US3915844A - Method for treatment of heavy oils - Google Patents

Method for treatment of heavy oils Download PDF

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Publication number
US3915844A
US3915844A US419657A US41965773A US3915844A US 3915844 A US3915844 A US 3915844A US 419657 A US419657 A US 419657A US 41965773 A US41965773 A US 41965773A US 3915844 A US3915844 A US 3915844A
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metal compound
alkali metal
coke
gasification
coking
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US419657A
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Mikio Ueda
Shigenori Suzuki
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Mitsui Engineering and Shipbuilding Co Ltd
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Mitsui Engineering and Shipbuilding Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
    • C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water

Definitions

  • the present invention relates to method for treatment of heavy oils.
  • sulfur contained in the heavy oil at such a high content as 3 to 7% by weight is incorporated as hydrogen sulfide in the cracked gas and as an organic sulfur compound in the cracked oil and sulfur is further concentrated in the coke and the sulfur content is twice as high as in the starting oil.
  • the majority of sulfur left in the coke is sandwiched between carbon lattice layers to form compounds together with carbon. Therefore, in case such coke is gasified, the porosity of the coke is damaged by such sulfur compounds and it is therefore not expected to increase the surface area, though the increase of the surface area is very advantageous for the coke gasification reaction.
  • This invention is to provide a method for the treatment of heavy oils comprising coking a heavy oil such as asphalt, gasifying the resulting coke and thus recovering a readily desulfurizable light oil and a gas,
  • alkali metal compound used in the instant specification are meant carbonates, hydroxides and oxides of alkali metals such as Na, Li and K, compounds convertible to such compounds and mixtures thereof.
  • a powdery or granular alkali metal compound in the heated state is fed to the coker independently from the starting oil and it is utilized as seed particles capable of promoting formation of granular coke, whereby an effect of desulfurization of the starting oil and an effect of forming readily gasifiable coke can be attained, and then the resulting granular coke is gasified with use of steam and oxygen or air.
  • mist or vapor of the starting oil adheres on fine particles of the alkali metal compound and the volatile components of the starting oil are evaporated by the heat of the alkali metal compound, resulting in formation of fine particles of the coke. Further, fine particles of the alkali metal compound and mist or vapor of the starting oil are further stuck to the so formed fine particles of the coke and thus formed particles are stuck to each other to grow into larger particles and dry distillation is also performed at the same time.
  • coke particles are formed in the form of aggregates of fine cokes which each coke is formed by utilizing one or more particles of the alkali metal compound as the seed.
  • the heat for gasification of volatile components is supplied from the alkali metal compound which is fed in the heated state to the coker and instantaneously incorporated and introduced into the starting oil, and therefore, the volatile components are transferred from the interior of oil drops toward the outer surface while undergoing dehydrogenation. Since the volatile components are thus gasified and they undergo the dehydrogenation reaction more extensively than in the conventional fluid coking process, the resulting coke has a better porosity and a low bulk density, which are charateristic properties of the coke obtained according to this invention.
  • the alkali metal compound acts not only as the seed for formation of coke particles but also as the heating medium for promoting the dehydro- 'genation reaction in asphalt and gasifying volatile components in asphalt. Therefore, the granulation effect attained in the coker is much enhanced as compared with the case where only the starting oil is fed to the coker.
  • the sulfur components contained in the starting heavy oil are combined with the alkali metal compound just before formation of coke during the advance of the decomposition reaction and alkali metal sulfide compounds are formed, with the result that sulfur is not contained in the cracked gas or light cracked oil formed by coking of the heavy hydrocarbon, or in the resulting coke. If sulfur be contained in the resulting coke, its constant can be maintained at a very low level. It has been confirmed that during the coking reaction the alkali metal compound promotes the dehydrogenation reaction in the starting heavy hydrocarbon.
  • the hydrogen content can be increased in the cracked gas, and also the oxygen content in the coke is 4 to by weight, which value is much higher than the oxygen content of about 1% by weight or less in ordinary cokes.
  • the reaction is conducted at a temperature of about 800 to about 1200C, preferably 900 to 1000C.
  • the coke prepared in the coker, which contains the alkali metal compound and a small amount of sulfide thereof is partially burnt with an aid of an oxidant such as oxygen or air and the unburnt coke is heated by the heat of this partial combustion, with the result that the coke is gasified by the reaction between the so heated high temperature coke and steam.
  • the alkali metal compound fed to the coker and its sulfide is forwarded to the gasification furnace in the form of the seed of the coke particle or in the state stuck to the formed coke particle.
  • Such alkali metal compound and its sulfide exhibit a catalytic activity for forming such gases as carbon monoxide, hydrogen, car bon dioxide and methane by the reaction between the heated coke and steam, and therefore, the gasification of the coke can be performed advantageously.
  • the alkali metal compound there are employed carbonates and hydroxides of Na, Li, K and the like. They can be used singly or in the form of admixtures of two or more of them.
  • the alkali metal compound can be directly fed to the coker as it is. It is also possible to feed the alkali metal compound in the state supported on an inorganic refractory or an alkaline earth metal compound.
  • the inorganic refractory there can be mentioned, for example, alumina,glasse, zirconia, chamotte, etc.
  • the alkaline earth metal compound there can be mentioned, for example, CaO, CaCO MgO, MgCO dolomite, etc. We have found that when the alkali metal compound is employed in the state supported on one or more of these compounds, the effect by addition of the alkali metal compound can be greatly enhanced.
  • the alkali metal compound to be fed to the coker as the seed for formation of particles and for reducing the sulfur content in the cracked products is utilized as the gasification catalyst in the gasification furnace and the sulfurized alkali metal compound is regenerated to the original alkali metal compound by an action of the reducing gas formed by the gasification reaction, which is recycled to the coker and used again as the heating medium for supplying the heat to the coker.
  • the method of this invention is characterized in that the alkali metal compound heated at a temperature higher by at least C than the inside temperature of the coker is fed to the coker as the seed particle for formation and growth of granular coke independently from the starting heavy oil.
  • numerous fine particles of the alkali metal compounds are mingled in the heavy oil as seed particles for formation of coke particles at the step of coking of the heavy oil, whereby coke having a good porosity and being readily gasifiable can be obtained.
  • the alkali metal compound acts as the desulfurizing agent for reducing the sulfur content mainly in the cracked gas and light cracked oil.
  • the alkali metal compound acts as a catalyst for promoting the gasification of coke in the gasification furnace, and it is regenerated and heated in the gasification furnace and recycled to the coker as the heating medium.
  • the alkali metal compound exhibits collective effects.
  • the main feature of this invention resides in the use of an alkali metal compound in the process in which coke obtained by treating a heavy hydrocarbon in a fluidized bed coker is gasified according to the fluidized bed method.
  • the drawing is a simple flow sheet illustrating the method of this invention.
  • the alkali metal compound is fed from an appropriate position 9 of a coker l independently from the starting oil fed from a position 4 of the coker.
  • the alkali metal compound is fed in the state heated at a temperature higher by 100 to 500C than the interior temperature of the coker.
  • the light cracked oil and cracked gas are withdrawn through a discharge system 7 and are treated at the subsequent steps.
  • a gasification furnace 2 cokeformed in the coker l and transferred through a transfer conduit 12 is gasified at 800 to 1200C, preferably 850 to ll00C, by a gas, such as oxygen and steam, fed from a gas introduction system 5, and the resulting gas is withdrawn from a discharge system 8 and treated at the subsequent steps.
  • a gas such as oxygen and steam
  • the alkali metal compound or sulfide fed to the gasification furnace in the state stuck to, or incorporated in the coke is partially regenerated by the so formed gas.
  • the alkali metal compound acting as the catalyst and regenerated in the gasification furnace 2 is then withdrawn from the gasification furnace.
  • the flow 6 recycled to the coker contains a large amount of unburnt coke and has a large particle size, it fails to act as the seed in the coker.
  • the so heated alkali metal compound is fed to the coker.
  • EXAMPLE 1 Reduced pressure distillation residual oil of Gattisalan crude oil, which has properties shown in Table l, was fed at a rate of 3.0 kg/hr, together with fluidizing steam fed at a rate of 3.0 kg/hr, to a reaction vessel heated by an Elema type electric furnace, which comprises a stainless steel round tube having a length of 850 mm, a reaction zone inner diameter of 3 inches and an upper free board inner diameter of 6 inches and being equipped with a glass-blowing bottom opening having a reverse frustoconical form, an oil-blowing tube, a pipe for withdrawal of coke particles, a gas discharge pipe and a thermocouple-protecting pipe.
  • Elema type electric furnace which comprises a stainless steel round tube having a length of 850 mm, a reaction zone inner diameter of 3 inches and an upper free board inner diameter of 6 inches and being equipped with a glass-blowing bottom opening having a reverse frustoconical form, an oil-blowing tube, a pipe for withdrawal of co
  • An equimolar powdery mixture of Na CO and CaCO heated at 620C was continuously fed at a rate of 0.5 kg/hr to the reaction vessel from a powder feed pipe mounted on the upper portion of the reaction vessel indpendently from the starting oil and steam.
  • coking of the starting oil was conducted at a reaction temperature of 500C for an average coking time of minutes according to the method using a fluidized bed composed mainly of coke particles.
  • the resulting granular coke was continuously withdrawn from the reaction vessel and as a result of tests of the properties of the product, it was found that the product had an average particle size of 650 microns, a sulfur content of 0.4% by weight and a surface area of 230 m /gr.
  • the coke was packed in a cylindricalglasse reaction tube having an inner diameter of 3 inches and length of 750 mm, and steam was introduced thereinto at a rate of 120 gr/hr while the reaction tube was heated from the outside by means of an Elema type electric furnace.
  • the coke was gasified at 850C, 1000C and l200C to examine the influence of the gasification temperature on the degree of advance of the gasification reaction. It was found that the time required for completion of gasification of the coke was minutes at 850C, 31 minutes at 1000C and 10 minutes at 1200C.
  • EXAMPLE 2 The same reduced pressure distillation residual oil of Gattisalan crude oil as used in Example 1 was employed as the starting oil, and the same fluidized bed type reaction vessel as used in Example 1 was employed. An equimolar mixture of Na CO supported on alumina powder having a particle size not exceeding 30 microns was heated at 620C and was continuously fed at a rate of 0.5 kg/hr to the reaction vessel from a powder feed pipe mounted on the upper portion of the reaction vessel independently from the starting oil and steam. In this manner, coking of the starting oil was conducted at a reaction temperature of 500C for an average coking time of 20 minutes according to the method using a fluidized bed composed mainly of coke particles.
  • the resulting granular coke was continuously withdrawn from the reaction vessel, and as a result of tests of properties of the product, it was found that the product has an average particle size of 270 microns, a sulfur content of 0.5% by weight and a surface area of 200 m /gr.
  • COMPARATIVE EXAMPLE 1 With use of the same fluidized bed type reaction vessel as employed in Example 1, the same reduced pressure distillation residual oil of Gattisalan crude oil as employed in Example 1 was coked at a starting oil feed rate of 3.0 kg/hr and a fluidizing steam feed rate of 3.0 kg/hr, at a reaction temperature of 500C for an average coking time of 20 minutes according to the method using a fluidized bed composed of coke particles.
  • the resulting granular coke was continuously withdrawn from the reaction vessel and as a result of tests of properties of the product it was found that the product has an average particle size of 650 microns, a sulfur content of 7.5% by weight and a surface area of 4.2 m /gr. Effects of reducing the sulfur content and increasing the surface area, such as attained in Examples 1 and 2, could not be attained in this Comparative Example.
  • Example 2 Under the same gasification conditions as employed in Example 1, 100gr of the resulting coke was gasified with use of the same gasification furnace as employed in Example 1. The time required for complete gasificaing conditions and properties of the resulting coke are shown in Table 2 together with data of Examples and other Comparative Examples.
  • COMPARATIVE EXAMPLE 2 10 With use of the same fluidized bed type reaction vessel as used in Example 1, the same reduced pressure distillation residual oil of Gattisalan crude oil as employed in Example 1 was coked at a starting oil feed rate of 3.0 kg/hr and a fluidizing steam feed rate of 3.0 kg/hr, at a reaction temperature of 500C for an average coking time of minutes, while introducing a powder of an equimolar mixture of Na Co and CaCO maintained at room temperature at a rate of 0.5 kg/hr to the reaction vessel from a powder feed pipe mounted on the upper portion of the reaction vessel, according to the method using a fluidized bed composed mainly of coke particles.
  • the resulting granular coke was continuously withdrawn from the reaction vessel, and as a result of tests of properties of the product it was found that the product has an average particle size of 300 microns, a sulfur content of 0.5% by weight and a surface area of 130 m /gr.
  • the effect of desulfurization of coke attained in this Comparative Example was comparable to that attained in Example 1 or 2, but the surface area was smaller than that obtained in Example 1 or 2.
  • COMPARATIVE EXAMPLE 3 With use of the same fluidized bed type reaction vessel as employed in Example 1, the same reduced pressure distillation residual oil of Gattisalan crude oil was coked at a starting oil feed rate of 3.0 kg/hr and a fluidizing steam feed rate of 3.0 kg/hr at a reaction temperature of 500C for an average coking time of 20 minutes according to the method using a fluidized bed composed mainly of coke particles. At this coking operation, an equimolar mixture of Na CO and CaCO was incorporated into the starting oil prior to its feeding to the reaction vessel, and mixture was fed to the reaction vessel together with the starting oil so that the feed rate of the mixture was 0.5 kg/hr.
  • the resulting coke was continuously withdrawn from the reaction vessel, and as a result of tests of properties of the product, it was found that the product has an average particle size of 700 microns, a sulfur content of 0.7% by weight and a surface area of 73 m /gr. No effect of increasing the surface area was observed in this Comparative Example.
  • said particulate alkali metal compound is a member of the group consisting of the carbonates, hydroxides and oxides of the alkali metals or mixtures thereof.
  • said inorganic refractory support medium is a member of the group of alumina, zirconia,glasse and chamotte.
  • alkaline earth metal compound support medium is a member of the group of calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate and dolomite.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Coke Industry (AREA)
US419657A 1972-11-30 1973-11-28 Method for treatment of heavy oils Expired - Lifetime US3915844A (en)

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Cited By (19)

* Cited by examiner, † Cited by third party
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US4003823A (en) * 1975-04-28 1977-01-18 Exxon Research And Engineering Company Combined desulfurization and hydroconversion with alkali metal hydroxides
US4046670A (en) * 1975-04-30 1977-09-06 Kureha Kagaku Kogyo Kabushiki Kaisha Method for the treatment of heavy petroleum oil
US4220518A (en) * 1977-09-28 1980-09-02 Hitachi, Ltd. Method for preventing coking in fluidized bed reactor for cracking heavy hydrocarbon oil
US4305809A (en) * 1980-03-06 1981-12-15 Mobil Oil Corporation Fixed sulfur petroleum coke fuel and method for its production
US4479804A (en) * 1980-03-06 1984-10-30 Mobil Oil Corporation Fixed sulfur petroleum coke fuel and method for its production
US4521383A (en) * 1979-06-08 1985-06-04 Alberta Research Council Lime addition to heavy crude oils prior to coking
US5284574A (en) * 1990-10-01 1994-02-08 Exxon Research And Engineering Company Improved integrated coking-gasification process with mitigation of slagging
US5466361A (en) * 1992-06-12 1995-11-14 Mobil Oil Corporation Process for the disposal of aqueous sulfur and caustic-containing wastes
US5788724A (en) * 1995-06-01 1998-08-04 Eniricerche S.P.A. Process for the conversion of hydrocarbon materials having a high molecular weight
US20020100711A1 (en) * 2000-09-18 2002-08-01 Barry Freel Products produced form rapid thermal processing of heavy hydrocarbon feedstocks
US20040069686A1 (en) * 2002-10-11 2004-04-15 Barry Freel Modified thermal processing of heavy hydrocarbon feedstocks
US20040069682A1 (en) * 2002-10-11 2004-04-15 Barry Freel Modified thermal processing of heavy hydrocarbon feedstocks
EP1386955A3 (en) * 2002-07-30 2004-12-15 Center for Coal Utilization, Japan Process for preparing hydrogen through thermochemical decomposition of water
US8715616B2 (en) * 2011-02-11 2014-05-06 Phillips 66 Company Soak and coke
CN103933995A (zh) * 2014-04-12 2014-07-23 深圳市绿野清风环保工程有限公司 一种垃圾气化催化剂及其制备方法
WO2015195326A1 (en) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Fluidized bed coking with fuel gas production
US9707532B1 (en) 2013-03-04 2017-07-18 Ivanhoe Htl Petroleum Ltd. HTL reactor geometry
WO2018162208A3 (en) * 2017-03-06 2019-08-22 Sibelco Nederland N.V. Particles for fluidised bed reaction methods and fluidised bed reaction methods
WO2019221882A1 (en) * 2018-05-16 2019-11-21 Exxonmobil Research And Engineering Company Fluidized coking with catalytic gasification

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59106638U (ja) * 1982-12-30 1984-07-18 橋本フオ−ミング工業株式会社 サツシユ等の形成素材に対する複合加工装置
JPH0385115U (en, 2012) * 1989-12-18 1991-08-28
JPH0412314U (en, 2012) * 1990-04-18 1992-01-31

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US3707462A (en) * 1970-01-27 1972-12-26 Exxon Research Engineering Co Conversion of heavy petroleum feedstocks
US3723291A (en) * 1971-04-16 1973-03-27 Continental Oil Co Process for desulfurizing coke
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Publication number Priority date Publication date Assignee Title
US2320118A (en) * 1940-04-22 1943-05-25 Phillips Petroleum Co Hydrocarbon conversion and catalyst therefor
US2527575A (en) * 1945-12-04 1950-10-31 Standard Oil Dev Co Method for handling fuels
US2921017A (en) * 1957-02-13 1960-01-12 Socony Mobil Oil Co Inc Process of producing desulfurized coke from petroleum
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US3179584A (en) * 1962-02-23 1965-04-20 Exxon Research Engineering Co Oil coking with increased hydrogen production
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US4003823A (en) * 1975-04-28 1977-01-18 Exxon Research And Engineering Company Combined desulfurization and hydroconversion with alkali metal hydroxides
US4046670A (en) * 1975-04-30 1977-09-06 Kureha Kagaku Kogyo Kabushiki Kaisha Method for the treatment of heavy petroleum oil
US4220518A (en) * 1977-09-28 1980-09-02 Hitachi, Ltd. Method for preventing coking in fluidized bed reactor for cracking heavy hydrocarbon oil
US4521383A (en) * 1979-06-08 1985-06-04 Alberta Research Council Lime addition to heavy crude oils prior to coking
US4521382A (en) * 1979-06-08 1985-06-04 Alberta Research Council Formation of coke from heavy crude oils in the presence of calcium carbonate
US4305809A (en) * 1980-03-06 1981-12-15 Mobil Oil Corporation Fixed sulfur petroleum coke fuel and method for its production
US4479804A (en) * 1980-03-06 1984-10-30 Mobil Oil Corporation Fixed sulfur petroleum coke fuel and method for its production
US5284574A (en) * 1990-10-01 1994-02-08 Exxon Research And Engineering Company Improved integrated coking-gasification process with mitigation of slagging
US5466361A (en) * 1992-06-12 1995-11-14 Mobil Oil Corporation Process for the disposal of aqueous sulfur and caustic-containing wastes
US5788724A (en) * 1995-06-01 1998-08-04 Eniricerche S.P.A. Process for the conversion of hydrocarbon materials having a high molecular weight
US20020100711A1 (en) * 2000-09-18 2002-08-01 Barry Freel Products produced form rapid thermal processing of heavy hydrocarbon feedstocks
US7270743B2 (en) 2000-09-18 2007-09-18 Ivanhoe Energy, Inc. Products produced form rapid thermal processing of heavy hydrocarbon feedstocks
EP1386955A3 (en) * 2002-07-30 2004-12-15 Center for Coal Utilization, Japan Process for preparing hydrogen through thermochemical decomposition of water
US20040069682A1 (en) * 2002-10-11 2004-04-15 Barry Freel Modified thermal processing of heavy hydrocarbon feedstocks
US20040069686A1 (en) * 2002-10-11 2004-04-15 Barry Freel Modified thermal processing of heavy hydrocarbon feedstocks
US7572362B2 (en) * 2002-10-11 2009-08-11 Ivanhoe Energy, Inc. Modified thermal processing of heavy hydrocarbon feedstocks
US7572365B2 (en) 2002-10-11 2009-08-11 Ivanhoe Energy, Inc. Modified thermal processing of heavy hydrocarbon feedstocks
US8715616B2 (en) * 2011-02-11 2014-05-06 Phillips 66 Company Soak and coke
US20140205536A1 (en) * 2011-02-11 2014-07-24 Phillips 66 Company Soak and coke
AU2012214798B2 (en) * 2011-02-11 2015-04-30 Phillips 66 Company Soak and coke
US9707532B1 (en) 2013-03-04 2017-07-18 Ivanhoe Htl Petroleum Ltd. HTL reactor geometry
CN103933995A (zh) * 2014-04-12 2014-07-23 深圳市绿野清风环保工程有限公司 一种垃圾气化催化剂及其制备方法
WO2015195326A1 (en) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Fluidized bed coking with fuel gas production
WO2018162208A3 (en) * 2017-03-06 2019-08-22 Sibelco Nederland N.V. Particles for fluidised bed reaction methods and fluidised bed reaction methods
WO2019221882A1 (en) * 2018-05-16 2019-11-21 Exxonmobil Research And Engineering Company Fluidized coking with catalytic gasification

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JPS5139644B2 (en, 2012) 1976-10-29
DE2359571B2 (de) 1976-12-02
GB1449894A (en) 1976-09-15
JPS4980102A (en, 2012) 1974-08-02
DE2359571A1 (de) 1974-06-06

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