US20130032510A1 - Advanced method and apparatus to process Bitumen containing impurities - Google Patents

Advanced method and apparatus to process Bitumen containing impurities Download PDF

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Publication number
US20130032510A1
US20130032510A1 US13/136,407 US201113136407A US2013032510A1 US 20130032510 A1 US20130032510 A1 US 20130032510A1 US 201113136407 A US201113136407 A US 201113136407A US 2013032510 A1 US2013032510 A1 US 2013032510A1
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bitumen
set forth
char
fuel
gas
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Albert Calderon
Richard Owen McCarthy
Terry James Laubis
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05CNITROGENOUS FERTILISERS
    • C05C11/00Other nitrogenous fertilisers
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00Carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/06Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of oil shale and/or or bituminous rocks
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60Processes
    • C10J3/64Processes with decomposition of the distillation products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/002Removal of contaminants
    • C10K1/003Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004Sulfur containing contaminants, e.g. hydrogen sulfide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/20Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/32Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/001Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
    • C10K3/003Reducing the tar content
    • C10K3/008Reducing the tar content by cracking
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/094Char
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0956Air or oxygen enriched air
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0969Carbon dioxide

Definitions

  • This invention relates to the mining industry which deals with extracting and processing bitumen from various sources, and by way of example such extracting and processing is herein focused with the recovery of oil from oil sands, which is also known as “tar sands,” whose bitumen contains sand, clay and moisture, and is mined in open-pit practice.
  • bitumen to wash out the bitumen as a first step and is followed by a second step to heat the water into steam to about 900° F. and compress the raw bitumen to some 1,500 PSI to upgrade the oil in the bitumen by subtracting carbon to result in a lighter hydrocarbon liquid.
  • the main object of the present invention is to produce valuable, desulfurized light liquids directly from open-pit mining of crushed run-of-mine bitumen.
  • Another object of this invention is to do away with the use of water in the processing of the oil sands which contain the bitumen.
  • Another object of the present invention is to provide a superior technology and apparatus that will lower the processing cost of oil sand bitumen.
  • Yet another object of the instant invention is to eliminate the use of tailings ponds which contain clay and sand particles that take several years to settle, and when they do settle, produce bodies of water containing toxic chemicals such as naphthenic acid and polycyclic hydrocarbons.
  • Another object of the present invention is to reduce the energy consumption in the processing of bitumen from the oil sands.
  • Still another object of the instant invention is to produce a clean, hydrogen rich synthetic gas as a by-product that can be converted to a clean transport fuel such as gasoline, or dimethyl ether which can replace dirty diesel to fuel the large trucks that transport the oil sands from where it is mined to the processing complexes.
  • a clean transport fuel such as gasoline, or dimethyl ether
  • Another object of the present invention is to provide an environmentally closed method and equipment to carry the method.
  • Another object of the instant invention is to provide a continuous method and equipment to carry the method.
  • FIG. 1 is a general layout of the present invention.
  • FIG. 2 illustrates a pyrolyzing reactor in perspective which can efficiently process the bitumen from open-pit mining.
  • FIG. 3 is a partial, longitudinal section of the pyrolyzing reactor, including a cross-section view taken at A-A of FIG. 3 .
  • FIG. 4 illustrates the end view of a battery of pyrolyzing reactors to satisfy large production needs.
  • FIG. 1 wherein the following numerals represent the main components: 10 marks the pyrolyzer; 11 marks the char gasifier; 12 marks the char quencher; 13 , the hot gas cleanup; 14 , the separator of the syngas from the light liquids; 15 , the combined cycle electric power generation; 16 , the alternating reducing reactors comprising a portion of the fertilizer plant; 17 , the fertilizer (oxamide) reactor; 18 , the dual beds of activated carbon for mercury removal; and 19 is the equipment to feed the raw materials to be processed in pyrolyzer 10 .
  • 10 the pyrolyzer
  • 11 the char gasifier
  • 12 the char quencher
  • 13 the hot gas cleanup
  • 14 the separator of the syngas from the light liquids
  • 15 the combined cycle electric power generation
  • 16 the alternating reducing reactors comprising a portion of the fertilizer plant
  • 17 the fertilizer (oxamide) reactor
  • 18 the dual beds of activated carbon for mercury removal
  • 19 is the equipment to
  • Pyrolyzer 10 is made up of charger 20 , pyrolyzing chamber 21 , radiant zone 22 , downcomer 23 , and flow control valve 24 , from which bifurcated pipe 25 forms a delivery pipe assembly, with pipe 26 connecting downcomer 23 thence to char gasifier 11 by way of control valve 28 , and pipe 27 connecting downcomer 23 to char quencher 12 by way of control valve 29 .
  • Gasifier 11 comprises vessel 30 , which is equipped with injection points at different levels for a gas containing oxygen, such as air, to react with hot char to produce a fuel gas; gasifier 11 possesses at its bottom discharge cooler 31 , with exit port 32 . Below cooler 31 , lockhopper 33 is provided, which is controlled by upper valve 34 and by lower valve 35 . At about mid-point of gasifier 11 , a special manifold marked by numeral 36 serves for the injection of flue gases containing CO 2 for reducing the CO 2 into 2CO.
  • Quencher 12 comprises vessel 37 , which is equipped with multi-level manifolds, like manifold 38 , that gradually cool the char below ignition point prior to being periodically discharged to the atmosphere by means of valve 39 .
  • the equipment to feed the mined raw materials is marked by numeral 19 , and comprises skip 40 , which elevates the raw bitumen that contains sand, clay and moisture from ground to conveyor 42 and skip 41 , which elevates the char (fuel) from ground to conveyor 43 , which in turn conveyor 42 discharges to feeder 44 and conveyor 43 discharges to feeder 45 .
  • Gas cleanup 13 is made up of three vessels, marked by numerals 46 , 47 , and 48 .
  • Vessel 46 cracks and simultaneously desulfurizes the volatile matter from pyrolyzer 10 ;
  • vessel 47 cleans the fuel gas made up of nitrogen (N 2 ) and carbon monoxide (CO) gas from gasifier 11 ;
  • vessel 48 serves to regenerate the sorbent and produce elemental sulfur directly. All three vessels are equipped with feeders denoted by numeral 49 .
  • Vessel 48 interconnects with vessels 46 and 47 via the inverted Y-pipe that is marked by numeral 50 , which is equipped with diversion valves 51 .
  • Gas cleanup 13 is equipped with pneumatic transporters 52 to convey the spent sorbent from vessels 46 and 47 to regenerator 48 .
  • Cyanogen make-up equipment 16 comprises reactor 53 “A” and reactor 53 “B” with gas temperature moderator denoted by numeral 54 being upstream of “A” and “B,” and chiller-liquefier which is denoted by numeral 55 being downstream.
  • a separator marked by numeral 56 is provided to segregate the liquefied cyanogen from the unreacted gases which are directed (not shown) to pyrolyzer 10 .
  • oxamide maker 17 Downstream of separator 56 , oxamide maker 17 is located. It consists of reactor 57 , settling tank 58 , filter press 59 , drier 60 , and stacker 61 .
  • Pump 62 is provided to separator 56 to pump the liquefied cyanogen to evaporator 63 , and pump 64 serves to circulate the liquid catalyst to the top of reactor 57 ; a heater denoted by numeral 65 serves to adjust the temperature of the liquid catalyst.
  • the mercury removal system marked by numeral 18 which consists of activated carbon beds, comprises beds “a” and “b,” with the practice being when bed “a” is in absorption of mercury, bed “b” is in regeneration mode, and when bed “b” is in absorption, while bed “a” is in regeneration mode.
  • the electric power generation system in this invention is preferably fueled with a clean, lean gas (fuel gas) fed from cleanup vessel 47 and comprises gas turbine numeral 66 , heat recovery steam generator 67 , and steam turbine 68 , forming a combined cycle configuration which is a most efficient way of generating power.
  • a clean, lean gas fuel gas
  • the electric power generation system in this invention is preferably fueled with a clean, lean gas (fuel gas) fed from cleanup vessel 47 and comprises gas turbine numeral 66 , heat recovery steam generator 67 , and steam turbine 68 , forming a combined cycle configuration which is a most efficient way of generating power.
  • FIG. 2 illustrates in perspective the pyrolyzer denoted by numeral 10 and is made up of feeders 44 and 45 , charger 20 , pyrolyzation chamber denoted by numeral 21 , radiant zone 22 , and control valve 24 .
  • the oil sands and the char are fed by way of pipes 81 and 85 , respectively, using a “Y” piping configuration.
  • the exit port for the H 2 rich volatile matter is marked by numeral 86 .
  • lance 71 in addition to its capability to inject oxygen through its tip denoted by numeral 82 , is equipped with injection nozzles on its side denoted by numeral 83 .
  • Lance 71 like mandrel 70 and ram 69 , is adapted to advance and retract independently, and because of the high temperature surrounding lance 71 , it is cooled preferably with water circulating through it in a closed loop.
  • bitumen is heated peripherally by means of injection nozzles disposed through shell 77 and refractory 75 , one of which being marked by numeral 80 , with such nozzles being supplied with a gas containing oxygen furnished by manifold 79 , thus providing direct, pressurized, bi-directional, efficient heating that increases the release of the volatile matter from the bitumen to such an extent that virtually all the oils in the bitumen are recovered in vapor form while its tar is carbonized, producing carbonized sand and clay.
  • numeral 21 is the pyrolyzing chamber
  • numeral 20 is the charger
  • numeral 81 is the feed hopper
  • numeral 69 is the ram
  • numeral 70 is the mandrel
  • numeral 71 is the injection lance
  • numeral 82 is the nozzle at the tip of lance 71
  • numeral 83 is one of the several nozzles disposed at the side of lance 71
  • numeral 72 is the char fuel
  • numeral 73 is the charged bitumen containing sand, clay and water
  • numeral 75 is the refractory/insulation which is configured as a monolithic structure that is reinforced with metallic needles such as stainless steel needles, marked by numeral 84 (shown in SECTION A-A), somewhat similar to imbedding steel wire in reinforced concrete; this
  • oxygen is introduced through shell 77 by means of injectors, one such injector being marked by numeral 80 supplied by manifold 79 .
  • injectors one such injector being marked by numeral 80 supplied by manifold 79 .
  • the combustion effected by injectors, such as injector 80 consumes the ring of char, instead of combusting the bitumen.
  • numeral 74 represents the manifold for distributing hot heating gas into a plurality of small-diameter flues installed in refractory/insulation 75 , one such flue being marked by numeral 76 carrying hot gases that heat refractory 75 , which in turn heats indirectly the bitumen marked my numeral 78 shown in Section A-A.
  • the bitumen has been completely devolatilized, yielding a residual consisting of a char made up of carbonized sand and clay devoid of any oil.
  • FIG. 4 it illustrates a group of pyrolyzers configured in battery form to provide a modular structure in order to enable it to efficiently scale-up productive capacity by replication.
  • the syngas and vaporized light liquids are desulfurized and upgraded in a first hot gas cleanup, while a part of the hot char is gasified with air into a fuel gas and oil-free, tar-free tailings containing clean sand and clean clay; the other part of the char is used as fuel for heating the pyrolyzer.
  • the fuel gas from the gasifier is passed through a second hot gas cleanup, producing a clean, desulfurized lean gas which is ideal to generate clean, efficient electric power with the emitted CO 2 from power generation collected and converted to slow-release fertilizer that can be mixed with top soil, which had been removed prior to mining the bitumen, to form a rich top soil.
  • the oil-free, tar-free tailings consisting of clean sand and clean clay, are used in the reclamation of the open-pit mine and topped with the rich soil to enhance and accelerate plant growth to create forest land.

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Abstract

This invention relates to open-pit mining wherein crushed bitumen is fed into an enclosed pyrolyzer and heated under pressure in a reduced atmosphere where the cracking of asphalt results in a tar-free bitumen in the form of volatile matter containing a hydrogen rich, non-condensable syngas with vaporized light liquids and incandescent char. The syngas and vaporized light liquids are desulfurized and upgraded in a first hot gas cleanup, while part of the hot char is gasified with air into a fuel gas and into oil-free, tar-free, dry, solid tailings; the other part used as fuel for heating the pyrolyzer. The fuel gas passes through a second hot gas cleanup, producing clean, desulfurized lean gas ideal to generate clean, efficient electric power. Emitted CO2 is collected and converted to slow-release fertilizer. The tailings (clean sand and clay) reclaim the mine, while fertilizer enriched soil, topping the tailings, accelerates forest growth.

Description

    INTRODUCTION
  • This invention relates to the mining industry which deals with extracting and processing bitumen from various sources, and by way of example such extracting and processing is herein focused with the recovery of oil from oil sands, which is also known as “tar sands,” whose bitumen contains sand, clay and moisture, and is mined in open-pit practice.
  • BACKGROUND
  • In open-pit mining, large, hydraulic/electric shovels do the digging and the loading of trucks that deliver the mined oil sands to processing complexes. These complexes use very large quantities of water to wash the sand from the bitumen. After the separation of the sand from the bitumen, the water is too dirty to discharge into a body of water, such as a river, from where the water was derived. Current practice is to store such dirty/oily water in ponds, which are called tailings ponds, that can be as big as the mines themselves, creating a major negative environmental problem. Further, the processing complexes utilize large quantities of natural gas to heat the water to about 170° F. to wash out the bitumen as a first step and is followed by a second step to heat the water into steam to about 900° F. and compress the raw bitumen to some 1,500 PSI to upgrade the oil in the bitumen by subtracting carbon to result in a lighter hydrocarbon liquid.
  • OBJECTIVE
  • The main object of the present invention is to produce valuable, desulfurized light liquids directly from open-pit mining of crushed run-of-mine bitumen.
  • Another object of this invention is to do away with the use of water in the processing of the oil sands which contain the bitumen.
  • Therefore another object of the present invention is to provide a superior technology and apparatus that will lower the processing cost of oil sand bitumen.
  • Yet another object of the instant invention is to eliminate the use of tailings ponds which contain clay and sand particles that take several years to settle, and when they do settle, produce bodies of water containing toxic chemicals such as naphthenic acid and polycyclic hydrocarbons.
  • Further another object of the present invention is to reduce the energy consumption in the processing of bitumen from the oil sands.
  • Still another object of the instant invention is to produce a clean, hydrogen rich synthetic gas as a by-product that can be converted to a clean transport fuel such as gasoline, or dimethyl ether which can replace dirty diesel to fuel the large trucks that transport the oil sands from where it is mined to the processing complexes.
  • Further still another object of the present invention is to provide an environmentally closed method and equipment to carry the method.
  • Further yet another object of the instant invention is to provide a continuous method and equipment to carry the method.
  • It is therefore another object of the present invention to co-produce electric power as a by-product that is useful in the recovery and processing of the bitumen.
  • It is yet another object of the instant invention to co-produce a fertilizer as a by-product which is useful in the acceleration of mined land reclamation.
  • It is still another object of the present invention to co-produce a fuel in the form of a char from the mined bitumen which is utilized as the energy source in the pyrolysis step which de-asphalts the bitumen.
  • Other objects of this invention will appear from the following detailed description and appended claims. Reference is made to the accompanying drawings forming a part of this specification wherein like reference characters designate corresponding parts in the various figures.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a general layout of the present invention.
  • FIG. 2 illustrates a pyrolyzing reactor in perspective which can efficiently process the bitumen from open-pit mining.
  • FIG. 3 is a partial, longitudinal section of the pyrolyzing reactor, including a cross-section view taken at A-A of FIG. 3.
  • FIG. 4 illustrates the end view of a battery of pyrolyzing reactors to satisfy large production needs.
  • DETAILED DESCRIPTION OF THE DRAWINGS
  • Reference is made to FIG. 1 wherein the following numerals represent the main components: 10 marks the pyrolyzer; 11 marks the char gasifier; 12 marks the char quencher; 13, the hot gas cleanup; 14, the separator of the syngas from the light liquids; 15, the combined cycle electric power generation; 16, the alternating reducing reactors comprising a portion of the fertilizer plant; 17, the fertilizer (oxamide) reactor; 18, the dual beds of activated carbon for mercury removal; and 19 is the equipment to feed the raw materials to be processed in pyrolyzer 10.
  • Pyrolyzer 10 is made up of charger 20, pyrolyzing chamber 21, radiant zone 22, downcomer 23, and flow control valve 24, from which bifurcated pipe 25 forms a delivery pipe assembly, with pipe 26 connecting downcomer 23 thence to char gasifier 11 by way of control valve 28, and pipe 27 connecting downcomer 23 to char quencher 12 by way of control valve 29.
  • Gasifier 11 comprises vessel 30, which is equipped with injection points at different levels for a gas containing oxygen, such as air, to react with hot char to produce a fuel gas; gasifier 11 possesses at its bottom discharge cooler 31, with exit port 32. Below cooler 31, lockhopper 33 is provided, which is controlled by upper valve 34 and by lower valve 35. At about mid-point of gasifier 11, a special manifold marked by numeral 36 serves for the injection of flue gases containing CO2 for reducing the CO2 into 2CO. Quencher 12 comprises vessel 37, which is equipped with multi-level manifolds, like manifold 38, that gradually cool the char below ignition point prior to being periodically discharged to the atmosphere by means of valve 39.
  • The equipment to feed the mined raw materials is marked by numeral 19, and comprises skip 40, which elevates the raw bitumen that contains sand, clay and moisture from ground to conveyor 42 and skip 41, which elevates the char (fuel) from ground to conveyor 43, which in turn conveyor 42 discharges to feeder 44 and conveyor 43 discharges to feeder 45.
  • Gas cleanup 13 is made up of three vessels, marked by numerals 46, 47, and 48. Vessel 46 cracks and simultaneously desulfurizes the volatile matter from pyrolyzer 10; vessel 47 cleans the fuel gas made up of nitrogen (N2) and carbon monoxide (CO) gas from gasifier 11; and vessel 48 serves to regenerate the sorbent and produce elemental sulfur directly. All three vessels are equipped with feeders denoted by numeral 49. Vessel 48 interconnects with vessels 46 and 47 via the inverted Y-pipe that is marked by numeral 50, which is equipped with diversion valves 51. Gas cleanup 13 is equipped with pneumatic transporters 52 to convey the spent sorbent from vessels 46 and 47 to regenerator 48.
  • Cyanogen make-up equipment 16 comprises reactor 53 “A” and reactor 53 “B” with gas temperature moderator denoted by numeral 54 being upstream of “A” and “B,” and chiller-liquefier which is denoted by numeral 55 being downstream. A separator marked by numeral 56 is provided to segregate the liquefied cyanogen from the unreacted gases which are directed (not shown) to pyrolyzer 10.
  • Downstream of separator 56, oxamide maker 17 is located. It consists of reactor 57, settling tank 58, filter press 59, drier 60, and stacker 61. Pump 62 is provided to separator 56 to pump the liquefied cyanogen to evaporator 63, and pump 64 serves to circulate the liquid catalyst to the top of reactor 57; a heater denoted by numeral 65 serves to adjust the temperature of the liquid catalyst.
  • The mercury removal system marked by numeral 18, which consists of activated carbon beds, comprises beds “a” and “b,” with the practice being when bed “a” is in absorption of mercury, bed “b” is in regeneration mode, and when bed “b” is in absorption, while bed “a” is in regeneration mode.
  • The electric power generation system in this invention, marked by numeral 15, is preferably fueled with a clean, lean gas (fuel gas) fed from cleanup vessel 47 and comprises gas turbine numeral 66, heat recovery steam generator 67, and steam turbine 68, forming a combined cycle configuration which is a most efficient way of generating power.
  • FIG. 2 illustrates in perspective the pyrolyzer denoted by numeral 10 and is made up of feeders 44 and 45, charger 20, pyrolyzation chamber denoted by numeral 21, radiant zone 22, and control valve 24. The oil sands and the char are fed by way of pipes 81 and 85, respectively, using a “Y” piping configuration. The exit port for the H2 rich volatile matter is marked by numeral 86.
  • Referring now to FIG. 3, lance 71, in addition to its capability to inject oxygen through its tip denoted by numeral 82, is equipped with injection nozzles on its side denoted by numeral 83. Lance 71, like mandrel 70 and ram 69, is adapted to advance and retract independently, and because of the high temperature surrounding lance 71, it is cooled preferably with water circulating through it in a closed loop.
  • It is to be noted that in providing lance 71 wherein the char charged is combusted under suppressed conditions (in a pressurized, controlled reducing atmosphere), heat transfer within chamber 21 is markedly improved, thus enhancing the rate at which the bitumen, containing sand, clay and water, devolatilizes into volatile matter, while vigorously cracking tars to such an extent that carbon is deposited on the sand and clay while the water turns into water-gas (H2+CO) within chamber 21. Further, the bitumen is heated peripherally by means of injection nozzles disposed through shell 77 and refractory 75, one of which being marked by numeral 80, with such nozzles being supplied with a gas containing oxygen furnished by manifold 79, thus providing direct, pressurized, bi-directional, efficient heating that increases the release of the volatile matter from the bitumen to such an extent that virtually all the oils in the bitumen are recovered in vapor form while its tar is carbonized, producing carbonized sand and clay.
  • In the instant application, wherein carbon in the char (as a core within chamber 21) is combusted in a pressurized reducing atmosphere, the combustion of bitumen which surrounds the core is virtually prevented. To achieve this objective, numeral 21 is the pyrolyzing chamber, numeral 20 is the charger, numeral 81 is the feed hopper, numeral 69 is the ram, numeral 70 is the mandrel, numeral 71 is the injection lance, numeral 82 is the nozzle at the tip of lance 71, and numeral 83 is one of the several nozzles disposed at the side of lance 71, numeral 72 is the char fuel, numeral 73 is the charged bitumen containing sand, clay and water, and numeral 75 is the refractory/insulation which is configured as a monolithic structure that is reinforced with metallic needles such as stainless steel needles, marked by numeral 84 (shown in SECTION A-A), somewhat similar to imbedding steel wire in reinforced concrete; this structure is cast in place against shell 77.
  • In the case of heating the material peripherally directly by combusting char (not shown), oxygen is introduced through shell 77 by means of injectors, one such injector being marked by numeral 80 supplied by manifold 79. When combustion takes place peripherally and the material is bitumen, it is possible to also charge char around the perimeter of the bitumen annulus by providing an additional mandrel that circumscribes ram 69 to form a ring of char around the periphery of the bitumen. In so doing, the combustion effected by injectors, such as injector 80, consumes the ring of char, instead of combusting the bitumen.
  • In the case of heating the material peripherally indirectly, numeral 74 represents the manifold for distributing hot heating gas into a plurality of small-diameter flues installed in refractory/insulation 75, one such flue being marked by numeral 76 carrying hot gases that heat refractory 75, which in turn heats indirectly the bitumen marked my numeral 78 shown in Section A-A. It is to be noted that towards the exit end of pyrolyzing chamber 21, the bitumen has been completely devolatilized, yielding a residual consisting of a char made up of carbonized sand and clay devoid of any oil. Referring to FIG. 4, it illustrates a group of pyrolyzers configured in battery form to provide a modular structure in order to enable it to efficiently scale-up productive capacity by replication.
  • OPERATION
  • To describe the operation of this invention based on extensive test work that had taken place and referenced hereinafter begins with using unprepared, crushed run-of-mine bitumen preferably of three inches and under that is directly fed into a battery of pyrolyzers where the cracking of asphalt results in a tar-free bitumen in the form of volatile matter containing a hydrogen rich, non-condensable raw syngas together with vaporized light liquids and incandescent char. The syngas and vaporized light liquids are desulfurized and upgraded in a first hot gas cleanup, while a part of the hot char is gasified with air into a fuel gas and oil-free, tar-free tailings containing clean sand and clean clay; the other part of the char is used as fuel for heating the pyrolyzer. The fuel gas from the gasifier is passed through a second hot gas cleanup, producing a clean, desulfurized lean gas which is ideal to generate clean, efficient electric power with the emitted CO2 from power generation collected and converted to slow-release fertilizer that can be mixed with top soil, which had been removed prior to mining the bitumen, to form a rich top soil. The oil-free, tar-free tailings, consisting of clean sand and clean clay, are used in the reclamation of the open-pit mine and topped with the rich soil to enhance and accelerate plant growth to create forest land.
  • The test work performed in the Applicant's pilot in cooperation with Sun refining proved that the method described herein, which uses CaO as sorbent, produced light liquids from cracking residuum (heavy bitumen) from its Philadelphia Refinery against CaO as sorbent. Such light liquids were referred to by Sun as “excellent feedstocks and can be separated by a simple distillation process into valuable intermediates”; see Exhibit 1, page 1 of 2.
  • Data that was produced by way of the tests (see Exhibit 1, page 2 of 2) showed that the Ramsbottom Carbon (by weight percentage) of the residuum was converted from 18.2% to 1.24% in test Run #3, to 0.59% in test Run #4, and to 0.31% in test Run #5. Further, for the Pour Point temperature in ° F., the residuum was 145° F., and in tests #3, #4, and #5, the temperature was reduced to −20° F. Also, the INITIAL BOILING POINT of the residuum dropped from 802° F.: in test #3 to 108° F., in test #4 to 154° F., and in test #5 to 135° F. This data show that the method herein described—which is based on the replication of the test work performed, except at commercial scale—should produce outstanding results in producing light liquids from bitumen. It is also important to disclose herein that the syngas (Rich Gas Sample—Test Run #3) produced in Mole % as follows: H2—57.3%; CH4—36.6%; N2—3%; C2H4—1.8%; CO—1.6%; and CO2—only 0.7%.
  • With respect to residual bitumen after pyrolysis, tests were conducted in 1997 at Applicant's Process Development Unit (Exhibit 2) making metallurgical coke from coal; the coke produced was tested for various properties including residual volatile matter after pyrolysis. In testing the coke made from Bethlehem Steel's coal, the residual volatile matter was 0.58%, and with coke made from U.S. Steel's three coals, the residual volatile matter was 0.55% from Blue Tag Coal, 0.48% from Low-Vol coal, and 0.70% from White Tag coal; see Exhibit 3. In the tests conducted, whether the feedstock was heavy oil (bitumen) or coal, these feedstocks were pyrolyzed in sealed tubes in which cracking of tars took place as proposed herein; in the case of sulfur removal, the gas produced had no H2S, as reported in Exhibit 1, page 1 of 2. Production of elemental sulfur during regeneration was reported by Sun; see Exhibit 4, and the chemistry for such results are published in The Making, Shaping and Treating of Steel, 11th edition; see Exhibit 5.
  • In conclusion, based on the test work done and the herein description, the objectives listed towards the beginning of this disclosure are achievable. It is submitted herein that the instant method and apparatus provide major improvements over the conventional practice of processing open-pit mining of bitumen including oil sands. The details of construction mentioned above are for the purpose of description and not limitation, since other configurations are possible without departing from the spirit of the invention. Further, other materials besides bitumen from oil sands can be processed in the apparatus herein described.

Claims (45)

1. A method for processing a bitumen containing any one and possibly all of the following impurities, such as tars, oily sand, oily clay, oily water, and any other unspecified impurity, into a clean, desulfurized synthetic gas and clean, desulfurized light liquids comprising the following step:
force-feeding the bitumen into an enclosed pyrolyzing reactor having a charging end and a discharging end, with the discharging end integrated to a char gasifier;
heating said bitumen within said pyrolyzing reactor under pressure in a reducing atmosphere in such a way as to have the charging end at low temperature and the discharging end at high temperature to cause the release of a volatile matter from said bitumen which is made up of a raw, non-condensable H2 rich synthetic gas (syngas) together with vaporized, condensable liquids, and the production of a hot, incandescent, residual char that converts steam from any water originating from said bitumen, present within said pyrolyzing reactor to water gas (H2+CO), while preventing the emission of noxious gases into the environment surrounding said pyrolyzing reactor;
advancing said bitumen within said pyrolyzing reactor from said charging end to said discharging end while cracking tars and heavy oils prior to said char being discharged into said char gasifier;
passing said raw, non-condensable syngas and vaporized liquids through a first hot gas cleanup to react with a hot sorbent to desulfurize both the syngas and the vaporized liquids and ensure the cracking of residual tar or heavy hydrocarbons in the syngas and/or in the vaporized liquids to convert them to a substantially clean, desulfurized syngas and substantially clean, desulfurized light liquids;
gasifying said hot char into a fuel gas while producing an inert ash made up of a combination of dry sand and dry clay with both being substantially devoid of oil;
passing said fuel gas through a second hot gas cleanup to produce a desulfurized fuel gas; and
separating said substantially clean, desulfurized syngas from said substantially clean, desulfurized, vaporized light liquids by way of condensation of said vaporized light liquids, resulting in a clean, desulfurized syngas per se and a clean, desulfurized condensate made up of light liquids.
2. The method as set forth in claim 1 wherein said bitumen is recovered from an open-pit mine and delivered to a processing plant.
3. The method as set forth in claim 2 wherein said bitumen is recovered from an open-pit mine whose resource is oil sands, which are also known as tar sands.
4. The method as set forth in claim 3 wherein said oil sands are processed as crushed run-of-mine bitumen without further preparation.
5. The method as set forth in claim 1 wherein the step of force-feeding the bitumen into an enclosed pyrolyzing reactor is further characterized by the step of employing a charger which continually compresses the bitumen charged into said pyrolyzing reactor to increase the bulk density of said bitumen within said pyrolyzing reactor while causing the advancement of the compressed bitumen towards the discharging end of said pyrolyzing reactor to result in discharging hot char from the discharge end of said pyrolyzing reactor into said gasifier.
6. The method as set forth in claim 1 comprising the step of heating said bitumen within said pyrolyzing reactor wherein the production of a hot, incandescent char occurs and is further characterized by the step of dividing the stream of said char into two parts, the first part of said char being directed to a gasifier and the second part of said char being directed to a quencher where the char is cooled below its ignition point, producing a cold char prior to being discharged into the atmosphere.
7. The method as set forth in claim 6 wherein said second part of said char being directed to a quencher, serves after being cooled, as a carbon fuel in said pyrolyzing reactor to devolatilize bitumen when this carbon fuel is combusted.
8. The method as set forth in claim 7 wherein said carbon fuel is co-fed with bitumen into said pyrolyzing reactor.
9. The method as set forth in claim 8 wherein said carbon fuel co-fed with said bitumen into said pyrolyzing reactor, are charged into said pyrolyzing reactor in such a way as to have the carbon fuel forming a core surrounded by an annulus of said bitumen.
10. The method as set forth in claim 9 wherein said core is configured with a bore through its center and extending along the longitudinal axis of said core.
11. The method as set forth in claim 10 wherein said bore accommodates a cooled lance to inject a gas containing oxygen in order to combust said core within said pyrolyzing reactor under reducing conditions to cause an internal release of thermal energy that heats said bitumen annulus.
12. The method as set forth in claim 11 wherein said bore accommodates a cooled lance to inject a gas containing oxygen is further characterized by said lance having an injection port at its tip and additional injection ports dispersed along its length in order to increase heating area of the bitumen contained within said pyrolyzing reactor.
13. The method as set forth in claim 11 wherein said internal release of the thermal energy that heats said bitumen annulus is complemented by heating said bitumen annulus peripherally in order to provide thermal energy bi-directionally to efficiently cause the release of volatile matter from said bitumen.
14. The method as set forth in claim 13 wherein the step to provide thermal energy bi-directionally to efficiently cause the release of volatile matter from said bitumen is further characterized by maintaining a positive pressure within said pyrolyzing reactor to further accelerate the release of volatile matter from the bitumen.
15. The method as set forth in claim 1 wherein the step of passing said raw, non-condensable syngas and vaporized liquids through a first hot gas cleanup to react with said hot sorbent is further characterized by said sorbent being a CaO which absorbs sulfur and cracks hydrocarbons, becoming a CaS carbon impregnated.
16. The method as set forth in claim 15 wherein CaS carbon impregnated is regenerated back to CaO while heated to elevated temperature by virtue of the carbon burning during regeneration yielding also a lean fuel gas with entrained vaporized elemental sulfur.
17. The method as set forth in claim 16 wherein said lean fuel gas with entrained vaporized elemental sulfur is separated from said vaporized elemental sulfur by means of condensation of the elemental sulfur, resulting in a useful, clean, lean fuel gas.
18. The method as set forth in claim 1 wherein the step of gasifying said hot char into a fuel gas and passing it through a second hot gas cleanup to produce a desulfurized fuel gas is further characterized by combining this fuel gas with the lean fuel gas generated according to claim 17, results in producing a clean and adequate gaseous fuel resource destined to: (i) generate electric power and (ii) serve as a feedstock to produce fertilizer.
19. The method as set forth in claim 18 wherein said clean gaseous fuel resource destined to generate electric power preferably is used in the generation of power via the combined cycle mode, and said clean gaseous fuel resource destined to serve as a feedstock to produce fertilizer, preferably is used in the production of oxamide which is a slow-release fertilizer.
20. The method as set forth in claim 18 wherein said gaseous resource destined to generate electric power is further characterized by the production of CO2 when combusted to generate power includes the collecting of the CO2 and injecting it into hot, incandescent char contained in the gasifier referenced in claim 1, in order to convert the CO2 to 2CO which is a useful chemical or fuel.
21. The method as set forth in claim 1 wherein the desulfurized syngas and the desulfurized light liquids are converted to useful by-products such as with the syngas converted to transport fuels like methanol/gasoline, dimethyl ether or chemicals, and with the desulfurized light liquids converted to downstream products such as gasoline, jet fuel, fuel oil, etc.
22. The method as set forth in claim 1 wherein the step of gasifying said hot char into a fuel gas while producing an inert ash made up of a combination of dry sand and dry clay with both being substantially devoid of oil is further characterized by eliminating oily, dirty tailings, making it possible to reclaim mined property soon after the extraction of the bitumen from the mine, while fertilizer-enriched soil topping the dry sand and dry clay accelerates forest growth.
23. The method as set forth in claim 1 wherein no water is used to process the extracted bitumen from open-pit mining.
24. The method as set forth in claim 1 wherein the source of fuel for the processing of bitumen extracted from open-pit mining originates from the bitumen itself.
25. Apparatus to process a bitumen containing impurities that produces from said bitumen a volatile matter which after cleanup yields a clean desulfurized synthetic gas and clean desulfurized light liquids comprising the following:
a pyrolyzing reactor within which the bitumen is pyrolyzed to release volatile matter, having: (i) a charging end equipped with a charging mechanism adapted to force-feed and compress said bitumen within said pyrolyzing reactor, causing the advancement of said bitumen along the length of said pyrolyzing reactor, and (ii) a discharging end integrally connected to a gasifier which is adapted to receive residual char produced in said pyrolyzing reactor, and to gasify said char while producing from it a fuel gas together with an inert ash;
means adapted to heat said bitumen within said pyrolyzing reactor;
a first hot gas cleanup adapted to desulfurize and crack residual heavy hydrocarbons producing a clean synthesis gas and clean light liquids from said volatile matter;
a second hot gas cleanup adapted to desulfurize fuel gas produced in said gasifier; and
a sorbent regeneration means adapted to regenerate a carbon-impregnated sulfidated sorbent in the form of C+CaS by combusting said carbon to result in heating the regenerated sorbent (CaO) while producing a fuel gas containing elemental sulfur which is separated from the fuel gas in a condenser.
26. The apparatus as set forth in claim 25 wherein said charging mechanism comprises a pushing ram that cycles between advances and retractions to effect the force-feed action to introduce and compress the bitumen into said pyrolyzing reactor.
27. The apparatus as set forth in claim 26 wherein said ram is constructed as a cylinder with a bore along its longitudinal axis to accommodate a mandrel that is circumscribed by said ram that is adapted to advance and retract independently from the advancement and retraction of said ram.
28. The apparatus as set forth in claim 27 wherein said mandrel is constructed as a cylinder with a bore along its longitudinal axis to accommodate a lance which is adapted to advance and retract independently from the advancement and retraction of said mandrel.
29. The apparatus as set forth in claim 28 wherein said lance possesses the capability to inject a gas containing oxygen in order to combust a fuel to heat said bitumen.
30. The apparatus as set forth in claim 29 wherein said fuel is char.
31. The apparatus as set forth in claim 30 wherein said char is a product derived from the bitumen.
32. The apparatus as set forth in claim 28 wherein said lance is adapted to inject a gas containing oxygen from its tip.
33. The apparatus as set forth in claim 32 wherein said lance is adapted to inject a gas containing oxygen from nozzle means provided in the sides of said lance.
34. The apparatus as set forth in claim 27 wherein said mandrel together with said ram are adapted to form a core of fuel surrounded by an annulus of bitumen.
35. The apparatus as set forth in claim 25 wherein said pyrolyzing reactor is adapted to be co-fed with both fuel and bitumen.
36. The apparatus as set forth in claim 25 wherein the discharging end of said pyrolyzing reactor is adapted to discharge hot incandescent char to said gasifier and also to a cooling quencher to produce a cool char prior to exposing such char to the atmosphere.
37. The apparatus as set forth in claim 36 wherein a conveying system is included to deliver the cool char to said charging mechanism referenced in claim 25.
38. The apparatus as set forth in claim 25 wherein means are included to utilize said fuel gas produced to generate electric power.
39. The apparatus as set forth in claim 25 wherein means are provided to air blow said gasifier to produce a lean gas containing nitrogen (N2) and ash devoid of oil, with the N2 constituting a portion of a feedstock gas to make fertilizer.
40. The apparatus as set forth in claim 25 wherein injection means are provided to inject the produced CO2 into said gasifier to react with hot incandescent char to reduce the CO2 to 2CO within said gasifier, with such 2CO becoming part of the feedstock to make fertilizer.
41. The apparatus as set forth in claims 39 and 40 wherein facilities are provided to utilize said feedstock to produce fertilizer.
42. The apparatus as set forth in claim 25 wherein equipment adapted to remove mercury from gas is included.
43. The apparatus as set forth in claim 25 wherein means are included to operate the equipment under pressure.
44. The apparatus as set forth in claim 25 wherein said pyrolyzing reactor is configured with a taper extending from its charging end to its discharging end to provide an ever-increasing dimension towards the discharging end to facilitate the movement of the bitumen towards the discharging end of said pyrolyzing reactor.
45. The apparatus as set forth in claim 25 wherein said pyrolyzing reactor is replicated to form an assembly of reactors in battery form to meet a specific production capacity.
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