EP0810278B1 - Procédé d'élimination de mercure d'hydrocarbures liquides - Google Patents

Procédé d'élimination de mercure d'hydrocarbures liquides Download PDF

Info

Publication number
EP0810278B1
EP0810278B1 EP19970102446 EP97102446A EP0810278B1 EP 0810278 B1 EP0810278 B1 EP 0810278B1 EP 19970102446 EP19970102446 EP 19970102446 EP 97102446 A EP97102446 A EP 97102446A EP 0810278 B1 EP0810278 B1 EP 0810278B1
Authority
EP
European Patent Office
Prior art keywords
mercury
liquid hydrocarbons
activated carbon
adsorption
treatment zone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19970102446
Other languages
German (de)
English (en)
Other versions
EP0810278A3 (fr
EP0810278A2 (fr
Inventor
Kenji Ikushima
Akihisa Nagai
Kazuyuki Fukuda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TAIYO ENGINEERING COMPANY LIMITED
Original Assignee
Taiyo Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Engineering Co Ltd filed Critical Taiyo Engineering Co Ltd
Publication of EP0810278A2 publication Critical patent/EP0810278A2/fr
Publication of EP0810278A3 publication Critical patent/EP0810278A3/fr
Application granted granted Critical
Publication of EP0810278B1 publication Critical patent/EP0810278B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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

  • the present invention concerns a process for eliminating mercury and mercury compounds from liquid hydrocarbons containing a great amount of sulfur compounds and asphaltene such as natural gas condensates, particularly, heavy condensates recovered from natural gases.
  • the present invention relates more specifically to a process for substantially complete elimination of mercury and mercury compounds coexisting with asphaltene and the like in natural gas condensates continuously for a long period of time.
  • natural gas condensates contain elemental mercury and mercury compounds such as organic and inorganic mercury, and the content sometimes reaches as high as from several tens ppb to several thousands ppb while depending on the place of origin.
  • natural gas condensates or naphthas obtained by distillation of them containing such mercury and mercury compounds are used as a feedstock for olefins for petrochemical products, for example, ethylene or propylene, or when they are used as a feedstock for a reformer for hydrogen production
  • aluminum material used for the constituent material of the apparatus may bring about amalgam corrosion or poisoning is caused to noble metal catalysts used for hydrogenation in the case where they are used as feedstocks for petrochemical product.
  • mercury adsorbents various kinds of mercury adsorbents and processes for eliminating mercury by using them have been proposed.
  • sulfides of heavy metals such as molybdenum, tungsten and vanadium carried on supports such as alumina have been proposed as the mercury adsorbent (refer, for example, to Japanese Patent Publication No.24623/1994) and, further, mercury adsorbents comprising sulfur carried on porous supports, for example, a sulfur-carrying activated carbon obtained by mixing activated carbon with fine sulfur particles and heating them to a predetermined temperature (refer to Japanese Patent Laid-Open No. (7891/1984) or activated carbon containing organic sulfur compounds (refer to Japanese Patent Laid-Open No.114632/1987) have been disclosed.
  • the process for eliminating mercury in natural gas condensates there has been proposed, for example, a process of bringing mercury compound-containing natural gas condensates into contact with a ⁇ -alumina catalyst, a zeolite catalyst and/or a silica catalyst at a temperature from 150°C to 300°C thereby decomposing the mercury compounds into elemental mercury and then eliminate the resultant elemental mercury with an adsorbent mainly comprising molybdenum sulfide (refer to Japanese Patent Laid-Open No.33091/1994).
  • EP-A-325 486 discloses a process of bringing a mercury-containing hydrocarbon into contact with an adsorbent containing a cupric compound and/or stannous compound supported by activated carbon, in order to eliminate the mercury from the hydrocarbon.
  • Figure 3 discloses a preferred embodiment in which two adsorption columns are used.
  • An object of the present invention is to provide a process for eliminating mercury and mercury compounds existing in liquid hydrocarbons containing heavy ingredients such as asphaltene and resinous materials with no effect of asphaltene and the like and efficiently for a long period of time irrespective of the form of them existing therein.
  • Another object of the present invention is to provide a process for adsorption - elimination of mercury and mercury compounds existing in liquid hydrocarbons containing asphaltene and resinous materials in a simple device, by convenient operation and efficiently for a long period of time.
  • a further object of the present invention is to provide a process for eliminating mercury and mercury compounds in natural gas condensates containing mercury substantially completely by using an adsorbent.
  • a still further object of the present invention is to provide an adsorbent for adsorption-elimination of mercury and mercury compounds coexisting with asphaltene and resinous materials in liquid hydrocarbons.
  • ⁇ means 0.1nm.
  • the present invention concerns a process for eliminating mercury and mercury compounds in liquid hydrocarbons using a selective combination of two or more different kinds of specific mercury adsorbents, comprising contacting liquid hydrocarbons containing mercury and asphaltene in a first adsorption treatment zone with a porous inorganic adsorbent which is at least one of materials selected from the group consisting of activated carbon, activated clay, alumina, silica gel, silica alumina and zeolite, and then contacting the adsorption-treated liquid hydrocarbons in a second adsorption treatment zone with an activated carbon having a specific surface area from 200 m 2 /g to 2500 m 2 /g, an average pore diameter from 10 ⁇ to 100 ⁇ and a pore volume from 0.4 ml/g to 1.5 ml/g.
  • a porous inorganic adsorbent which is at least one of materials selected from the group consisting of activated carbon, activated clay, alumina, silica gel,
  • the unique feature of the present invention is based on the finding obtained by the study of the present inventors, et al, that the mercury adsorbability of an activated carbon having high adsorbability is remarkably lowered in case of elimination of mercury from liquid hydrocarbons in which heavy ingredients such as asphaltene and resinous materials coexist with mercury, whereas an activated carbon having not so high mercury adsorbability can not completely eliminate mercury but the adsorbability is not so hindered even under the coexistence of asphaltene and the like, and resides in that a mercury elimination process capable of operating continuously for a long period of time can be attained by using a selective combination of two or more different kinds of specific mercury adsorbents.
  • the present invention further provides, as another preferred embodiment, a process for eliminating mercury in liquid hydrocarbons comprising:
  • the present invention provides, as a preferred embodiment, a process for eliminating mercury in liquid hydrocarbons comprising;
  • the liquid hydrocarbon used for the process for eliminating mercury and mercury compounds in the liquid hydrocarbons according to the present invention has no particular restriction and there can be mentioned, for example, natural gas condensates recovered from natural gases.
  • natural gas condensates recovered from natural gases.
  • some of natural gas condensates from South Asia usually contain 1 % to 3 % by weight of asphaltene.
  • Asphaltene is an asphaltic carbonaceous ingredient which is soluble to benzene but insoluble to pentane and heptane, mainly comprises a number of relatively high molecular weight condensated ring aromatic compounds and contains a great amount of sulfur, oxygen and nitrogen compounds.
  • the natural gas condensates also contain, for example, carben as an asphalt analogous material and resinous materials as a precursor for asphaltene.
  • the process for eliminating mercury in the liquid hydrocarbons according to the present invention is extremely effectively applicable to elimination of mercury in natural gas condensates having compositions as described above, but it can also be used for any of liquid hydrocarbon, naphtha, kerosene, light oil, vacuum distillation oil, pyrolytic gasoline, catalytic naphtha or the like obtained from natural gases or petroleum entraining gases with similar effects.
  • Mercury in the natural gas condensates is contained in the form of elemental mercury, as well as mercury compounds such as organic or inorganic mercury and the content may sometimes reach from several tens ppb to several thousands ppb while varying according to places of origin but mercury existing in any of the forms can be treated by the process for eliminating mercury in the liquid hydrocarbons according to the present invention without requiring a step of reduction and decomposition of mercury compounds as proposed so far. Further, according to the present invention, mercury in the natural gas condensates can be treated over a wide range of concentration with no restriction of the mercury concentration, and mercury contained even in a great amount can be eliminated substantially completely.
  • the porous inorganic adsorbent used in the first adsorption treatment zone is selected from the group consisting of activated carbon, activated clay, alumina, silica gel, silica-alumina and zeolite.
  • Porous inorganic adsorbents having specified pore structure are preferred and those having characteristic values with a specific surface area of more than 200 m 2 /g and a pore diameter from 2 ⁇ to 1000 ⁇ can be mentioned.
  • a relatively large pore diameter is set such that pores of the adsorbent are not closed by heavy ingredients such as asphaltene.
  • Preferred average pore diameter is from 10 ⁇ to 200 ⁇ .
  • the activated carbon used in the first adsorption treatment zone of the present invention those having a specific surface area of more than 200 m 2 /g, particularly, from 500 m 2 /g to 2500 m 2 /g are more preferred.
  • a preferred range for the pore diameter is from 2 ⁇ to 1000 ⁇ , particularly, from 5 ⁇ to 500 ⁇ and, further preferably from 10 ⁇ to 300 ⁇ .
  • the average pore diameter is from 100 ⁇ to 200 ⁇ and a relatively large diameter within a range of 150 ⁇ to 200 ⁇ is preferred.
  • the raw material of the activated carbon there can be used, for example, coal, coke, charcoal, coconut shell, wood, resin and bone black.
  • the activated carbon having the pore structure as described above can be prepared by using an activating gas having a steam content from 15% to 60% by volume as an activating condition in the production process of the activated carbon.
  • the efficiency for the adsorptive separation of asphaltene or the like and elimination of mercury can be improved further by using the activated carbon having such a pore structure.
  • Pelleted carbon or molded carbon can be prepared by adding from 30 parts to 60 parts of petroleum pitch or coaltar as a binder based on 100 parts of carbon material, kneading, molding and then activating them in accordance with an ordinary method.
  • the activated clay is obtained by treating acidic clay as a sort of clays with sulfuric acid or the like to further improve the activity.
  • An activated clay having a chemical composition comprising SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, MgO and K 2 O and having a pore structure with a specific surface area from 500 m 2 /g to 2500 m 2 /g, a pore diameter from 5 ⁇ to 500 ⁇ and an average pore diameter from 50 ⁇ to 150 ⁇ can be used as a porous inorganic adsorbent in the first adsorption treatment zone in the present invention.
  • the silica gel used in the first adsorption treatment zone in the present invention is prepared by coagulating a colloidal solution of silicic acid.
  • the silica gel contains silicon dioxide as the main ingredient, has a pore structure with a specific surface area from 550 m 2 /g to 700 m 2 /g, and a pore volume usually of more than 0.3 ml/g, and has a high adsorbability.
  • any of powdery, columnar or like other shape may be used like that in the case of the activated carbon.
  • the zeolite used in the first adsorption treatment zone of the present invention is aluminosilicate which is a material having a three dimensional skeleton and a pore structure formed in the gap thereof. It has a large specific surface area amounting to 500 m 2 /g or greater and a high adsorbability based thereon.
  • aluminosilicate which is a material having a three dimensional skeleton and a pore structure formed in the gap thereof. It has a large specific surface area amounting to 500 m 2 /g or greater and a high adsorbability based thereon.
  • the composition and the structure and any of natural or synthetic products can be used. Further they can be used with no particular restriction on the pore volume, grain size and the configuration, but a pore volume of more than 0.3 ml and the grain size of less than 50 mesh (grain size of more than about 0.3 mm) are preferred.
  • the zeolite mainly comprises an aluminosilicate of alkali metal or alkaline earth metal as described above and constitutes a three dimensional regular skeleton structure having a large cavity, in which an SiO 2 tetrahedron and an AlO 4 tetrahedron of methane structure have one carbon atom in common with each other.
  • the zeolite is specified by the chemical composition and X-ray diffraction pattern.
  • the zeolite has a defined pore diameter within a range from 3 ⁇ to 10 ⁇ depending on the cyclic structure of oxygen and has an adsorbability and molecular sieve property based on the pore structure.
  • Alumina used in the first adsorption treatment zone of the present invention comprises aluminum oxide as the main ingredient, has a pore structure and shows a high adsorbability at a pore volume usually of more than 0.3 ml/g. Those having a specific surface area of more than 200 m 2 /g, a pore diameter from 2 ⁇ to 1000 ⁇ and an average pore diameter from 40 ⁇ to 120 ⁇ are used.
  • Alumina having such a pore structure can be prepared by optionally controlling conditions for preparation and aging of aluminum hydrates from alkali aluminates such as sodium aluminate and potassium aluminate, inorganic salts of aluminum such as aluminum sulfate and aluminum nitrate.
  • the silica-alumina used in the first adsorption treatment zone of the present invention comprises a chemical composition of SiO 2 and Al 2 O 3 , has a porous structure of composite silica gel and alumina gel, and shows high adsorbability.
  • the silica content in the silica-alumina is selected within the range from 5% to 50% by weight, preferably, 10% to 40% by weight to adjust the acid point. In the present invention, a range from 25% to 30% by weight is particularly preferred. There can be mentioned a specific surface area of more than 200 m 2 /g, a pore diameter of more than 2 ⁇ and an average pore diameter of more than 100 ⁇ .
  • the silica-alumina having such characteristic values can be prepared by optionally specifying the preparing conditions and the aging conditions of silica-alumina hydrates.
  • any of the porous inorganic adsorbents has a porous structure and a large specific surface area and shows a high adsorbability.
  • a porous material having a specific surface area of more than 100 m 2 /g, more preferably, from 200 m 2 /g to 1500 m 2 /g is preferred since it is possible to improve the adsorptive elimination of asphaltene and mercury eliminating rate.
  • liquid natural gas condensates and the porous inorganic adsorbent can be brought into contact with each other by any known system such as fixed bed, moving bed, fluidized bed or ebullated bed.
  • the liquid hydrocarbons can be supplied continuously as an ascending stream or descending stream to a filled layer constituted by filling to fix porous inorganic adsorbent particles to the adsorption treatment zone to conduct adsorption treatment.
  • the porous inorganic adsorbent particles and the liquid hydrocarbons can be brought into contact with each other continuously while the adsorbent particle group charged from above is successively dropped gravitationally when the adsorbent particles are added intermittently or substantially continuously to one end of the adsorption treatment zone and then taken out intermittently or substantially continuously from the other end.
  • the porous inorganic adsorbent particles are caused to suspend by the stream of the liquid hydrocarbons thereby bringing them into contact with each other.
  • the fixed bed method is suitable among each of the contact systems described above since the structure of the adsorption treatment zone is simple and the operation is easy as well.
  • the porous inorganic adsorbent fixed bed can be disposed by filling powdery, pulverized, cylindrical, globular, fibrous or honeycomb-shaped adsorbent in the adsorption treatment zone and fixing in accordance with an ordinary method.
  • Adsorbents having a grain size from 0.15 mm to 4.75 mm, preferably 0.5 mm to 4.5 mm can be used. More specifically, a glass wool is laid at the bottom of the adsorption treatment zone and silica balls are disposed to prevent the adsorbent from flowing out of the adsorption treatment zone.
  • the natural gas condensates can be supplied as a descending flow from above or as an ascending flow from below, and brought into contact with the porous inorganic adsorbent in the fixed bed, the descending flow being preferred in view of stabilization of the adsorbent in the adsorption column.
  • porous inorganic adsorbent such as activated carbon, active white clay, silica gel, zeolite, alumina or silica-alumina can be used alone, two or more of them may be used in admixture.
  • the conditions for the adsorption treatment in the first adsorption treatment zone can be selected optionally. While an elevated temperature may be used, treatment under a normal temperature is sufficient and the purpose of the adsorption treatment can be attained sufficiently under a normal pressure. Further, in the case of using the fixed bed for the adsorbent, an LV value can be set to less than 100 cm/min, preferably, less than 50 cm/min. The LV value means a value obtained by dividing the amount of the liquid hydrocarbons treated with a cross sectional area of the adsorbent layer.
  • the mercury content in the liquid hydrocarbons flowing out of the first adsorption treatment zone after the adsorption treatment can be reduced to 4 ppb - 20 ppb although different depending on the kind of the adsorbent used. Further, asphaltene and like other material are adsorbed on the porous inorganic adsorbent and are scarcely present in the liquid hydrocarbons after the adsorption treatment.
  • the activated carbon used in the second adsorption treatment zone has pore characteristics with a specific surface area of 200 m 2 /g to 2500 m 2 /g, a pore diameter from 5 ⁇ to 1000 ⁇ and an average pore diameter from 10 ⁇ to 100 ⁇ . Further, among the activated carbons having such pore characteristics, those having a specific surface area from 500 m 2 /g to 1500 m 2 /g, an average diameter from 10 ⁇ to 50 ⁇ and a pore volume from 0.4 ml/g to 1.5 ml/g are particularly preferred for the selective adsorption of mercury.
  • the raw material for preparing the activated carbon having the pore characteristics described above has no particular restriction and coal, coke, charcoal, bone black or carbonized products such as coconut shell, wood and resin can be used.
  • the activated carbon can be obtained by way of a steam step of activating the carbonized products by using a gas with a steam content of less than 15% by volume.
  • the gas for activating the activated carbon contains steams and gaseous carbon dioxide. While the content of the gaseous carbon dioxide is not restricted particularly for the activated carbon used in the second absorption treatment zone of the present invention, it is necessary to activate the carbonaceous material with a gas having a steam content of less than 15% by volume.
  • the activating gas usually used for activating a carbonaceous material has a composition containing steams of 40 % to 60% by volume or higher. This is because the steam partial pressure is set as high as possible for the activating gas composition since the activating rate for the carbonaceous material with steams is much higher than that of the gaseous carbon dioxide. Accordingly, the activating condition for the activated carbon is remarkably moderated in the present invention as compared with that of the conventional method.
  • the activating gas preferably has a composition comprising 50 % to 85 % by volume of nitrogen gas, 3 % to 15 % by volume of steams, 3 % to 30 % by volume of gaseous carbon dioxide (carbonic acid gas), 0 % to 2 % by volume of oxygen gas and 0 % to 2 % by volume of hydrogen gas.
  • the activating treatment is conducted by heating the carbonaceous material as described above, that is, the carbonaceous material to 700°C - 1200°C in the activating gas followed by cooling.
  • Activated carbon having a specific surface area from 200 m 2 /g to 2500 m 2 /g, a pore diameter from 5 ⁇ to 1000 ⁇ , an average pore diameter from 10 ⁇ to 50 ⁇ and a pore volume from 0.4 ml/g to 1.5 ml/g can be obtained by the activating treatment.
  • the activated carbon obtained under the activating condition described above has the foregoing pore characteristics, so that pores suitable to the adsorption of mercury have a highly developed pore structure and the performance of eliminating mercury in the liquid hydrocarbons is enhanced by the pore structure.
  • the activated carbon is cooled also after the activation in a gas having a similar composition as that of the activating gas till the temperature of the activated carbon is lowered to less than 300°C and then taken out of the system.
  • the gas similar with the activating gas that is, an atmosphere required during cooling may be an atmosphere of a nitrogen gas, gaseous carbon dioxide or a gas mixture thereof used upon activation (content of oxygen or hydrogen of less than 1% - 2%), and it is not always necessary that the gas used for activation and the gas used for cooling have a composition just identical with that of the activating gas.
  • the activated carbon may be used alone or may be used as a mercury adsorbent in which an alkali metal sulfide and/or alkaline earth metal sulfide is carried on the activated carbon subjected to the activating treatment as described above.
  • a metal sulfide has an effect of improving the mercury adsorption performance of the activated carbon.
  • the alkali metal sulfide or the alkaline earth metal sulfide carried on the activated carbon and there can be mentioned, for example, Li 2 S, Na 2 S and K 2 S as the alkali metal sulfide and MgS and CaS as the alkaline earth metal sulfide.
  • Such alkali metal sulfide and alkaline earth metal sulfide may be used alone or in admixture of two or more of them, with Na 2 S being most preferred among the compounds.
  • the amount of the alkali metal sulfide or the alkaline earth metal sulfide to be carried has no particular restriction and it is preferably within a range from 0.1% to 30% by weight based on the activated carbon. If the carried amount is less than 0.1% by weight, the mercury adsorption performance tends to be lowered and, if the carried amount is more than 30% by weight, the mercury adsorption performance is also lowered. Further, if the carried amount is more than 30% by weight, the mercury adsorption performance of the activated carbon tends to be hindered by the metal sulfide thereby saturating the effect of improving the mercury adsorption performance.
  • contact between the liquid hydrocarbons and the mercury adsorbent in the second adsorption treatment zone may be conducted by any of the fixed bed, moving bed, fluidized bed or ebullated bed system in the same manner as in the first adsorption treatment zone, and the fixed bed system is suitable since the structure of the adsorption treatment zone is simple and the operation is easy as well.
  • the fixed bed can be constituted and disposed in the same manner as the fixed bed in the first adsorption treatment zone.
  • the mercury adsorbent packed layer in the second adsorption treatment zone of the present invention is constituted by filling and fixing the mercury adsorbent comprising the activated carbon as described above.
  • the mercury adsorbent comprising the activated carbon as described above.
  • two or more of mercury adsorbents can be used as the activated mercury adsorbent described above.
  • an adsorption treatment zone constituted by filling and fixing mercury adsorbent of activated carbon carrying alkali metal sulfide and/or alkaline earth metal sulfide on the activated carbon to the inlet of the adsorption treatment zone, and filling and fixing a mercury adsorbent only consisting of activated carbon to the exit of the adsorption treatment zone.
  • the volume ratio between the activated carbon packed layer, and the layer filled with activated carbon carrying, for example, the alkali metal sulfide is preferably 1 part to 2 parts by weight of the latter relative to one part by weight of the former.
  • the conditions for the adsorption treatment in the second adsorption treatment zone can be selected optionally like that in the first adsorption treatment zone, a sufficient effect for the adsorption treatment can be obtained under the normal temperature and the normal pressure. Further, in the case of the fixed bed, it is preferred to set the LV value to less than 100 cm/min, particularly, less than 50 cm/min.
  • Reaction system fixed bed system containing an adsorbent having a grain size from 0.5 mm to 2 mm.
  • Reaction system fixed bed system containing an adsorbent having a grain size from 0.5 mm to 3 mm.
  • an activated clay is, instead of the activated carbon shown above, is preferably used.
  • the specific surface area was measured by a BET method with a nitrogen gas.
  • the pore volume and pore diameter distribution were calculated based on an isothermal adsorption curve of nitrogen gas measured by BELLSORB 28SA measuring equipment.
  • a natural gas condensate from Australia (density: 0.7418 g/cm 3 at 15°C, mercury content: 27.5 ppb, asphaltene content: 1 % by weight) was passed at a normal temperature and at a flow rate of 1 ml/min through a first adsorption treatment column (adsorption glass tube of 10 mm inner diameter, filled with 24 ml of activated carbon A* 1 (grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 100 ⁇ .
  • the mercury content in the natural gas condensate obtained from the first adsorption treatment column was reduced to 1 ppb but the content exceeded 1 ppb after a lapse of 3 days and continuous treatment was impossible.
  • the condensate was passed at a normal temperature at a flow rate of 1 ml/min (LV value: 1.2 cm/min) through a second adsorption column (adsorption glass tube of 10 ml inner diameter filled with 24 ml of activated carbon X* 5 shown in Table 1), to obtain a condensate having a mercury content of 0.2 ppb at the exit of the second adsorption column.
  • the mercury content in the treated oil could be maintained to less than 1 ppb for 100 days as shown in Table 1.
  • Example 2 The same natural gas condensate as used in Example 1 was passed at a normal temperature and at a flow rate of 1 ml/min through a first adsorption column (adsorption glass tube of 10 mm inner diameter filled with 24 ml of alumina) (grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 90 ⁇ , manufactured by Sumitomo Chemical Co., Ltd.)).
  • adsorption glass tube of 10 mm inner diameter filled with 24 ml of alumina (grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 90 ⁇ , manufactured by Sumitomo Chemical Co., Ltd.)).
  • the mercury content in the condensate obtained from the first adsorption column was 10 ppb.
  • the condensate was passed at a normal temperature and at a flow rate of 1 ml/min through the same second adsorption column as in Example 1, to obtain a condensate having a mercury content of 0.2 ppb at the exit of the second adsorption column.
  • the mercury content in the treated oil could be maintained to less than 1 ppb for 100 days as shown in Table 1.
  • Example 2 The same natural gas condensate as used in Example 1 was passed at a normal temperature and at a flow rate of 1 ml/min through a first adsorption column (adsorption glass tube of 10 mm inner diameter filled with 24 ml of silica alumina (grain size: 2 mm, specific surface area: 310 m 2 /g, average pore diameter: 100 ⁇ )).
  • adsorption glass tube of 10 mm inner diameter filled with 24 ml of silica alumina (grain size: 2 mm, specific surface area: 310 m 2 /g, average pore diameter: 100 ⁇ )
  • the mercury content in the condensate obtained from the first adsorption treatment column was 8 ppb.
  • the condensate was passed at a normal temperature and at a flow rate of 1 ml/min through the same second adsorption treatment column as in Example 1, to obtain a condensate having a mercury content of 0.2 ppb at the exit of the second adsorption column.
  • the mercury content in the treated oil could be maintained to less than 1 ppb for 100 days as shown in Table 1.
  • Example 2 The same natural gas condensate as used in Example 1 was passed at a normal temperature and at a flow rate of 1 ml/min through a first adsorption column (adsorption glass tube of 10 mm inner diameter filled with 24 ml of silica gel (grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 85 ⁇ ).
  • adsorption glass tube of 10 mm inner diameter filled with 24 ml of silica gel (grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 85 ⁇ ).
  • the mercury content in the condensate obtained from the first adsorption column was 8 ppb, which was passed at a normal temperature and at a flow rate of 1 ml/min through the same second adsorption column as in Example 1, to obtain a condensates having a mercury content of 0.2 ppb at the exit of the second adsorption column.
  • the mercury content in the treated oil could be maintained to less than 1 ppb for 100 days as shown in Table 1.
  • Example 2 The same natural gas condensate as used in Example 1 was passed at a normal temperature and at a flow rate of 1 ml/min through a first adsorption column (adsorption glass tube of 10 mm inner diameter filled with 24 ml of zeolite (grain size: 2 mm, specific surface area: 1400m 2 /g, average pore diameter: 10 ⁇ , manufactured by Union Showa Co.)
  • the mercury content in the condensate obtained from the first adsorption treatment column was 7 ppb, which was passed at a normal temperature and at a flow rate of 1 ml/min through the same second adsorption treatment column, to obtain a condensate having a mercury content of 0.2 ppb at the exit of the second adsorption column.
  • the mercury content in the treated oil could be maintained to less than 1 ppb for 100 days as shown in Table 1.
  • Example 2 The same natural gas condensate as used in Example 1 was passed at a normal temperature and at a flow rate of 1 ml/min through a first adsorption column (adsorption glass tube of 10 mm inner diameter filled with 24 ml of activated clay (grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 95 ⁇ (Nikkanite, manufactured by Toyo Hakudo Co.Ltd.)).
  • adsorption glass tube of 10 mm inner diameter filled with 24 ml of activated clay (grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 95 ⁇ (Nikkanite, manufactured by Toyo Hakudo Co.Ltd.)).
  • the mercury content in the condensate obtained from the first adsorption column was 11 ppb, which was passed at a normal temperature and at a flow rate of 1 ml/min through the same second adsorption column as in Example 1, to obtain a condensate having a mercury content of 0.2 ppb at the exit of the second adsorption column.
  • the mercury content in the treated oil could be maintained to less than 1 ppb for 100 days as shown in Table 1.
  • Example 1 Quite in the same manner as in Example 1 except for using activated carbon B* 2 (grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 100 ⁇ ) instead of the activated carbon A in the first adsorption column, a treated oil with a mercury content of 0.2 ppb was obtained from the exit of the second adsorption column.
  • activated carbon B* 2 grain size: 2 mm, specific surface area: 1400 m 2 /g, average pore diameter: 100 ⁇
  • Example 1 Quite in the same manner as in Example 1 except for using activated carbon C* 3 instead of activated carbon A in the first absorption column , a treated oil with a mercury content of 0.2 ppb was obtained from the exit of the second adsorption column. The results are shown in Table 1.
  • Example 1 Quite in the same manner as in Example 1 except for using activated carbon D* 4 instead of activated carbon A in the first adsorption column , the mercury content in the adsorption-treated oil obtained from the first adsorption column was 20 ppb and a treated oil with a mercury content of 0.2 ppb was obtained from the exit of the second adsorption column. The results are shown in Table 1.
  • Adsorption treatment for the natural gas condensate was conducted quite in the same manner as in Example 1 except for not using the first adsorption column but using only the second adsorption column filled with activated carbon X *5 (adsorption glass tube of 10 mm inner diameter, filled with 24 ml of activated carbon X* 5 ).
  • the results of the adsorption treatment are shown in Table 2.
  • the residual mercury content in the treated oil is high only with the treatment by the activated carbon in the second adsorption column as shown in Table 2.
  • Examples and Comparative Examples described above show that specific combination of mercury adsorbents is necessary in each of the examples for the elimination of mercury from natural gas condensates in which asphaltene is present together and that long time continuous operation is possible as a result of the specific combination.
  • mercury can be eliminated substantially completely over a long period of time from liquid hydrocarbons containing mercury and asphaltene, for example, natural gas condensates even under the coexistence of asphaltene, by bringing the gas condensates into contact in a first adsorption column with at least one of materials selected from the group consisting of activated carbon, activated clay, alumina, silica-alumina, silica gel and zeolite and then bringing them into contact in a second adsorption column with an activated carbon having a specific surface area of not less than 500 m 2 /g and an average pore diameter from 10 ⁇ to 100 ⁇ .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (10)

  1. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides en utilisant une association de deux ou plus de deux types différents d'adsorbants du mercure, comprenant les étapes consistant :
    (a) à mettre en contact des hydrocarbures liquides contenant du mercure et des composés de mercure, ainsi qu'un asphaltène, dans une première zone de traitement par adsorption, avec un adsorbant inorganique poreux qui consiste en au moins une des matières choisies dans le groupe consistant en le charbon actif, une argile activée, l'alumine, le gel de silice, la silice-alumine et une zéolite, puis,
    (b) à mettre en contact les hydrocarbures liquides traités avec adsorption provenant de ladite zone de traitement par adsorption, dans une seconde zone de traitement par adsorption, avec un charbon actif ayant une surface spécifique comprise dans l'intervalle de 200 m2/g à 2500 m2/g, un diamètre moyen des pores compris dans l'intervalle de 1 nm à 10 nm (10 Å à 100 Å), et un volume des pores compris dans l'intervalle de 0,4 ml/g à 1,5 ml/g.
  2. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant la revendication 1, dans lequel les hyhrocarbures liquides consistent en condensats d'un gaz naturel.
  3. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant la revendication 1 ou 2, dans lequel l'adsorbant inorganique poreux a une surface spécifique supérieure à 200 m2/g et un diamètre des pores compris dans l'intervalle de 0,2 nm à 100 nm (2 Å à 1000 Å).
  4. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant une ou plusieurs des revendications 1 à 3, dans lequel le charbon actif utilisé dans la première zone de traitement par adsorption a un diamètre moyen des pores supérieur à 10 nm (100 Å).
  5. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant une ou plusieurs des revendications 1 à 4, dans lequel le charbon actif utilisé dans la seconde zone de traitement par adsorption a un volume des pores compris dans l'intervalle de 0,6 ml/g à 1,2 ml/g.
  6. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant une ou plusieurs des revendications 1 à 5, dans lequel le charbon actif utilisé dans la seconde zone de traitement par adsorption a un diamètre moyen des pores compris dans l'intervalle de 1 nm à 5 nm (10 Å à 50 Å).
  7. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant une ou plusieurs des revendications 1 à 6, dans lequel le charbon actif utilisé dans la seconde zone de traitement par adsorption est obtenu en soumettant une matière carbonée à un traitement d'activation au moyen d'un gaz d'activation ayant une teneur en vapeur d'eau inférieure à 15 % en volume.
  8. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant une ou plusieurs des revendications 1 à 5 et 7, dans lequel le traitement d'activation de la matière carbonée comprend le chauffage de cette matière carbonée dans un gaz d'activation comprenant 50 % à 85 % en volume d'azote gazeux, 3 % à 15 % en volume de vapeur d'eau, 3 % à 30 % en volume de dioxyde de carbone gazeux, 0 % à 2 % en volume d'oxygène gazeux, 0 % à 2 % en volume d'hydrogène gazeux, à une température comprise dans l'intervalle de 700°C à 1200°C, et ensuite un refroidissement, ce qui permet de préparer un charbon actif ayant une surface spécifique comprise dans l'intervalle de 200 m2/g à 2500 m2/g et un diamètre moyen des pores de 1 nm à 10 nm (10 Å à 100 Å).
  9. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant une ou plusieurs des revendications 1 à 8, dans lequel les hydrocarbures liquides contenant du mercure sont mis en contact avec l'adsorbant solide dans la première zone de traitement par adsorption et avec le charbon actif dans la seconde zone de traitement par adsorption, chacun ayant un diamètre des grains de 0,15 mm à 4,75 mm.
  10. Procédé pour éliminer le mercure et les composés de mercure présents dans des hydrocarbures liquides, répondant à la définition suivant une ou plusieurs des revendications précédentes, dans lequel l'argile activée est utilisée dans la première zone d'adsorption et le charbon actif est utilisé dans la seconde zone d'adsorption.
EP19970102446 1996-05-30 1997-02-14 Procédé d'élimination de mercure d'hydrocarbures liquides Expired - Lifetime EP0810278B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP158862/96 1996-05-30
JP15886296 1996-05-30
JP15886296 1996-05-30

Publications (3)

Publication Number Publication Date
EP0810278A2 EP0810278A2 (fr) 1997-12-03
EP0810278A3 EP0810278A3 (fr) 1998-03-25
EP0810278B1 true EP0810278B1 (fr) 2002-05-08

Family

ID=15681029

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19970102446 Expired - Lifetime EP0810278B1 (fr) 1996-05-30 1997-02-14 Procédé d'élimination de mercure d'hydrocarbures liquides

Country Status (2)

Country Link
EP (1) EP0810278B1 (fr)
DE (1) DE69712405T2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7510992B2 (en) 2007-06-05 2009-03-31 Amcol International Corporation Sulfur-impregnated and coupling agent-reacted organoclay mercury and/or arsenic ion removal media
US7553792B2 (en) 2007-06-05 2009-06-30 Amcol International Corporation Sulfur-impregnated and coupling agent-reacted organoclay mercury and/or arsenic ion removal media
US7871524B2 (en) 2007-06-05 2011-01-18 Amcol International Corporation Method for removing merury and/or arsenic from water using a silane coupling agent reacted organoclay
US7910005B2 (en) 2007-06-05 2011-03-22 Amcol International Corporation Method for removing mercury and/or arsenic from contaminated water using an intimate mixture of organoclay and elemental sulfur
US8025160B2 (en) 2007-06-05 2011-09-27 Amcol International Corporation Sulfur-impregnated organoclay mercury and/or arsenic ion removal media
US8382990B2 (en) 2007-06-05 2013-02-26 Amcol International Corporation Method of removing mercury and/or arsenic from water or mercury from a gas using an extruded onium ion intercalated silane coupling agent reacted layered phyllosilicate

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2649024B2 (ja) * 1995-07-27 1997-09-03 太陽石油株式会社 液体炭化水素中の水銀除去方法
US6740406B2 (en) * 2000-12-15 2004-05-25 Kimberly-Clark Worldwide, Inc. Coated activated carbon
US8088277B2 (en) * 2008-06-11 2012-01-03 General Electric Company Methods and system for removing impurities from heavy fuel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4946582A (en) * 1988-01-22 1990-08-07 Mitsui Petrochemical Industries, Ltd. Method of removing mercury from hydrocarbon oils
US5107060A (en) * 1990-10-17 1992-04-21 Mobil Oil Corporation Thermal cracking of mercury-containing hydrocarbon
JP2649024B2 (ja) * 1995-07-27 1997-09-03 太陽石油株式会社 液体炭化水素中の水銀除去方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7510992B2 (en) 2007-06-05 2009-03-31 Amcol International Corporation Sulfur-impregnated and coupling agent-reacted organoclay mercury and/or arsenic ion removal media
US7553792B2 (en) 2007-06-05 2009-06-30 Amcol International Corporation Sulfur-impregnated and coupling agent-reacted organoclay mercury and/or arsenic ion removal media
US7871524B2 (en) 2007-06-05 2011-01-18 Amcol International Corporation Method for removing merury and/or arsenic from water using a silane coupling agent reacted organoclay
US7910005B2 (en) 2007-06-05 2011-03-22 Amcol International Corporation Method for removing mercury and/or arsenic from contaminated water using an intimate mixture of organoclay and elemental sulfur
US8025160B2 (en) 2007-06-05 2011-09-27 Amcol International Corporation Sulfur-impregnated organoclay mercury and/or arsenic ion removal media
US8382990B2 (en) 2007-06-05 2013-02-26 Amcol International Corporation Method of removing mercury and/or arsenic from water or mercury from a gas using an extruded onium ion intercalated silane coupling agent reacted layered phyllosilicate

Also Published As

Publication number Publication date
EP0810278A3 (fr) 1998-03-25
DE69712405D1 (de) 2002-06-13
EP0810278A2 (fr) 1997-12-03
DE69712405T2 (de) 2002-10-31

Similar Documents

Publication Publication Date Title
EP0568003B1 (fr) Absorption d'hydrogène sulfuré et composition absorbante utilisée à cette fin
KR100557835B1 (ko) 탄화수소 스트림용 흡착제 및 방법
US7820037B2 (en) Desulfurizing agent manufacturing method and hydrocarbon desulfurization method
RU2230608C2 (ru) Композиция сорбента, способ её получения и применения при десульфуризации
EP0794240B1 (fr) Adsorbent pour le mercure
JP4729232B2 (ja) 脱硫及び脱硫用収着剤
JP4469499B2 (ja) ガス流からの金属カルボニルの除去方法
EP0755994B1 (fr) Méthode pour l'élimination de mercure dans les hydrocarbures liquides
UA73141C2 (en) Method for production of a sorbent and method of desulfurization
WO2001070907A1 (fr) Desulfuration et produits absorbants associes
CZ289817B6 (cs) Způsob výroby sorbentové kompozice, sorbentová kompozice a její pouľití
BRPI0902204A2 (pt) adsorvente de dessulfurização, processo de preparação do adsorvente e método de dessufurização de óleo diesel ou gasolina de pirólise
EP0810278B1 (fr) Procédé d'élimination de mercure d'hydrocarbures liquides
KR20080047460A (ko) 탄화수소로부터 황을 제거하기 위한 재생가능한 흡착제 및이의 제조방법 및 그 용도
JP3624671B2 (ja) 炭化水素留分中の微量金属の吸着除去方法
JP5259090B2 (ja) 塩化物の除去方法及び塩化物吸収剤
JP2688749B2 (ja) 耐高温高次脱硫剤の製造方法
JPH1072588A (ja) 水銀の除去方法
JPH11181447A (ja) 炭化水素油中の水銀の除去方法
JPH10130660A (ja) 砒素および鉛の除去方法
JP2000017273A (ja) 水銀の除去方法
JPH10202003A (ja) 水銀吸着剤およびそれを用いる炭化水素油中の水銀の除去方法
JPH11193385A (ja) 含砒素液体炭化水素用砒素吸着剤およびそれを用いる含砒素液体炭化水素中の砒素の除去方法
JPH10202096A (ja) 微量金属吸着剤およびそれを用いる炭化水素油中の微量金属の除去方法
JPH10128003A (ja) 液体炭化水素中の砒素および鉛の除去方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE NL

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TAIYO ENGINEERING COMPANY LIMITED

17P Request for examination filed

Effective date: 19980918

17Q First examination report despatched

Effective date: 20000602

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE NL

REF Corresponds to:

Ref document number: 69712405

Country of ref document: DE

Date of ref document: 20020613

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20030131

Year of fee payment: 7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030428

Year of fee payment: 7

26N No opposition filed

Effective date: 20030211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040901

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040901

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20040901