EP0332526B1 - Verfahren zur Entfernung von Quecksilber und möglichem Arsen aus Kohlenwasserstoffen - Google Patents

Verfahren zur Entfernung von Quecksilber und möglichem Arsen aus Kohlenwasserstoffen 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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EP
European Patent Office
Prior art keywords
catalyst
capture mass
mass
metal
mercury
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP89400626A
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English (en)
French (fr)
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EP0332526A1 (de
Inventor
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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Priority to AT89400626T priority Critical patent/ATE75767T1/de
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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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)
  • Treating Waste Gases (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Gas Separation By Absorption (AREA)

Claims (9)

1. Verfahren zur Entfernung des Quecksilber-Gehalts aus einer Kohlenwasserstoff-Charge, dadurch gekennzeichnet, daß man ein Gemisch aus Wasserstoff und der besagten Charge mit einem Katalysator in Kontakt bringt, der zumindest ein Metall M enthält, das aus Nickel, Kobalt, Eisen und/oder Palladium besteht, wobei sich das Metall M zumindest zu 50 % seines Gesamtgehalts in reduziertem Zustand befindet, gefolgt von der Behandlung durch mindestens eine Fängermasse, die Schwefel oder ein Metallsulfid enthält, wobei folgende Verfahrensbedingungen eingehalten werden:
a) der Druck liegt zwischen 1 und 50 bar (absolut),
b) der Chargendurchsatz,bezogen auf die Fängermasse,liegt zwischen 1 und 50 Volumenteilen (flüssig) pro Volumenteil Fängermasse und pro Stunde,
c) der Wasserstoffdurchsatz,bezogen auf den Katalysator, liegt zwischen 1 und 500 Volumenteilen (gasförmig bei normalen Bedingungen) pro Katalysatorvolumen und pro Stunde,
d) die Temperatur liegt zwischen 130 und 250°C bezüglich des Katalysators und zwischen 0 und 175°C bezüglich der Fängermasse, wenn in getrennten Reaktoren gearbeitet wird, die Temperatur liegt zwischen 130 und 175°C, wenn in einem einzigen Reaktor gearbeitet wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Katalysator 0,1 bis 60 Gew.-% an Metall auf einem Träger enthält, der aus der Gruppe besteht, die aus Aluminiumoxid, Siliciumdioxid-Aluminiumoxid, Siliciumdioxid, Zeolithen, Tonen, Aktivkohle und Tonerdezement besteht.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Fängermasse 1 bis 40 % an Schwefel bezogen auf die Gesamtmasse enthält und der Rest aus zumindest einem Inhaltsstoff besteht, der der Gruppe angehört, die aus Aluminiumoxid, Siliciumdioxid-Aluminiumoxid, Siliciumdioxid, den Zeolithen, Aktivkohle, Tonen oder Tonerdezement besteht.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Fängermasse 0,1 bis 20 Gew.-% zumindest eines Metalls P enthält, das der Gruppe angehört, die aus Kupfer, Eisen und Silber gebildet ist, wobei das Metall P zumindest teilweise in Gestalt des Sulfids vorliegt.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Metall (M) des Katalysators aus Nickel und das Metall (P) der Fängermasse aus Kupfer besteht.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Metalle M, P und der Schwefel in fester Form vorliegen und zwar bezüglich des Katalysators und der Fängermasse.
7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Katalysator bzw. die Fängermasse in zwei Einzelreaktoren angeordnet sind, wobei die Charge zunächst mit dem Katalysator und sodann mit der Fängermasse in Berührung gebracht wird und der Katalysator bei 130 bis 250°C unter einem Wasserstoffdruck von 1 bis 50 bar (absolut) funktioniert und ferner die Fängermasse zwischen 0 und 175°C im gleichen Druckbereich funktioniert sowie das Katalysatorvolumen, bezogen auf das Volumen der Fängermasse 1 : 10 bis 5 : 1 beträgt.
8. Verfahren nach einem der Aansprüche 1 bis 7, dadurch gekennzeichnet, daß die Charge abgesehen von Quecksilber ferner auch einen Arsen-Gehalt aufweist.
9. Verfahren nach Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß man zum Zweck der Aufrechterhaltung einer konstanten Gesamtschwefelkonzentration in der Fängermasse, gleichzeitig mit der Charge eine Schwefel-Verbindung einführt, die der Gruppe angehört, die aus Schwefelwasserstoff und zumindest einem organischen Polysulfid besteht.
EP89400626A 1988-03-10 1989-03-06 Verfahren zur Entfernung von Quecksilber und möglichem Arsen aus Kohlenwasserstoffen Expired - Lifetime EP0332526B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89400626T ATE75767T1 (de) 1988-03-10 1989-03-06 Verfahren zur entfernung von quecksilber und moeglichem arsen aus kohlenwasserstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8803258 1988-03-10
FR8803258A FR2628338B1 (fr) 1988-03-10 1988-03-10 Procede pour l'elimination du mercure dans les hydrocarbures

Publications (2)

Publication Number Publication Date
EP0332526A1 EP0332526A1 (de) 1989-09-13
EP0332526B1 true EP0332526B1 (de) 1992-05-06

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EP89400626A Expired - Lifetime EP0332526B1 (de) 1988-03-10 1989-03-06 Verfahren zur Entfernung von Quecksilber und möglichem Arsen aus Kohlenwasserstoffen

Country Status (12)

Country Link
US (1) US4911825A (de)
EP (1) EP0332526B1 (de)
JP (1) JP3038390B2 (de)
CN (1) CN1021409C (de)
AT (1) ATE75767T1 (de)
AU (1) AU612244B2 (de)
CA (1) CA1335270C (de)
DE (1) DE68901407D1 (de)
DZ (1) DZ1327A1 (de)
FR (1) FR2628338B1 (de)
MY (1) MY104718A (de)
NO (1) NO173321C (de)

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NO890993L (no) 1989-09-11
MY104718A (en) 1994-05-31
NO173321C (no) 1993-12-01
CN1037466A (zh) 1989-11-29
FR2628338A1 (fr) 1989-09-15
FR2628338B1 (fr) 1991-01-04
ATE75767T1 (de) 1992-05-15
CN1021409C (zh) 1993-06-30
DZ1327A1 (fr) 2004-09-13
AU3117889A (en) 1989-09-14
CA1335270C (fr) 1995-04-18
DE68901407D1 (de) 1992-06-11
NO890993D0 (no) 1989-03-08
JPH01231920A (ja) 1989-09-18
US4911825A (en) 1990-03-27
AU612244B2 (en) 1991-07-04
JP3038390B2 (ja) 2000-05-08
EP0332526A1 (de) 1989-09-13
NO173321B (no) 1993-08-23

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