EP0332526B1 - Process for removing mercury and, optionally, arsenic from hydrocarbons - Google Patents

Process for removing mercury and, optionally, arsenic from hydrocarbons Download PDF

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Publication number
EP0332526B1
EP0332526B1 EP89400626A EP89400626A EP0332526B1 EP 0332526 B1 EP0332526 B1 EP 0332526B1 EP 89400626 A EP89400626 A EP 89400626A EP 89400626 A EP89400626 A EP 89400626A EP 0332526 B1 EP0332526 B1 EP 0332526B1
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Prior art keywords
catalyst
capture mass
mass
metal
mercury
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EP89400626A
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German (de)
French (fr)
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EP0332526A1 (en
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Michel Roussel
Philippe Courty
Jean-Paul Boitiaux
Jean Cosyns
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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
    • 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
    • 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
    • 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 2,534,826 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 4,069,140 describes the use of various absorbent masses.
  • the supported iron oxide is described, the use of lead oxide is described in US patent 3,782,076 and that of copper oxide in US patent 3,812,653.
  • the object of the invention is a process for removing the mercury contained in a hydrocarbon feed which remedies the defects of the previous processes.
  • a mixture of the charge with hydrogen is passed into contact with a catalyst containing at least one metal mainly in its reduced form and belonging to the group formed by iron, cobalt, nickel and palladium followed by- or mixed with- a capture mass containing sulfur or a metal sulphide, according to operating conditions which are specified below.
  • 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.
  • sulfur can be introduced either with the feedstock (organic polysulfide) and / or with hydrogen (H2S), upstream of the catalyst, it may also be preferable to introduce it between the reactor containing the catalyst and that containing the capture mass, in order to limit the sulfurization rate at equilibrium of said catalyst.
  • H2S hydrogen
  • the sulfur compound is introduced between the reactor containing the catalyst and the reactor containing the capture mass.
  • the catalyst used in the composition of the assembly which is the subject of the present invention consists of at least one metal M chosen from the group formed by iron, nickel, cobalt and palladium, used as it is or preferably deposited on a support.
  • the metal M must be in reduced form for at least 50% of its totality.
  • the support can be chosen from the group formed by alumina, silica-aluminas, silica, zeolites, activated carbon, clays and aluminous cements.
  • alumina silica-aluminas, silica, zeolites, activated carbon, clays and aluminous cements.
  • nickel or the combination of nickel with palladium is used.
  • the proportion of metal M relative to the total weight of catalyst is between 0.1 and 60%, more particularly between 5 and 60% and preferably from 5 to 30%. In the case of association with palladium, the proportion of this metal relative to the total weight of catalyst is between 0.01 and 10% and preferably from 0.05 to 5%.
  • the solid mineral dispersant may advantageously consist of an alumina or a calcium aluminate. It 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 catalyst Before use, the catalyst is, if necessary, reduced by hydrogen or by a gas, enclosing at a temperature of 150 to 600 ° C.
  • the capture mass 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 solid mineral support or dispersant chosen, for example, from the group formed by alumina, silica-aluminas, silica, zeolites, clays, active carbon, aluminous cements.
  • 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 constituted by the catalyst and the capture mass can be implemented 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 catalyst to the capture mass may vary between 1:10 and 5: 1.
  • the catalyst When operating in separate reactors, it will be possible, as regards the catalyst, to operate in a temperature range which may range from 130 to 250 ° C., more advantageously from 130 to 220 ° C. and preferably between 130 and 180 ° C.
  • the operating pressures will preferably be chosen from 1 to 50 bar absolute, more particularly from 2 to 40 bar and more advantageously from 5 to 35 bar.
  • the collecting mass will work at a temperature of 0 to 175 ° C, more particularly between 20 and 120 ° C and more advantageously between 20 and 90 ° C under pressures of 1 to 50 bar absolute, more particularly from 2 to 40 bar and preferably 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 (volumes - liquid - per mass volume and per hour).
  • the flow of hydrogen, relative to the catalyst is for example between 1 and 500 volumes (gas under normal conditions) per volume of catalyst and per hour.
  • the charges to which the invention applies more particularly contain from 10 ⁇ 3 to 1 milligram of mercury per kilogram of charge and, optionally from 10 ⁇ 2 to 10 milligrams of arsenic per kilogram of charge.
  • the catalyst is then subjected to a treatment under hydrogen under the following conditions: Pressure: 2 bars Hydrogen flow: 20 l / h Temperature: 400 ° C.
  • the duration of the treatment is 8 hours until at least 90% of the nickel oxide is converted into nickel metal.
  • a heavy condensate of liquefied gas boiling in the range of boiling points from 30 to 350 ° C. and containing 50 ppb of mercury is then passed over the catalyst, in upward flow, with hydrogen under the following conditions: Charging flow: 500 cm3 / h Temperature: 180 ° C Hydrogen pressure: 30 bars Hydrogen flow 2 liters / hour
  • the mercury content leaving the reactor is approximately 50 ppb.
  • 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 capture mass does not allow total decontamination to be obtained during the duration of the test.
  • the nickel catalyst of Example 1 is loaded, according to the technique described in said example.
  • Example 2 In a second reactor, 50 cm3 of the capture mass of Example 2 is loaded according to the technique described in said example.
  • the operating conditions are as follows: Charging flow (reduced to the collection mass): 500 cm3 / h Nickel catalyst Temperature: 180 ° C Hydrogen pressure: 30 bar absolute Hydrogen flow: 2 liters / hour Copper sulfide capture mass Temperature: 20 ° C Hydrogen pressure: 30 bar absolute Hydrogen flow: 2 liters / hour.
  • test is then stopped and after drying of the catalyst and of the capture mass by nitrogen sweeping, these are discharged bed by bed.
  • the mercury content is measured on each of these.
  • the results are collated in Table 2 as regards the capture mass, no trace of mercury is detected on the catalyst.
  • Example 3 The procedure is as in Example 3 but with a heavy condensate of liquefied gas containing 400 ppb of mercury.
  • the nickel catalyst of Example 1 is loaded according to the technique described in said example.
  • This capture mass is arranged in 5 separate beds according to the technique used in Example 1, its total volume is equal to that of the catalyst contained in the first reactor.
  • the mercury content by weight on each of the capture mass beds are shown in Table 2.
  • Example 5 The procedure is as in Example 5 except that 50 cm 3 of catalyst containing 20% by weight of nickel and 80% by weight of calcium aluminate are used.
  • the mercury content by weight on each of the beds of the capture mass are collated in Table 2.
  • Example 3 The procedure is as in Example 3 except that the heavy condensate of liquefied gas is replaced by a boiling naphtha in the range of boiling points 50 at 180 ° C., containing 5 ppm of arsenic and 50 ppb of mercury and that the amount of nickel catalyst is 100 cm3 instead of 50 cm3.
  • the combination of the catalyst and the capture mass makes it possible to obtain satisfactory decontamination of the naphtha into arsenic and mercury.
  • Example 7 The procedure is as in Example 7 except that the charge flow rate reduced to the collection mass is 1 l / hour (VVH 20).
  • 100 cm 3 of a catalyst containing 20% by weight of nickel and 0.5% by weight of palladium are prepared on an alumina support which is loaded into a first steel reactor 3 cm in diameter. five equal beds each separated by a glass wool pad.
  • Example 2 After the catalyst has been reduced according to the conditions of Example 1 but with a maximum temperature of 350 ° C., the two reactors are placed in series under hydrogen.
  • the naptha is allowed to pass for 400 hours.
  • the results of mercury analyzes in the product after 50, 100, 200 and 400 hours are summarized in Table 1.
  • 50 cm3 of a mass capable of playing both the role of catalyst and of capture mass consisting of a mixture of metallic nickel, copper sulphide and aluminous cement, are prepared.
  • 100 g of finely dispersed copper sulfide is prepared by reacting basic copper carbonate with a 30% by weight solution of ditertiononyl polysulfide (commercial product TPS 37 from Elf Aquitaine).
  • the paste obtained is dried under nitrogen at 150 ° C for 16 hours and then activated under steam at 150 ° C for 5 hours.
  • the steam flow rate is 1000 volumes per volume of dry product.
  • the two products are mixed with 5000 g of commercial calcium aluminate (Secar 80) and water.
  • the dough obtained, extruded into rods of 2.5 mm in diameter, is matured for 16 hours in a ventilated oven under a mixture of nitrogen and 10% steam at 80 ° C and then dried under nitrogen at 120 ° C for 5 hours. and finally activated at 400 ° C under nitrogen for 2 hours.
  • the product obtained consisting of extrudates with diameters 2.1-2.3 mm and a length of less than 5 mm, contains 14.3% CuS, 14.3% nickel and 71.4% calcium aluminate.
  • This mixed mass is then loaded into a single steel reactor 3 cm in diameter and arranged in 5 equal beds each separated by a glass wool pad.
  • a naphtha with characteristics identical to those described in Example 7 and containing 5 ppm of arsenic and 50 ppb of mercury is then passed in ascending flow under hydrogen.
  • the operating conditions are as follows: Charging flow: 500 cm3 / hour Temperature: 80 ° C Hydrogen pressure: 30 bars Hydrogen flow: 2 liters / hour.

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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)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

Process for elimination of mercury in hydrocarbon charges wherein said charge is contacted, under hydrogen, with a catalyst containing at least one metal from the group consisting of nickel, cobalt, iron and palladium followed by-or mixed with-a capture mass containing sulfur or a metal sulfide.

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 indifféremment : 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 la démercurisation: le brevet US 3,194,629 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 made up of sulfur or of iodine deposited on activated carbon.

Le brevet US 4,474,896 décrit des masses constituées de sulfures et de cations de métal appartenant au groupe IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA ou VA capables de former des polysulfures insaturés.US Patent 4,474,896 describes masses consisting of sulfides and metal cations belonging to the group IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA or VA capable of forming unsaturated polysulfides.

Le brevet US 4,094,777 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.The patent US Pat. No. 4,094,777 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 desdites masses.French application 87-07442 of the applicant describes a specific method of preparation of said masses.

Le brevet FR 2.534.826 décrit d'autres masses constituées de soufre élémentaire et d'un support minéral.Patent FR 2,534,826 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 4,069,140 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 3,782,076 et celui d'oxyde de cuivre dans le brevet US 3,812,653.US Patent 4,069,140 describes the use of various absorbent masses. The supported iron oxide is described, the use of lead oxide is described in US patent 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 gas 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 the demercurization or else for the de-arsenification of gas (for example hydrogen) or gaseous mixtures (for example natural gas) and more particularly when 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 the arsenic, arsines comprising hydrocarbon chains containing two or more of two carbon atoms or, for mercury, dimethylmercury and the other mercury compounds comprising hydrocarbon chains containing two or more of two carbon atoms and, optionally d 'other non-metallic elements (sulfur, nitrogen ...).

L'objet de l'invention est un procédé d'élimination du mercure contenu dans une charge hydrocarbonée qui remédie aux défauts des procédés antérieurs. Selon ce procédé on fait passer un mélange de la charge avec de l'hydrogène au contact d'un catalyseur renfermant au moins un métal en majeure partie sous sa forme réduite et appartenant au groupe formé par le fer, le cobalt, le nickel et le palladium suivi de- ou mélangé à- une masse de captation renfermant du soufre ou un sulfure de métal, selon des conditions opératoires qui sont précisées par la suite.The object of the invention is a process for removing the mercury contained in a hydrocarbon feed which remedies the defects of the previous processes. According to this process, a mixture of the charge with hydrogen is passed into contact with a catalyst containing at least one metal mainly in its reduced form and belonging to the group formed by iron, cobalt, nickel and palladium followed by- or mixed with- a capture mass containing sulfur or a metal sulphide, according to operating conditions which are specified below.

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.

Dans la présente invention on a également constaté que, afin de maintenir dans la masse de captation une concentration constante en soufre total (soufre élémentaire et éventuellement soufre sulfure) il peut se révéler avantageux d'introduire simultanément avec la charge :

  • du soufre sous forme de sulfure d'hydrogène (H₂S) et/ou
  • du soufre sous forme de polysulfure organique (par exemple, un dialkyl polyusulfure).
In the present invention, it has also been found that, in order to maintain a constant concentration of total sulfur (elemental sulfur and possibly sulfur sulfide) in the capture mass, it may prove advantageous to introduce simultaneously with the charge:
  • sulfur in the form of hydrogen sulfide (H₂S) and / or
  • sulfur in the form of an organic polysulphide (for example, a dialkyl polyusulphide).

Bien que le soufre puisse être introduit soit avec la charge (polysulfure organique) et/ou soit avec l'hydrogène (H₂S), en amont du catalyseur, il peut également se révéler préférable de l'introduire entre le réacteur contenant le catalyseur et celui contenant la masse de captation, afin de limiter le taux de sulfuration à l'équilibre dudit catalyseur.Although sulfur can be introduced either with the feedstock (organic polysulfide) and / or with hydrogen (H₂S), upstream of the catalyst, it may also be preferable to introduce it between the reactor containing the catalyst and that containing the capture mass, in order to limit the sulfurization rate at equilibrium of said catalyst.

En fonction des conditions opératoires, et notamment de la pression partielle d'hydrogène et/ou de la pression partielle d'eau (si de l'eau est présente), la proportion de soufre introduite pourra être ajustée, comme il est connu de l'homme de métier, de façon à contrôler les équilibres de désulfuration de la masse de captation et de maintenir dans celle-ci une concentration constante en soufre, comme il vient d'être dit, en relation avec les équilibres : CuS + H₂O ⇄ CuO + H₂O Kp = p. H 2 S p. H 2 O

Figure imgb0001
CuS + H₂ ⇄ Cu + H₂S Kp = p. H 2 S p. H 2
Figure imgb0002
 Depending on the operating conditions, and in particular the partial pressure of hydrogen and / or the partial pressure of water (if water is present), the proportion of sulfur introduced can be adjusted, as is known from l '' skilled in the art, so as to control the desulfurization equilibria of the capture mass and to maintain therein a constant concentration of sulfur, as has just been said, in relation to the equilibria: CuS + H₂O ⇄ CuO + H₂O Kp = p. H 2 S p. H 2 O
Figure imgb0001
 CuS + H₂ ⇄ Cu + H₂S Kp = p. H 2 S p. H 2
Figure imgb0002

De préférence, le composé du soufre est introduit entre le réacteur contenant le catalyseur et le réacteur contenant la masse de captation.Preferably, the sulfur compound is introduced between the reactor containing the catalyst and the reactor containing the capture mass.

Il a enfin été découvert, d'une façon surprenante, qu'en présence de concentrations élevées en arsenic ou encore en présence de vitesses volumétriques horaires "liquides" élevées provoquant une captation imparfaite de l'arsenic (par exemple moins de 90%) sur le catalyseur, la masse de captation du mercure fonctionne également de manière très satisfaisante pour la captation de l'arsenic.It was finally discovered, surprisingly, that in the presence of high arsenic concentrations or in the presence of high "liquid" hourly volumetric velocities causing an imperfect uptake of arsenic (for example less than 90%) on the catalyst, the mercury capture mass also works very satisfactorily for the capture of arsenic.

Le catalyseur entrant dans la composition de l'ensemble faisant l'objet de la présente invention est constitué d'au moins un métal M choisi dans le groupe formé par le fer, le nickel, le cobalt et le palladium, utilisé tel quel ou de préférence déposé sur un support. Le métal M doit se trouver sous forme réduite au moins pour 50% de sa totalité.The catalyst used in the composition of the assembly which is the subject of the present invention consists of at least one metal M chosen from the group formed by iron, nickel, cobalt and palladium, used as it is or preferably deposited on a support. The metal M must be in reduced form for at least 50% of its totality.

Le support peut être choisi dans le groupe formé par l'alumine, les silices-alumines, la silice, les zéolithes, le charbon actif, les argiles et les ciments alumineux. On utilise de préférence le nickel ou l'association du nickel avec le palladium.The support can be chosen from the group formed by alumina, silica-aluminas, silica, zeolites, activated carbon, clays and aluminous cements. Preferably nickel or the combination of nickel with palladium is used.

La proportion de métal M par rapport au poids total de catalyseur est comprise entre 0,1 et 60%, plus particulièrement entre 5 et 60% et de façon préférée de 5 à 30%. Dans le cas de l'association avec du palladium, la proportion de ce métal par rapport au poids total de catalyseur est comprise entre 0,01 et 10% et de façon préférée de 0,05 à 5%.The proportion of metal M relative to the total weight of catalyst is between 0.1 and 60%, more particularly between 5 and 60% and preferably from 5 to 30%. In the case of association with palladium, the proportion of this metal relative to the total weight of catalyst is between 0.01 and 10% and preferably from 0.05 to 5%.

Le dispersant minéral solide pourra être constitué avantageusement par une alumine ou un aluminate de calcium. Il 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.The solid mineral dispersant may advantageously consist of an alumina or a calcium aluminate. It 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.

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 est, si nécessaire, réduit par de l'hydrogène ou par un gaz en renfermant à une température de 150 à 600°C.Before use, the catalyst is, if necessary, reduced by hydrogen or by a gas, enclosing at a temperature of 150 to 600 ° C.

La masse de captation 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 dispersant minéral solide choisi, par exemple, dans le groupe formé par l'alumine, les silice-alumines, la silice, les zéolithes, les argiles, les charbons actifs, les ciments alumineux.The capture mass 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 solid mineral support or dispersant chosen, for example, from the group formed by alumina, silica-aluminas, silica, zeolites, clays, active carbon, aluminous cements.

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.One can use as capture mass sulfur deposited on a support and for example a commercial product such as HGR calgon and more generally any product consisting of 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 pourra être mis en oeuvre soit dans deux réacteurs soit en un seul.The assembly constituted by the catalyst and the capture mass can be implemented 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 du catalyseur à la masse de captation 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 catalyst to the capture mass may vary between 1:10 and 5: 1.

Lorsque l'on opère en réacteurs séparés, on pourra, en ce qui concerne le catalyseur, opérer dans un domaine de température pouvant aller de 130 à 250°C, plus avantageusement de 130 à 220°C et de façon préférée entre 130 et 180°C.When operating in separate reactors, it will be possible, as regards the catalyst, to operate in a temperature range which may range from 130 to 250 ° C., more advantageously from 130 to 220 ° C. and preferably between 130 and 180 ° C.

Les pressions opératoires seront choisies de préférence de 1 à 50 bars absolus, plus particulièrement de 2 à 40 bars et de façon plus avantageuse de 5 à 35 bars.The operating pressures will preferably be chosen from 1 to 50 bar absolute, more particularly from 2 to 40 bar and more advantageously from 5 to 35 bar.

La masse de captation travaillera à une température de 0 à 175°C, plus particulièrement entre 20 et 120°C et plus avantageusement entre 20 et 90°C sous des pressions de 1 à 50 bars absolus, plus particulièrement de 2 à 40 bars et préférentiellement de 5 à 35 bars.The collecting mass will work at a temperature of 0 to 175 ° C, more particularly between 20 and 120 ° C and more advantageously between 20 and 90 ° C under pressures of 1 to 50 bar absolute, more particularly from 2 to 40 bar and preferably from 5 to 35 bars.

Les vitesses spatiales calculées par rapport à la masse de captation peuvent être de 1 à 50 h⁻¹ et plus particulièrement de 1 à 30 h⁻¹ (volumes - liquide - par volume de masse et par heure).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 (volumes - liquid - per mass volume and per hour).

Le débit d'hydrogène, rapporté au catalyseur est compris par exemple entre 1 et 500 volumes (gaz aux conditions normales) par volume de catalyseur et par heure.The flow of hydrogen, relative to the catalyst, is for example between 1 and 500 volumes (gas under normal conditions) per volume of catalyst and per hour.

Lorsqu'on opère en un réacteur unique, on a intérêt à adopter plus particulièrement une gamme de températures comprise entre 130 et 175°C et de façon préférée entre 130 et 150°C.When operating in a single reactor, it is advantageous to adopt more particularly a temperature range between 130 and 175 ° C and preferably between 130 and 150 ° C.

Les charges auxquelles s'applique plus particulièrement l'invention renferment de 10⁻³ à 1 milligramme 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 applies more particularly contain from 10⁻³ to 1 milligram of mercury per kilogram of charge and, optionally from 10⁻² to 10 milligrams of arsenic per kilogram of charge.

EXEMPLE 1 (comparaison) EXAMPLE 1 (comparison)

5 kilogrammes d'un support d'alumine macroporeux (préparé par autoclavage à la vapeur d'alumine de transition) sous forme de billes de 2-4 mm de diamètre, présentant une surface spécifique de 160 m2/g et un volume poreux total de 1,05 cm³/g - volume macroporeux (pores de diamètres supérieurs à 0,1 µm ) :0,4 cm³/g - sont imprégnés par 20% en poids de nickel sous forme d'une solution aqueuse de nitrate. Après séchage à 120°C durant 5 heures et activation thermique à 450°C pendant deux heures sous balayage d'air, on obtient 6,25 kg de billes contenant 20% de nickel en poids.5 kilograms of a macroporous alumina support (prepared by autoclaving with steam of transition alumina) in the form of beads of 2-4 mm in diameter, having a specific surface of 160 m2 / g and a total pore volume of 1.05 cm³ / g - macroporous volume (pores with diameters greater than 0.1 µm): 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 hours and thermal activation at 450 ° C for two hours with air sweeping, 6.25 kg of beads containing 20% nickel by weight are obtained.

50 cm³ de catalyseur sont alors chargés dans un réacteur en acier de 3 cm de diamètre, en 5 lits égaux séparés chacun par un tampon de laine de verre.50 cm³ of catalyst are then loaded into a steel reactor 3 cm in diameter, in 5 equal beds each separated by a glass wool pad.

On fait ensuite subir au catalyseur un traitement sous hydrogène dans les conditions suivantes :
   Pression : 2 bars
   Débit d'hydrogène : 20 l/h
   Température : 400°C.The catalyst is then subjected to a treatment under hydrogen under the following conditions:
Pressure: 2 bars
Hydrogen flow: 20 l / h
Temperature: 400 ° C.

La durée du traitement est de 8 heures jusqu'à conversion d'au moins 90% de l'oxyde de nickel en nickel métal.The duration of the treatment is 8 hours until at least 90% of the nickel oxide is converted into nickel metal.

On fait ensuite passer sur le catalyseur, en flux ascendant, un condensat lourd de gaz liquéfié bouillant dans la gamme des points d'ébullition de 30 à 350°C et contenant 50 ppb de mercure, avec de l'hydrogène dans les conditions suivantes :
   Débit de charge : 500 cm³/h
   Température : 180°C
   Pression d'hydrogène : 30 bars
   Débit d'hydrogène 2 litres/ heureA heavy condensate of liquefied gas boiling in the range of boiling points from 30 to 350 ° C. and containing 50 ppb of mercury is then passed over the catalyst, in upward flow, with hydrogen under the following conditions:
Charging flow: 500 cm³ / h
Temperature: 180 ° C
Hydrogen pressure: 30 bars
Hydrogen flow 2 liters / hour

On laisse passer le condensat et l'hydrogène durant 200 heures. Les résultats d'analyses du mercure dans le produit au bout de 50, 100, 200 et 400 heures sont résumés dans le tableau 1.The condensate and the hydrogen are allowed to pass for 200 hours. The results of analyzes of mercury in the product after 50, 100, 200 and 400 hours are summarized in Table 1.

Pendant les 400 heures de l'essai, la teneur en mercure sortant du réacteur est d'environ 50 ppb.During the 400 hours of the test, the mercury content leaving the reactor is approximately 50 ppb.

Le test est alors arrêté et après séchage du catalyseur par balayage à l'azote, ce dernier est déchargé lit par lit. Sur chacun d'eux, on mesure la teneur pondérale en mercure. Les résultats sont rassemblés dans le Tableau 2.The test is then stopped and after drying of the catalyst by nitrogen sweeping, the latter is discharged bed by bed. On each of them, the mercury content by weight is measured. The results are collated in Table 2.

On voit que ce catalyseur présente une efficacité très faible pour retenir le mercure.We see that this catalyst has a very low efficiency in retaining mercury.

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.

50 cm³ de cette masse sont alors chargés dans un réacteur identique à celui décrit dans l'exemple 1.50 cm³ of this mass are then loaded into a reactor identical to that described in Example 1.

La disposition de la masse en 5 lits séparés ainsi que son volume total sont en tous points comparables à l'exemple 1. On fait ensuite passer sur la masse, en flux ascendant, un condensat lourd de gaz liquéfié identique à celui décrit dans l'exemple 1 et contenant 50 ppb de mercure dans les conditions suivantes :
   Débit de charge : 500 cm³/h
   Pression totale : 30 bars absolus
   Température : ambianteThe arrangement of the mass in 5 separate beds as well as its total volume are in all respects comparable to Example 1. Next, a heavy liquefied gas condensate identical to that described in the Example 1 and containing 50 ppb of mercury under the following conditions:
Charging flow: 500 cm³ / h
Total pressure: 30 bar absolute
Ambient temperature

On laisse passer le condensat durant 400 heures. Les résultats d'analyses du mercure dans le produit au bout de 50, 100, 200 et 400 heures sont résumés dans le tableau 1.The condensate is allowed to pass for 400 hours. The results of analyzes of mercury in the product after 50, 100, 200 and 400 hours are summarized in Table 1.

On constate que la masse de captation ne permet pas d'obtenir une décontamination totale pendant la durée du test.It is noted that the capture mass does not allow total decontamination to be obtained during the duration of the test.

Le test est ensuite arrêté et, après séchage de la masse de captation par balayage à l'azote, celle ci est déchargée lit par lit. Sur chacun, on mesure la teneur pondérale en mercure, les résultats sont rassemblés dans le tableau 2.The test is then stopped and, after drying of the capture mass by nitrogen sweeping, this is discharged bed by bed. On each, the mercury content by weight is measured, the results are collated in Table 2.

On constate la présence de mercure sur l'ensemble des 5 lits, indice d'une certaine saturation de la masse de captation.We note the presence of mercury on all 5 beds, an indication of a certain saturation of the capture mass.

EXEMPLE 3 (selon l'invention) EXAMPLE 3 (according to the invention)

Dans un premier réacteur, on charge le catalyseur au nickel de l'exemple 1, selon la technique décrite dans ledit-exemple.In a first reactor, the nickel catalyst of Example 1 is loaded, according to the technique described in said example.

Dans un second réacteur, on charge 50 cm3 de la masse de captation de l'exemple 2 selon la technique décrite dans ledit exemple.In a second reactor, 50 cm3 of the capture mass of Example 2 is loaded according to the technique described in said example.

Après que le catalyseur ait été réduit selon les conditions de l'exemple 1, les deux réacteurs sont mis en série sous hydrogène.After the catalyst has been reduced under the conditions of Example 1, the two reactors are placed in series under hydrogen.

On fait alors passer en flux ascendant sous hydrogéne le même condensat lourd de gaz liquéfié que dans l'exemple 1 renfermant 50 ppb de mercure, 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 containing 50 ppb of mercury, successively on the catalyst then on the capture mass.

Les conditions opératoires sont les suivantes :
   Débit de charge (ramené à la masse de captation): 500 cm3/h
   Catalyseur au nickel
   Température : 180°C
   Pression d'hydrogène : 30 bars absolus
   Débit d'hydrogène : 2 litres/heure
   Masse de captation au sulfure de cuivre
   Température : 20°C
   Pression d'hydrogène : 30 bars absolus
   Débit d'hydrogène : 2 litres/heure.The operating conditions are as follows:
Charging flow (reduced to the collection mass): 500 cm3 / h
Nickel catalyst
Temperature: 180 ° C
Hydrogen pressure: 30 bar absolute
Hydrogen flow: 2 liters / hour
Copper sulfide capture mass
Temperature: 20 ° C
Hydrogen pressure: 30 bar absolute
Hydrogen flow: 2 liters / hour.

On laisse passer le condensat durant 400 heures. Les résulats d'analyses de mercure dans le produit au bout de 50, 100, 200 et 400 heures sont résumés dans le tableau 1 ci-après.The condensate is allowed to pass for 400 hours. The results of mercury analysis in the product after 50, 100, 200 and 400 hours are summarized in Table 1 below.

On constate, d'une façon inattendue, que l'association du catalyseur et d'une masse de captation permet d'obtenir une décontamination satisfaisante du condensat.It is found, unexpectedly, that the combination of the catalyst and a collection mass makes it possible to obtain satisfactory decontamination of the condensate.

Le test est ensuite arrêté et après séchage du catalyseur et de la masse de captation par balayage à l'azote, celles-ci sont déchargée lit par lit.The test is then stopped and after drying of the catalyst and of the capture mass by nitrogen sweeping, these are discharged bed by bed.

Sur chacun de ceux-ci on mesure la teneur en mercure. Les résultats sont rassemblés dans le tableau 2 pour ce qui concerne la masse de captation, aucune trace de mercure n'est détectée sur le catalyseur.The mercury content is measured on each of these. The results are collated in Table 2 as regards the capture mass, no trace of mercury is detected on the catalyst.

On voit que plus de 90% du mercure sont fixés sur le premier lit de la masse de captation soit 1/5 de ladite masse. Les 4/5 de la masse restent donc encore disponibles pour fixer le mercure au bout de 400 heures. On peut donc s'attendre à des durées de fonctionnement efficace très importantes.It can be seen that more than 90% of the mercury is fixed on the first bed of the capture mass, ie 1/5 of said mass. 4/5 of the mass are therefore still available to fix the mercury after 400 hours. We can therefore expect very long effective operating times.

EXEMPLE 4 selon l'invention EXAMPLE 4 according to the invention

On opère comme dans l'exemple 3 mais avec un condensat lourd de gaz liquéfié renfermant 400 ppb de mercure.The procedure is as in Example 3 but with a heavy condensate of liquefied gas containing 400 ppb of mercury.

L'efficacité de la masse de captation ainsi que le gradient des concentrations en mercure restent, toutes proportions gardées, sensiblement égales à ceux indiqués dans l'exemple 3.The efficiency of the capture mass as well as the gradient of the mercury concentrations remain, all things considered, substantially equal to those indicated in Example 3.

EXEMPLE 5 selon l'invention EXAMPLE 5 according to the invention

Dans un premier réacteur, on charge le catalyseur au nickel de l'exemple 1 selon la technique décrite dans ledit exemple.In a first reactor, the nickel catalyst of Example 1 is loaded according to the technique described in said example.

Dans un second réacteur identique au premier, on charge une masse de captation composée de 13% en poids de soufre sur charbon actif, de type Calgon HGR, préparée selon le brevet US 3194629.In a second reactor identical to the first, a capture mass composed of 13% by weight of sulfur on activated carbon, of Calgon HGR type, is prepared according to US Pat. No. 3,194,629.

Cette masse de captation est disposé en 5 lits séparés selon la technique utilisée dans l'exemple 1, son volume total est égal à celui du catalyseur contenu dans le premier réacteur.This capture mass is arranged in 5 separate beds according to the technique used in Example 1, its total volume is equal to that of the catalyst contained in the first reactor.

Après que le catalyseur ait été réduit selon les conditions de l'exemple 1, les deux réacteurs sont mis en série sous hydrogène.After the catalyst has been reduced according to the conditions of Example 1, the two reactors are placed in series under hydrogen.

On fait alors passer le même condensat renfermant 50 ppb de mercure selon des conditions en tous points identiques à celles décrites dans l'exemple 3 et ceci durant 400 heures.The same condensate containing 50 ppb of mercury is then passed through under conditions identical in all respects to those described in Example 3 and this for 400 hours.

Les résultats d'analyses de mercure dans le produit au bout de 50, 100, 200 et 400 heures sont résumés dans le tableau 1.The results of mercury analyzes in the product after 50, 100, 200 and 400 hours are summarized in Table 1.

Le test est arrêté après 400 heures de fonctionnement; catalyseur et masse de captation sont séchés puis déchargés selon le protocole de l'exemple 3.The test is stopped after 400 hours of operation; catalyst and capture mass are dried and then discharged according to the protocol of Example 3.

Les teneurs pondérales en mercure sur chacun des lits de la masse de captation sont indiquées dans le tableau 2.The mercury content by weight on each of the capture mass beds are shown in Table 2.

EXEMPLE 6 selon l'invention EXAMPLE 6 according to the invention

On opère comme dans l'exemple 5 à ceci près que l'on utilise 50 cm3 de catalyseur renfermant 20% en poids de nickel et 80% en poids d'aluminate de calcium.The procedure is as in Example 5 except that 50 cm 3 of catalyst containing 20% by weight of nickel and 80% by weight of calcium aluminate are used.

Les résultats d'analyses de mercure dans le produit au bout de 50, 100, 200, 400 heures sont indiqués dans le tableau 1.The results of mercury analyzes in the product after 50, 100, 200, 400 hours are shown in Table 1.

Après 400 heures de fonctionnement , le test est arrêté, catalyseur et masse de captation sont séchés et déchargés selon la méthode décrite dans l'exemple 3.After 400 hours of operation, the test is stopped, catalyst and capture mass are dried and discharged according to the method described in Example 3.

Les teneurs pondérales en mercure sur chacun des lits de la masse de captation sont regroupées dans le tableau 2.The mercury content by weight on each of the beds of the capture mass are collated in Table 2.

EXEMPLE 7 selon l'invention EXAMPLE 7 according to the invention

On opère comme dans l'exemple 3 à ceci près que le condensat lourd de gaz liquéfié est remplacé par un naphta bouillant dans la gamme de points d'ébullition 50 à 180°C, contenant 5 ppm d'arsenic et 50 ppb de mercure et que la quantité de catalyseur au nickel est de 100 cm3 au lieu de 50 cm3.The procedure is as in Example 3 except that the heavy condensate of liquefied gas is replaced by a boiling naphtha in the range of boiling points 50 at 180 ° C., containing 5 ppm of arsenic and 50 ppb of mercury and that the amount of nickel catalyst is 100 cm3 instead of 50 cm3.

Les résultats d'analyses d'arsenic et de mercure dans le produit au bout de 50, 100, 200 et 400 heures sont résumés dans le tableau 2.The results of arsenic and mercury analyzes in the product after 50, 100, 200 and 400 hours are summarized in Table 2.

On constate que l'association du catalyseur et de la masse de captation permet d'obtenir une décontamination satisfaisante du naphta en arsenic et en mercure.It is noted that the combination of the catalyst and the capture mass makes it possible to obtain satisfactory decontamination of the naphtha into arsenic and mercury.

Après séchage et déchargement des réacteurs selon le protocole de l'exemple 3, on mesure sur chaque lit les teneurs pondérales en arsenic et en mercure.After drying and discharging the reactors according to the protocol of Example 3, the weight contents of arsenic and mercury are measured on each bed.

Les résultats figurent sur le tableau 2.The results are shown in Table 2.

On voit que 90% de l'arsenic sont fixés sur le premier lit de catalyseur et 90% du mercure sont fixés sur le premier lit de la masse de captation .It can be seen that 90% of the arsenic is fixed on the first bed of catalyst and 90% of the mercury is fixed on the first bed of the capture mass.

EXEMPLE 8 selon l'invention EXAMPLE 8 according to the invention

On opère ainsi que dans l'exemple 7 à ceci près que le débit de charge ramené à la masse de captation est de 1 l/heure (VVH 20).The procedure is as in Example 7 except that the charge flow rate reduced to the collection mass is 1 l / hour (VVH 20).

EXEMPLE 9 selon l'invention EXAMPLE 9 according to the invention

On opère ainsi que dans l'exemple 7 mais le débit de charge ramené à la masse de captation est de 250 cm3/heure (VVH 5).The procedure is as in Example 7, but the charge flow rate reduced to the collection mass is 250 cm3 / hour (VVH 5).

Les analyses d'arsenic et de mercure donnent les résultats mentionnés dans le tableau 1.The arsenic and mercury analyzes give the results mentioned in Table 1.

Les teneurs pondérales en arsenic et mercure dans chacun des lits du catalyseur et de la masse de captation sont indiquées dans le tableau 2.The weight contents of arsenic and mercury in each of the catalyst beds and of the capture mass are shown in Table 2.

On voit que les taux d'épuration du mercure et de l'arsenic ne varient guère lorsqu'évolue la VVH.It can be seen that the purification rates of mercury and arsenic do not vary much when the HSV evolves.

EXEMPLE 10 selon l'invention EXAMPLE 10 according to the invention

Dans cet exemple on prépare 100 cm3 d'un catalyseur renfermant 20% en poids de nickel et 0,5% en poids de palladium sur un support d'alumine que l'on charge dans un premier réacteur en acier de 3 cm de diamètre en cinq lits égaux séparés chacun par un tampon de laine de verre.In this example, 100 cm 3 of a catalyst containing 20% by weight of nickel and 0.5% by weight of palladium are prepared on an alumina support which is loaded into a first steel reactor 3 cm in diameter. five equal beds each separated by a glass wool pad.

Dans un second réacteur identique au premier, on charge 50 cm3 d'une masse de captation obtenue par sulfuration au moyen d'un polysulfure organique d'un précurseur renfermant 10% en poids de cuivre sur un support d'alumine. Cette masse est elle-même répartie en cinq lits égaux.In a second reactor identical to the first, 50 cm3 of a capture mass obtained by sulphurization is charged using an organic polysulphide of a precursor containing 10% by weight of copper on an alumina support. This mass is itself divided into five equal beds.

Après que le catalyseur ait été réduit selon les conditions de l'exemple 1 mais avec une température maximum de 350°C, les deux réacteurs sont mis en série sous hydrogène.After the catalyst has been reduced according to the conditions of Example 1 but with a maximum temperature of 350 ° C., the two reactors are placed in series under hydrogen.

On fait alors passer, en flux ascendant, sous hydrogène, un naphta de caractéristiques identiques à celles décrites dans l'exemple 7, renfermant 5 ppm d'arsenic et 50 ppb de mercure, successivement sur le catalyseur puis sur la masse de captation.Then passing, in ascending flow, under hydrogen, a naphtha with characteristics identical to those described in Example 7, containing 5 ppm of arsenic and 50 ppb of mercury, successively on the catalyst and then on the capture mass.

Les conditions opératoires sont les suivantes :
   Débit de charge (ramené à la masse de captation):500 cm3/h
   Pour le catalyseur :
   Température : 100°C
   pression d'hydrogène : 30 bars absolus
   Débit d'hydrogène : 2 litres/heure
   Pour la masse de captation :
   Température : 60°C
   Pression d'hydrogène : 30 bars absolus
   Débit d'hydrogène : 2 litres/heureThe operating conditions are as follows:
Charging flow (reduced to the collection mass): 500 cm3 / h
For the catalyst:
Temperature: 100 ° C
hydrogen pressure: 30 bar absolute
Hydrogen flow: 2 liters / hour
For the capture mass:
Temperature: 60 ° C
Hydrogen pressure: 30 bar absolute
Hydrogen flow: 2 liters / hour

On laisse passer le naptha durant 400 heures. Les résultats d'analyses de mercure dans le produit au bout de 50, 100, 200 et 400 heures sont résumés dans le tableau 1.The naptha is allowed to pass for 400 hours. The results of mercury analyzes in the product after 50, 100, 200 and 400 hours are summarized in Table 1.

Après séchage puis déchargement des réacteurs, les teneurs pondérales en arsenic et mercure sont mesurées sur chaque lit, tant du catalyseur que de la masse de captation.After drying and then discharging the reactors, the weight contents of arsenic and mercury are measured on each bed, both of the catalyst and of the capture mass.

Les résultats figurent sur le tableau 2.The results are shown in Table 2.

On observe que les efficacités de captation du mercure et de l'arsenic sont en tous points comparables à celles du catalyseur et de la masse décrits dans l'exemple 7. De plus, l'ajout de palladium au nickel dans le catalyseur permet de travailler à plus basse température.It is observed that the capture efficiencies of mercury and arsenic are in all respects comparable to those of the catalyst and of the mass described in example 7. In addition, the addition of nickel palladium in the catalyst makes it possible to work at lower temperature.

EXEMPLE 11, suivant l'invention EXAMPLE 11 according to the invention

Dans cet exemple, on prépare 50 cm3 d'une masse susceptible de jouer à la fois le rôle de catalyseur et de masse de captation, constituée d'un mélange de nickel métallique, de sulfure de cuivre et de ciment alumineux.In this example, 50 cm3 of a mass capable of playing both the role of catalyst and of capture mass, consisting of a mixture of metallic nickel, copper sulphide and aluminous cement, are prepared.

On prépare d'abord 100 g de sulfure de cuivre finement dispersé en faisant réagir du carbonate basique de cuivre avec une solution à 30% en poids de ditertiononyl polysulfure (produit commercial TPS 37 d'Elf Aquitaine). La pâte obtenue est séchée sous azote à 150°C pendant 16 heures puis activée sous vapeur d'eau à 150°C pendant 5 heures. Le débit de vapeur est de 1000 volumes par volume de produit sec.First, 100 g of finely dispersed copper sulfide is prepared by reacting basic copper carbonate with a 30% by weight solution of ditertiononyl polysulfide (commercial product TPS 37 from Elf Aquitaine). The paste obtained is dried under nitrogen at 150 ° C for 16 hours and then activated under steam at 150 ° C for 5 hours. The steam flow rate is 1000 volumes per volume of dry product.

On prépare séparément 1000 g de nickel de Raney dépyrophorisé (NiPS2 de Procatalyse).1000 g of depyrophorized Raney nickel (NiPS2 from Procatalyse) are prepared separately.

Les deux produits sont malaxés avec 5000 g d'aluminate de calcium commercial (Sécar 80) et de l'eau. La pâte obtenue, extrudée en joncs de 2,5 mm de diamètre est mûrie 16 heures en étuve ventilée sous mélange d'azote et de 10% de vapeur d'eau à 80°C puis séchée sous azote à 120°C durant 5 heures et enfin activée à 400°C sous azote pendant 2 heures.The two products are mixed with 5000 g of commercial calcium aluminate (Secar 80) and water. The dough obtained, extruded into rods of 2.5 mm in diameter, is matured for 16 hours in a ventilated oven under a mixture of nitrogen and 10% steam at 80 ° C and then dried under nitrogen at 120 ° C for 5 hours. and finally activated at 400 ° C under nitrogen for 2 hours.

Le produit obtenu, constitué d'extrudés de diamètres 2,1-2,3 mm et de longueur inférieure à 5 mm contient 14,3% de CuS, 14,3% de nickel et 71,4% d'aluminate de calcium.The product obtained, consisting of extrudates with diameters 2.1-2.3 mm and a length of less than 5 mm, contains 14.3% CuS, 14.3% nickel and 71.4% calcium aluminate.

Cette masse mixte est alors chargée dans un seul réacteur en acier de 3 cm de diamètre et disposée en 5 lits égaux séparés chacun par un tampon de laine de verre.This mixed mass is then loaded into a single steel reactor 3 cm in diameter and arranged in 5 equal beds each separated by a glass wool pad.

On fait alors passer, en flux ascendant, sous hydrogène, un naphta de caractéristiques identiques à celles décrites dans l'exemple 7 et renfermant 5 ppm d'arsenic et 50 ppb de mercure.A naphtha with characteristics identical to those described in Example 7 and containing 5 ppm of arsenic and 50 ppb of mercury is then passed in ascending flow under hydrogen.

Les conditions opératoires sont les suivantes :
   Débit de charge : 500 cm3/heure
   Température : 80°C
   Pression d'hydrogène : 30 bars
   Débit d'hydrogène : 2 litres/heure.The operating conditions are as follows:
Charging flow: 500 cm3 / hour
Temperature: 80 ° C
Hydrogen pressure: 30 bars
Hydrogen flow: 2 liters / hour.

On laisse passer la charge durant 400 heures . Les résultats d'analyses sur les recettes figurent dans le tableau 1.The charge is allowed to pass for 400 hours. The results of revenue analyzes are shown in Table 1.

Après séchage et déchargement du réacteur, les teneurs en arsenic et mercure dans la masse sont mesurées dans chaque lit et répertoriées dans le tableau 2.

Figure imgb0003
Figure imgb0004
 After drying and unloading of the reactor, the arsenic and mercury contents in the mass are measured in each bed and listed in Table 2.
Figure imgb0003
Figure imgb0004

Claims (9)

1. Process for elimination of mercury from a hydrocarbon charge which contains it, characterized in that a mixture of hydrogen and said charge are contacted with a catalyst containing at least one metal M from the group consisting of nickel, cobalt, iron and palladium, and at least 50 % of the totality of the metal M should be in reduced form, followed by - or mixed with - a capture mass containing sulfur or a metal sulfide, and in that operating conditions are :
a) pressure ranges between 1 and 50 bars absolute,
b) charge flow rate, adjusted to the capture mass, ranges between 1 and 50 volumes (liquid) per volume of mass and per hour,
c) hydrogen flow rate, with respect to the catalyst, ranges between 1 and 500 volumes (under normal gas conditions) per volume of catalyst and per hour,
d) temperature ranges between 130 and 250° C with regard to the catalyst, and between 0 and 175° C with regard to the capture mass when operating in separated reactors or temperature ranges between 130 and 175° C when operating in a single reactor.
2. Process according to claim 1 wherein the catalyst contains from 0.1 to 60 % in weight of metal on a support chosen from the group consisting of alumina, silica-aluminas, silica, zeolites, clays, active carbon and alumina cements.
3. Process according to claim 1 or 2 wherein the capture mass comprises 1 to 40 % of sulfur with respect to its total mass and at least one support chosen from the group consisting of alumina, silica-aluminas, silica, zeolites, active carbon, clays, and alumina cements.
4. Process according to claim 3 wherein the capture mass also contains 0.1 to 20 % in weight of at least one metal P chosen from the group consisting of copper, iron and silver and in which the metal P is at least partly in the form of a sulfide.
5. Process according to one of claim 1 to 4 wherein the catalyst metal (M) is nickel and wherein the capture mass metal (P) is copper.
6 Process according to one of claims 1 to 5 wherein the metals M, P and the sulfur are present in the same solid, both in the catalyst and the capture mass.
7. Process according to one of claims 1 to 5 wherein the catalyst and the capture mass are arranged in two distinct reactors, the charge is contacted with the catalyst then with the capture mass, the catalyst functions between 130 and 250°C and under a hydrogen pressure from 1 to 50 absolute bars, the capture mass functions between 0 and 175°C in the same pressure range, and catalyst volume expressed with respect to capture mass volume is from 1:10 to 5:1.
8. Process according to one of claims 1 to 7 wherein the charge, apart from mercury, also contains arsenic.
9. Process according to one of claims 1 to 8 wherein in order to maintain a constant concentration in total sulfur in the capture mass, a sulfur compound chosen from the group consisting of hydrogen sulfide (H₂S) and at least one organic polysulfide is simultaneously introduced with the charge.
EP89400626A 1988-03-10 1989-03-06 Process for removing mercury and, optionally, arsenic from hydrocarbons Expired - Lifetime EP0332526B1 (en)

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