôle du rapport de pressions partielles pH₂S/pH₂ dans le mileu réactionnel. Comme indiqué ci-avant, pour le cas où la charge contient peu de soufre (par exemple moins de 20 ppm poids) il peut se révèler en outre avantageux de rajouter dans la charge et/ou dans l'hydrogène au moins un composé de soufre afin d'augmenter le dit rapport pH₂S/pH₂.Finally, as is known to those skilled in the art, it may prove to be advantageous to recycle at the top, at least in part, the hydrogen-rich gas recovered after separation of the purified liquid product. In addition to a significant reduction in hydrogen consumption, the said recycling allows better control of the partial pressure ratio pH partiS / pH₂ in the reaction medium. As indicated above, in the case where the feed contains little sulfur (for example less than 20 ppm by weight) it may also prove to be advantageous to add to the feed and / or in the hydrogen at least one sulfur compound in order to increase the said pH₂S / pH₂ ratio.

Les charges auxquelles s'applique plus particulièrement l'invention renferment de 10⁻³ à 2 milligrammes de mercure par kilogramme de charge et, éventuellement de 10⁻² à 10 milligrammes d'arsenic par kilogramme de charge.The charges to which the invention more particularly applies contain from 10⁻³ to 2 milligrams of mercury per kilogram of charge and, optionally from 10⁻² to 10 milligrams arsenic per kilogram of charge.

Les exemples qui font suite permettent d'illustrer les différents aspects de l'invention sans en limiter la portée. Il ira de soi pour l'homme de métier, vu les exemples, que si la masse de désarsénification seule est.suffisante pour traiter des charges ne contenant que de l'arsenic; il est par contre nécessaire d'utiliser la masse de démercurisation et la masse de désarsénification à propriétés catalytiques, pour démercuriser efficacement des charges ne contenant que du mercure. Des essais comparatifs identiques à la série d'exemples 1 à 4 ont été menés en l'absence d'arsenic dans la charge; ils ont conduit à des résultats semblables.The examples which follow make it possible to illustrate the various aspects of the invention without limiting its scope. It will go without saying for those skilled in the art, given the examples, that if the mass of de-arsenification alone is sufficient to treat charges containing only arsenic; on the other hand, it is necessary to use the mass of demercurization and the mass of desarsenification with catalytic properties, to effectively demercurize charges containing only mercury. Comparative tests identical to the series of examples 1 to 4 were carried out in the absence of arsenic in the charge; they have led to similar results.

Exemple 1 (comparaison) Example 1 (comparison)

250 cm3 de catalyseur HR 306, produit par PROCATALYSE, sont chargés dans un réacteur en acier de 3 cm de diamètre.250 cm3 of HR 306 catalyst, produced by PROCATALYSE, are loaded into a steel reactor 3 cm in diameter.

Le dit catalyseur HR 306, constitué d'extrudés de diamètre 1,2 mm et de longueur 2 à 10 mm, contient 2,36% de cobalt et 9,33% de molybdène en poids; la matrice est constituée d'alumine de transition. La surface spécifique est de 210 mètres carrés par gramme et le volume poreux, de 0,48/cm3/g.Said HR 306 catalyst, consisting of extrudates with a diameter of 1.2 mm and a length of 2 to 10 mm, contains 2.36% of cobalt and 9.33% of molybdenum by weight; the matrix consists of transition alumina. The specific surface is 210 square meters per gram and the pore volume is 0.48 / cm3 / g.

On fait ensuite subir au catalyseur un traitement de présulfuration. Un mélange sulfure d'hydrogène-hydrogène dans les proportions volumiques 3:97 est injecté à raison de 10 l/h. La vitesse de montée en température est de 1°C/mn et le palier final (350°C) est de 2 heures.The catalyst is then subjected to a presulfurization treatment. A hydrogen sulfide-hydrogen mixture in the volume proportions 3:97 is injected at a rate of 10 l / h. The temperature rise rate is 1 ° C / min and the final level (350 ° C) is 2 hours.

Le débit d'hydrogène étant seul maintenu, on fait enfin passer sur le catalyseur, en flux, ascendant, un condensat lourd de gaz liquéfié, dont les caractéristiques sont indiquées au tableau I, et de l'hydrogène dans les conditions suivantes :

Débit de charge
: 500 cm3/h
Température
: 320°C
Pression totale
: 30 bars absolus

Débit d'hydrogène 100 litres/litre de charge, soit 50 litres/heure.Since the hydrogen flow rate is only maintained, a heavy condensate of liquefied gas, the characteristics of which are indicated in Table I, and hydrogen under the following conditions are finally passed over the catalyst, in ascending flow.
Charge flow
: 500 cm3 / h
Temperature
: 320 ° C
Total pressure
: 30 bars absolute

Hydrogen flow 100 liters / liter of charge, i.e. 50 liters / hour.

On laisse passer le condensat et l'hydrogène durant 500 heures. Les résultats d'analyses de mercure et d'arsenic dans le produit au bout de 20, 50, 100, 200 et 500 heures sont résumés dans le tableau III.The condensate and the hydrogen are allowed to pass for 500 hours. The results of analyzes of mercury and arsenic in the product after 20, 50, 100, 200 and 500 hours are summarized in Table III.

On voit que ce catalyseur présente une efficacité très faible pour retenir le mercure; il présente par contre une bonne efficacité pour retenir l'arsenic.We see that this catalyst has a very low efficiency in retaining mercury; on the other hand, it has good effectiveness in retaining arsenic.

Exemple 2 (comparaison) Example 2 (comparison)

Dans cet exemple, on prépare une masse de captation constituée d'un sulfure de cuivre, déposé sur un support d'alumine telle que décrite dans le brevet US n° 4094777 de la demanderesse.In this example, a capture mass consisting of a copper sulphide is prepared, deposited on an alumina support as described in US Patent No. 4094777 of the Applicant.

La masse contient 12% poids de cuivre et 6% poids de soufre sous forme de sulfure. La matrice est constituée d'alumine de transition. La surface spécifique est de 70 m2/g et le volume poreux de 0,4 cm3/g.The mass contains 12% by weight of copper and 6% by weight of sulfur in the form of sulphide. The matrix consists of transition alumina. The specific surface is 70 m2 / g and the pore volume of 0.4 cm3 / g.

100 cm3 de cette masse sont alors chargés dans un réacteur identique à celui décrit dans l'exemple 1. On fait ensuite passer sur la masse, en flux ascendant, un condensat lourd de gaz liquéfié identique à celui utilisé dans l'exemple 1 (cf. Tableau I) dans les conditions suivantes :

Débit de charge :
500 cm3/h
Pression totale :
30 bars absolus
Température :
40°C
Débit d'hydrogène :
100 litres par litre de charge, soit 50 litres par heure
100 cm3 of this mass are then loaded into a reactor identical to that described in Example 1. Then, a heavy condensate of liquefied gas identical to that used in Example 1 is passed over the mass, in ascending flow. Table I) under the following conditions:
Charge flow:
500 cm3 / h
Total pressure:
30 bars absolute
Temperature :
40 ° C
Hydrogen flow:
100 liters per liter of charge, i.e. 50 liters per hour

On laisse passer le condensat durant 500 heures. Les résultats d'analyses de mercure et d'arsenic dans le produit au bout de 20, 50, 100, 200 et 500 heures sont résumés dans le tableau III.The condensate is allowed to pass for 500 hours. The results of analyzes of mercury and arsenic in the product after 20, 50, 100, 200 and 500 hours are summarized in Table III.

On constate que la masse de captation ne présente pas d'efficacité pour retenir l'arsenic. Elle présente par contre une efficacité transitoire pour retenir le mercure, mais celle-ci chute très rapidement avec le temps.It can be seen that the capture mass is not effective in retaining arsenic. On the other hand, it has transient effectiveness in retaining mercury, but it drops very quickly over time.

Exemple 3 (comparaison) Example 3 (comparison)

On répète l'expérimentation de l'exemple 2, mais en supprimant le débit d'hydrogène.The experiment of example 2 is repeated, but suppressing the flow of hydrogen.

Les résultats indiqués au tableau III montrent que les performances ne sont pas améliorées.The results indicated in Table III show that the performance has not improved.

Exemple 4 (selon l'invention) Example 4 (according to the invention)

Dans un premier réacteur, on charge puis on prétraite 250 cm3 du catalyseur HR 306 de l'exemple 1, selon la technique et le prétraitement décrits dans ledit exemple.In a first reactor, 250 cm3 of HR 306 catalyst of Example 1 are then charged and pretreated, according to the technique and the pretreatment described in said example.

Dans un second réacteur, on charge 100 cm3 de la masse de captation de l'exemple 2 selon la technique décrite dans ledit exemple.In a second reactor, 100 cm3 of the capture mass of Example 2 is charged according to the technique described in said example.

On fait alors passer en flux ascendant sous hydrogène le même condensat lourd de gaz liquéfié que dans l'exemple 1, successivement sur le catalyseur puis sur la masse de captation.The same heavy condensate of liquefied gas is then passed in ascending flow under hydrogen as in Example 1, successively over the catalyst then over the capture mass.

Les conditions opératoires sont les suivantes :

Débit de charge :
500 cm3/h
Catalyseur HR 306 :
250 cm3
Température :
320°C
Pression totale :
30 bars absolus
Débit d'hydrogène :
100 litres par litre de charge, soit 50 litres par heure.

   Masse de captation au sulfure de cuivre : 100 cm3
   Température : 40°C
   Pression totale : 30 bars absolus
   Débit d'hydrogène : 100 litres par litre de charge, soit 50 litres par heure.The operating conditions are as follows:
Charge flow:
500 cm3 / h
HR 306 catalyst:
250 cm3
Temperature :
320 ° C
Total pressure:
30 bars absolute
Hydrogen flow:
100 liters per liter of charge, i.e. 50 liters per hour.

Copper sulfide capture mass: 100 cm3
Temperature: 40 ° C
Total pressure: 30 bar absolute
Hydrogen flow: 100 liters per liter of charge, or 50 liters per hour.

On laisse passer le condensat durant 1000 heures. Les résultats d'analyses de mercure dans le produit au bout de 50, 100, 200, 500 et 1000 heures sont résumés dans le tableau III ci-après.The condensate is allowed to pass for 1000 hours. The results of analyzes of mercury in the product after 50, 100, 200, 500 and 1000 hours are summarized in Table III below.

On constate, d'une façon inattendue, que l'association du catalyseur HR 306 et d'une masse de captation permet d'obtenir un taux élevé de désarsénification et de démercurisation du condensat.It is found, unexpectedly, that the combination of the HR 306 catalyst and a capture mass makes it possible to obtain a high rate of desarsenification and demercurization of the condensate.

L'analyse du catalyseur HR 306 montre que plus de 90% de l'arsenic fixé est présent dans ledit catalyseur; la concentration en mercure est par contre inférieure à 20 ppm poids. L'analyse de la masse de démercurisation montre qu'elle contient pratiquement 100% du mercure et moins de 10% de l'arsenic fixés.Analysis of the HR 306 catalyst shows that more than 90% of the fixed arsenic is present in said catalyst; the mercury concentration, on the other hand, is less than 20 ppm by weight. Analysis of the demercurization mass shows that it contains practically 100% of the mercury and less than 10% of the fixed arsenic.

Ces métaux sont essentiellement présents dans les premiers 50 cm3 du lit. On peut donc s'attendre à une durée de vie très importante.These metals are mainly present in the first 50 cm3 of the bed. We can therefore expect a very long service life.

Exemple 5, selon l'invention. Example 5 , according to the invention.

Afin de démontrer la thiorésistance du système catalytique, on rajoute 0,5% poids de soufre sous forme de thiophène à la charge traitée dans l'exemple 1.In order to demonstrate the thioresistance of the catalytic system, 0.5% by weight of sulfur in the form of thiophene is added to the charge treated in Example 1.

Les conditions opératoires restent identiques, à l'exception de la température opératoire du catalyseur HR 306, portée à 340°C et au débit d'hydrogène, porté à 200 litres/litre de charge, soit 100 litres/heure.The operating conditions remain identical, with the exception of the operating temperature of the HR 306 catalyst, brought to 340 ° C. and to the hydrogen flow rate, brought to 200 liters / liter of charge, ie 100 liters / hour.

Les performances, résumées au tableau III, sont identiques à la précision des analyses.The performances, summarized in Table III, are identical to the precision of the analyzes.

Exemple 6, selon l'invention Example 6 , according to the invention

On reproduit l'expérimentation décrite à l'exemple 4. Le réacteur contenant 100 cm3 de masse de captation au sulfure de cuivre est maintenant chargé avec :
   100 cm3 de ladite masse et
   50 cm3 de masse de démercurisation composée de 13% poids en soufre sur charbon actif, de type CALGON HGR, préparée selon l'enseignement du brevet USP3194629.The experiment described in Example 4 is reproduced. The reactor containing 100 cm3 of copper sulphide capture mass is now loaded with:
100 cm3 of said mass and
50 cm3 of demercurization mass composed of 13% by weight of sulfur on activated carbon, of the CALGON HGR type, prepared according to the teaching of patent USP3194629.

Les autres conditions opératoires demeurent strictement identiques et l'essai est limité à 500 heures.The other operating conditions remain strictly identical and the test is limited to 500 hours.

Les résultats d'expérience reproduits au tableau III montrent que l'addition de la masse de démercurisation au charbon actif permet une légère amélioration des performances en démercurisation. Les performances en désarsénification demeurent, par contre, inchangées.The experimental results reproduced in Table III show that the addition of the demercurization mass to active carbon allows a slight improvement in demercurization performance. On the other hand, the de-arsenification performance remains unchanged.

Exemple 7, selon l'invention. Example 7 , according to the invention.

Le premier réacteur utilisé à l'exemple 3 est maintenant chargé avec 200 cm3 du catalyseur HMC 841, commercialisé par PROCATALYSE.The first reactor used in Example 3 is now loaded with 200 cm3 of the HMC 841 catalyst, sold by PROCATALYSE.

Ce catalyseur constitué de billes de diamètres 1,5 à 3 mm contient 1,96% de nickel et 8% de molybdène en poids; la matrice est constituée d'alumine de transition. La surface spécifique est de 140 m2/g et le volume poreux de 0,89 cm3/g. Le catalyseur HMC 841 a été présulfuré avant chargement (sulfuration ex-situ) selon le procédé SULFICAT (R) commercialisé par la société EURECAT; sa teneur en soufre est de 4,8% poids.This catalyst consisting of beads of diameters 1.5 to 3 mm contains 1.96% nickel and 8% molybdenum by weight; the matrix consists of transition alumina. The specific surface is 140 m2 / g and the pore volume of 0.89 cm3 / g. The HMC 841 catalyst was presulphurized before loading (ex-situ sulphurization) according to the SULFICAT (R) process sold by the company EURECAT; its sulfur content is 4.8% by weight.

Le deuxième réacteur est chargé avec 200 cm3 d'une masse de démercurisation contenant 8% de soufre, 14,5% de cuivre et 0,2% poids d'argent, préparée selon l'enseignement du brevet US 4094777 de la demanderesse, puis présulfurée par mise en contact avec un polysulfure organique selon l'enseignement du brevet français 87-07442 de la demanderesse.The second reactor is loaded with 200 cm3 of a demercurization mass containing 8% of sulfur, 14.5% of copper and 0.2% by weight of silver, prepared according to the teaching of US Pat. No. 4,094,777, then presulphurized by contacting an organic polysulphide according to the teaching of French patent 87-07442 of the applicant.

Les caractéristiques de la nouvelle charge traitée (condensat lourd de gaz liquéfié) sont indiquées au tableau II; le durée du test est de 1000 heures.The characteristics of the new charge treated (heavy liquefied gas condensate) are shown in Table II; the duration of the test is 1000 hours.

Les conditions opératoires retenues sont les suivantes :

Débit de charge :
0,6 litre/heure
Catalyseur HMC 841 :
200 cm3
Température :
390°C
Pression :
40 bars
Débit d'hydrogène :
150 litres par litre de charge, soit 90 litres/heure.

Masse de captation aux sulfures de cuivre et d'argent :
200 cm3
Température
: 100°C
Pression
: 40 bars.
The operating conditions used are as follows:
Charge flow:
0.6 liter / hour
HMC 841 catalyst:
200 cm3
Temperature :
390 ° C
Pressure:
40 bars
Hydrogen flow:
150 liters per liter of charge, i.e. 90 liters / hour.

Copper and silver sulphide capture mass:
200 cm3
Temperature
: 100 ° C
Pressure
: 40 bars.

Les résultats d'analyse de mercure et d'arsenic dans le produit au bout de 20, 50, 100, 200, 500 et 1000 heures sont résumés au tableau III. On voit que la désarsénification de la charge reste toujours supérieure à 99% et que la démercurisation reste toujours supérieure à 98,8%.The results of analysis of mercury and arsenic in the product after 20, 50, 100, 200, 500 and 1000 hours are summarized in Table III. It can be seen that the desarsenification of the charge always remains greater than 99% and that the demercurization always remains greater than 98.8%.

De plus, l'analyse de l'effluent liquide purifié, au bout de 500 heures d'essai, montre qu'il contient seulement 60 ppm (poids) de soufre et 33 ppm (poids) d'azote. Le taux d'hydrodésulfuration et le taux d'hydrodéazotation sont donc respectivement de 95,4 et de 24%. Par ailleurs l'effluent contient seulement 28% d'aromatiques (par rapport à 41% dans la charge fraîche) ce qui démontre, outre l'activité en désarsénification et en démercurisation, les propriétés additionnelles en hydrodésulfuration en hydrodéazotation et en hydrogénation des aromatiques de l'ensemble (catalyseur + masse de démercurisation) selon l'invention.In addition, the analysis of the purified liquid effluent, after 500 hours of testing, shows that it contains only 60 ppm (weight) of sulfur and 33 ppm (weight) of nitrogen. The hydrodesulfurization rate and the hydrodenitrogenation rate are therefore respectively 95.4 and 24%. Furthermore, the effluent contains only 28% of aromatics (compared to 41% in the fresh feed), which demonstrates, in addition to the activity in desarsenification and in demercurization, the additional properties in hydrodesulfurization in hydrodenitrogenation and in hydrogenation of aromatics of the assembly (catalyst + demercurization mass) according to the invention.

Exemple 8, selon l'invention Example 8 , according to the invention

La charge traitée est toujours celle décrite au tableau II.The charge treated is always that described in Table II.

On utilise maintenant un seul réacteur, de diamètre 4 cm, contenant de l'entrée à la sortie :
0,5 litre du catalyseur HMC 841, présulfuré hors site comme à l'exemple 7,
0,2 litre de la masse aux sulfures de cuivre et d'argent utilisée à l'exemple 7.We now use a single reactor, 4 cm in diameter, containing from inlet to outlet:
0.5 liters of catalyst HMC 841, presulfurized off site as in Example 7,
0.2 liters of the copper and silver sulfide mass used in Example 7.

La température opératoire est égale à 220°C, la pression opératoire égale à 50 bars (absolus) et le débit est de 200 litres par litre de charge, soit 120 litres par heure.The operating temperature is equal to 220 ° C., the operating pressure equal to 50 bars (absolute) and the flow rate is 200 liters per liter of charge, or 120 liters per hour.

Le débit de charge est de 0,6 litre par heure.The charge rate is 0.6 liters per hour.

L'analyse de l'hydrogène, récupéré en sortie après séparation (séparateur haute pression) de la charge purifiée, montre qu'il contient du sulfure d'hydrogène, formé par hydrodésulfuration de ladite charge en présence du catalyseur HMC 841.Analysis of the hydrogen, recovered at the outlet after separation (high pressure separator) of the purified feed, shows that it contains hydrogen sulfide, formed by hydrodesulfurization of said feed in the presence of the HMC 841 catalyst.

L'essai dure 500 heures et les performances obtenues sont résumées au tableau III.The test lasts 500 hours and the performances obtained are summarized in Table III.

On voit que l'utilisation des deux catalyseurs dans un réacteur unique conduit à une bonne efficacité pour la démercurisation et pour la désarsénification de la charge.

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
 It can be seen that the use of the two catalysts in a single reactor leads to good efficiency for the demercurization and for the de-arsenification of the feed.
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006

Claims (17)

  1. A method of removing mercury from a hydrocarbon charge containing the elements mercury and sulphur, characterised in that a mixture of hydrogen and said charge is reacted in the present of an arsenic collecting material with catalytic properties, described as "the catalyst", containing at least one metal M selected from the group formed by nickel, cobalt, iron, palladium and platinum, at least one metal N selected from the group formed by chromium, mobybdenum, tungsten and uranium, and possibly at least one active phase carrier based on at least one porous inorganic matrix, said arsenic collecting material with catalytic properties being followed along the path of the charge by, or mixed with, a mercury collecting material containing a sulphide of at least one metal P, selected from the group formed by copper, iron and silver, or sulphur, and an active phase carrier.
  2. A method according to Claim 1, wherein the charge contains arsenic as well as mercury and sulphur, characterised in that the arsenic and mercury are removed simultaneously, respectively by interaction with the dearsenification material with catalytic properties described as "the catalyst" and with the demercurisation material.
  3. A method according to Claims 1 and 2, wherein the charge is partly hydrodesulphurised, hydrodenitrified and hydrogenated in respect of its unsaturated hydrocarbon fraction, simultaneously with the elimination of the metals mercury and arsenic.
  4. A method according to Claims 1 to 3, wherein at least one sulphur compound, selected from the group formed by hydrogen sulphide and sulphurised organic compounds, may be added to the charge.
  5. A method according to Claims 1 to 4, wherein the catalyst contains 0.01 to 15% by weight of at least one metal M, and 2 to 30% by weight of at least one metal N, and wherein the atomic ratio M/N is 0.3:1 to 0.7:1.
  6. The method according to Claim 5, wherein the metals M are cobalt and nickel and the metals N are molybdenum and tungsten, and wherein the catalyst contains 0.5 to 15% by weight of at least one metal M and 5 to 25% by weight of at least one metal N.
  7. A method according to Claims 5 and 6, wherein the catalyst contains at least one noble metal, selected from palladium and platinum, among the metals M, and wherein said catalyst contains 0.01 to 5% of metals M.
  8. A method according to any of Claims 5 to 7, wherein the catalyst contains an active phase carrier in addition to the metals M and N, the carrier comprising a porous inorganic matrix including at least one of the elements in the group formed by alumina, silica, silica-alumina, magnesia, zirconia, titanium oxide, clays, aluminous cements, aluminates, and synthetic or natural zeolitic aluminosilicates.
  9. A method according to any of Claims 1 to 8, wherein the collecting material comprises 1 to 40% of sulphur relative to its total weight, and at least one carrier selected from the group formed by alumina, silica-aluminas, silica, titanium oxide, zirconia, zeolites, active carbons, clays and aluminous cements.
  10. A method according to Claim 9, wherein the collecting material also contains 0.1 to 20% by weight of at least one metal P, selected from the group formed by copper, iron and silver, and wherein the metal P is at least partly in sulphide form.
  11. A method according to any of the preceding Claims, wherein,:
    - the operating pressure is from 1 to 50 bars absolute
    - the hydrogen flow rate is from 1 to 1000 litres of hydrogen gas (NTP) per litre of liquid charge
    - the hourly volume speed, expressed in volumes of liquid charge, is from 0.1 to 30 volumes per volume of catalyst, and from 0.1 to 30 volume per volume of demercurisation material
    - the operating temperature of the catalyst is 180 to 450°C
    - the operating material of the demercurisation material is 0 to 400°C
    - the catalyst and demercurisation material are arranged in two separate reactors, the charge being put into contact first with the catalyst then with the collecting material.
  12. A method according to Claim 11, wherein
       - the catalyst and demercurisation material are arranged in one reactor, and wherein the operating temperature is from 180 to 400°C
  13. A method according to Claim 11 or 12, wherein the hydrogen-rich gas is separated from the effluent from the reactor of reactors, then at least partly recycled to the top of the first reactor.
  14. A method according to any of Claims 1 to 13, wherein the catalyst is pretreated at from 50 to 500°C, by a gaseous mixture containing at least one compound from the group formed by hydrogen, hydrogen sulphide and organic sulphur compounds, prior to the treatment by the hydrocarbon charge.
  15. A method according to any of Claims 1 to 14, wherein the charge comprises hydrocarbons which are at least partly liquid at ambient temperature and pressure, and contains 10⁻³ to 2 milligrams of mercury per kilogram of charge and possibly 10⁻² to 10 milligrams of arsenic per kilogram of charge.
  16. A method according to any of Claims 1 to 15, wherein the charges treated are heavy ones of effluents from thermal and/or catalytic conversion processes.
  17. A method according to any of Claims 1 to 15, wherein the charges treated are gas condensates.
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CA2012344A1 (en) 1990-09-16
EP0463044A1 (en) 1992-01-02
DZ1402A1 (en) 2004-09-13
DE69002941D1 (en) 1993-09-30
NO913622D0 (en) 1991-09-13
NO180121C (en) 1997-02-19
CN1045596A (en) 1990-09-26
AU5331990A (en) 1990-10-09
FR2644472B1 (en) 1991-06-21
NO913622L (en) 1991-09-13
WO1990010684A1 (en) 1990-09-20
ZA893265B (en) 1990-04-25
DE69002941T2 (en) 1993-12-23
MY106411A (en) 1995-05-30
AU634763B2 (en) 1993-03-04
CA2012344C (en) 2001-05-08
JP2620811B2 (en) 1997-06-18
CN1024675C (en) 1994-05-25
FR2644472A1 (en) 1990-09-21
NO180121B (en) 1996-11-11
JPH02248493A (en) 1990-10-04

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