CA2757824A1 - A hot solids process having an output suitable for the input to a petrochemical process - Google Patents

A hot solids process having an output suitable for the input to a petrochemical process Download PDF

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Publication number
CA2757824A1
CA2757824A1 CA2757824A CA2757824A CA2757824A1 CA 2757824 A1 CA2757824 A1 CA 2757824A1 CA 2757824 A CA2757824 A CA 2757824A CA 2757824 A CA2757824 A CA 2757824A CA 2757824 A1 CA2757824 A1 CA 2757824A1
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Prior art keywords
reactor
input
hot solids
petrochemical
output
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CA2757824A
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French (fr)
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CA2757824C (en
Inventor
John H. Chiu
Herbert E. Andrus, Jr.
Gregory N. Liljedahl
Paul R. Thibeault
Carl R. Bozzuto
Corinne Beal
Michal T. Bialkowski
Andreas Brautsch
Laurent Maghdissian
Michel Vandycke
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General Electric Technology GmbH
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Alstom Technology AG
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    • 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
    • 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/02Non-metals
    • 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
    • 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
    • C10J3/02Fixed-bed gasification of lump fuel
    • C10J3/06Continuous processes
    • C10J3/12Continuous processes using solid heat-carriers
    • 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80Additives
    • C10G2300/805Water
    • C10G2300/807Steam
    • 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
    • C10J2300/0983Additives
    • C10J2300/0993Inert particles, e.g. as heat exchange medium in a fluidized or moving bed, heat carriers, sand
    • 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
    • C10J2300/0983Additives
    • C10J2300/0996Calcium-containing inorganic materials, e.g. lime
    • 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
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water
    • 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
    • C10J3/72Other features
    • C10J3/725Redox processes

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

A hot solids process wherein a predetermined output, which is designed to be suitable for use as an input to a petrochemical process, is capable of being generated through the use of the hot solids process. The mode of operation of such a hot solids process is designed to be such that preferably a portion of the otherwise normally unusable product output, which is produced from a petrochemical process, is designed to be utilized as an input to the hot solids process for purposes of generating from the hot solids process the predetermined output that is suitable for use as an input to a petrochemical process.

Description

A HOT SOLIDS PROCESS HAVING AN OUTPUT SUITABLE FOR THE INPUT
TO A PETROCHEMICAL PROCESS
CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present invention claims the benefit of co-pending U.S. Provisional Patent Application Serial No. 61/165,042, entitled "HOT SOLIDS PROCESS
SELECTIVELY OPERABLE FOR COMBUSTION PURPOSES AND GASIFICATION
PURPOSES", and co-pending U.S. Provisional Patent Application 61/165,069, entitled "HOT SOLIDS PROCESS SELECTIVELY OPERABLE BASED ON THE TYPE OF
APPLICATION THAT IS INVOLVED", and co-pending U.S. Provisional Patent Application 61/165,094, entitled "HOT SOLIDS PROCESS SELECTIVELY
OPERABLE BASED ON WHAT THE SPECIFIC NATURE OF THE HOT SOLIDS
PROCESS' PRIMARY PURPOSE IS" all of which are incorporated herein by reference in their entirety.

TECHNICAL FIELD

[0002] This invention relates generally to a hot solids process that is capable of generating a predetermined output that is designed to be suitable for use as an input to a petrochemical process. Moreover, the present invention relates to such a hot solids process that is designed to employ a portion of the otherwise normally unusable product output, which is produced from such a petrochemical process, for purposes of generating, in accordance with the present invention, the output from the hot solids process that is designed to be suitable for use as an input to said petrochemical process.

BACKGROUND
[0003] The World today faces a critical challenge as all nations strive to satisfy basic human requirements - - food, shelter, clothing and work - - that are so dependent on adequate supplies of energy. The great increase in the use of energy has been met mostly by fossil fuels - - primarily, coal, oil and gas. The belief is that environmental concerns, security of supply, and economic impacts must all be balanced as the demand for energy continues to increase. Real economic growth and energy use nevertheless still remain inextricably linked.
[0004] While the quest for ultimate solutions to provide adequate energy supplies continues, near term, interim solutions must be considered for meeting the immediate growth in demand for energy. Technological improvements in the mining, drilling, moving, processing, and using of fossil fuels can, of course, stretch energy resource reserves, as can a determined effort at conservation of energy. Similarly, the utilization of advanced clean fossil fuel technologies involving the employment of various forms of hot solids processes such as, by way of exemplification and not limitation, fossil fuel gasification, fluidized-bed combustion, or hybrid combustion-gasification fossil fuel technologies, are capable of having the effect of that of widening the use of the World's vast fossil fuel resources.
[0005] In accordance with the mode of operation of electrical power generation systems, as is well known to most, the steam that is produced by steam generators, which are employed in such electrical power generation systems, from the combustion of fossil fuel therein is designed to be employed in steam turbines. Such steam, which commonly is both at a high temperature and at a high pressure, is expanded in the aforementioned steam turbine in order to thereby effect a rotation of the steam turbine. Such rotation of the steam turbine in turn is operative in a known manner to cause a generator that is suitably operatively connected to the steam turbine to rotate as well. Then, when the generator undergoes such rotation, a conductor is made to move through a magnetic field thereby causing an electric current to be generated. The aforedescribed mode of operation is fundamentally the basis upon which electrical power generation systems continue to be predicated even to this day.
[0006] In an effort to realize higher efficiencies for electrical power generation systems, attempts have been known to have been made to increase the temperatures and the pressures at which the steam generators that are employed in such electrical power generation systems are capable of being operated. Such efforts to date have resulted in steam generators being supplied commercially for employment in electrical power generation systems that are capable of being operated at subcritical pressure conditions or that are capable of being operated at supercritical pressure conditions.
Improvements in the strength of the materials from which such steam generators, which are intended for employment in electrical power generation systems, are designed to be constructed have permitted such materials, and thus such steam generators, to be operated both at such higher temperatures and at such higher pressures.
[0007] Discussing further the advanced clean fossil fuel technologies to which reference has been had above previously wherein various forms of hot solids processes are employed, and in particular to that of fossil fuel gasification technologies, attention is first directed in this connection, by way of exemplification and not limitation, to U.S.
Patent No. 2,602,809, which issued on July 8, 1952 to The M. W. Kellogg Company.
The teachings of U.S. Patent No. 2,602,809 are considered to be representative of an exemplification of an early development in the continuing development of fossil fuel gasification technologies of the type wherein hot solids processes are employed. To this end, in accordance with the teachings thereof, the teachings of U.S. Patent No. 2,602,809 are directed to a proves, which is said to be particularly suited for the gasification of low-grade solid carbon-containing materials. More specifically, insofar as the mode of operation of the process to which the teachings of U.S. Patent No. 2,602,809 are directed is concerned, the solid carbon-containing materials are designed to be oxidized in order to convert such solid carbon-containing materials to carbon oxides by virtue of the indirect oxidation thereof with air in such a manner that the nitrogen of the air does not contaminate the product gas. Such gasification of the solid carbon-containing materials is accomplished by virtue of the alternate oxidation and reduction of a fluidized metal oxide.
According to the teachings of U.S. Patent No. 2,602,809, solid fuels are subjected to being converted to gases as a consequence of the contacting by a metal oxide with finely-divided solid carbon-containing materials under conditions such as to cause the metal oxide to be reduced and the carbon of the solid fuel to be oxidized to carbon oxides, with the metal oxide being the principal source of oxygen that is required for the oxidation of the carbon. Then, after the metal oxide has been reduced, the reduced metal oxide is subjected to being re-oxidized whereupon the process cycle is capable of being repeated once again.
[0008] With further regard to the fossil fuel gasification technologies of the advanced clean fossil fuel technologies to which reference has been had above previously wherein various forms of hot solids processes are employed, attention is next directed herein, by way of exemplification and not limitation, to U.S. Patent No.
4,602,573, which issued on July 29, 1986 to Combustion Engineering, Inc. The teachings of U.S.
Patent No. 4,602,573 are considered to be representative of an exemplification of a further development in the continuing evolution of fossil fuel gasification technologies of the type wherein hot solids processes are employed. To this end, in accordance with the teachings thereof, the teachings of U.S. Patent No. 4,602,573 are stated to be directed to a method of gasifying and combusting a carbonaceous fuel and, more particularly to an integrated process wherein a sulfur and nitrogen-bearing carbonaceous fuel is gasified to produce a carbon monoxide-rich low BTU fuel gas that is deigned to be subsequently combusted with additional carbonaceous fuel in a steam generator. More specifically, insofar as the mode of operation of the process to which the teachings of U.
S. Patent No.
4,602,573 are directed is concerned, a first portion of sulfur and nitrogen-bearing carbonaceous fuel is gasified in a gasification reactor in a reducing atmosphere of air to produce a hot, char-containing, carbon monoxide-rich fuel gas having a low BTU
content.
Thereafter, a sulfur capturing material is introduced into the gasification reactor so that the gasifying of the carbonaceous fuel is carried out in the presence of the sulfur capturing material whereby a substantial portion of the sulfur in the carbonaceous fuel being gasified is captured by the sulfur capturing material.
[00091 Attention will next be directed herein further to the advanced clean fossil fuel technologies to which reference has been had above previously wherein various forms of hot solids processes are employed and in particular to that of fluidized-bed combustion technologies. Thus, more specifically, attention is therefore directed in this connection, by way of exemplification and not limitation, to U.S. Patent No.
4,111,158, which issued on September 5, 1978 to Metallgesellschaft Aktiengesellschaft.
The teachings of U.S. Patent No. 4,111,158 are considered to be representative of an exemplification of an early development in the continuing development of the fluidized-bed combustion technologies of the type wherein hot solids processes are employed. To this end, in accordance with the teachings thereof, the teachings of U.S.
Patent No.
4,111,158 are stated to be directed to a method of and an apparatus for carrying out an exothermic process in which a solid feed contains a combustible such as, for example, carbonaceous or sulfurous compounds. Continuing, insofar as the mode of operation of the method of and the apparatus for to which the teachings of U. S. Patent No.
4,111,158 are directed is concerned, the combustible compounds of the solid feed are designed to be burned under approximately stoichiometric conditions in a fluidized bed.
Thereafter, the solids, which are produced as a consequence of such burning of the combustible compounds of the solid feed and which are withdrawn from the fluidized bed are caused to be recycled back to the fluidized bed, while the heat that is produced from such burning of the combustible compounds of the solid feed is available to be recovered.

[0010] Regarding further the fluidized-bed combustion technologies of the advanced clean fossil fuel technologies to which reference has been had above previously wherein various forms of hot solids processes are employed, attention is next directed herein, by way of exemplification and not limitation, to U. S. Patent No.
5,533,471, which issued on July 9, 1996 to A. Ahlstrom Corporation. The teachings of U.S.
Patent No.
5,533,471 are considered to be representative of an exemplification of a further development in the continuing evolution of fluidized-bed combustion technologies of the type wherein hot solids processes are employed. To this end, in accordance with the teachings thereof, the teachings of U.S. Patent No. 5,533,471 are stated to be directed to a system and to a method that allow the temperature of the fluidized bed reactor to be controlled efficiently, allowing adequate heat transfer surface area for cooling of solid materials. More specifically, insofar as the mode of operation of the system and of the method to which the teachings of U.S. Patent No. 5,533,471 are directed is concerned, a circulating (fast) fluidized bed and a bubbling (slow) fluidized bed are utilized.
Continuing, these two (2) fluidized beds are mounted adjacent each other with first and second interconnections between them, typically with the fluidizing gas introducing grid of the bubbling fluidized bed being below that of the circulating fluidized bed. Because the bubbling fluidized bed has a substantially constant density throughout, with a clear demarcation line at the top thereof, the first interconnection is provided above the top of the bubbling fluidized bed so that the pressure and density conditions between the two (2) fluidized beds result in a flow of particles from the circulating fluidized bed to the bubbling fluidized bed through the first interconnection. However, since the average density in the bubbling fluidized bed is higher than the density in the circulating fluidized bed, the pressure and density conditions cause the particles after treatment in the bubbling fluidized bed (e.g., after the cooling of the particles therein) to return to the circulating fluidized bed through the second interconnection.
[0011] Discussing further the advanced clean fossil fuel technologies to which reference has been had above previously wherein various forms of hot solids processes are employed, and in particular that of hybrid combustion-gasification technologies, attention is first directed in this connection, by way of exemplification and not limitation, to U.S. Patent No. 4,272,399, which issued on June 8, 1981 to the Monsanto Company.
The teachings of U.S. Patent No. 4,272,399 are considered to be representative of an exemplification of an early development in the continuing evolution of the hybrid combustion-gasification technologies of the type wherein hot solids processes are employed. To this end, in accordance with the teachings thereof, the teachings of U.S.
Patent No. 4,272,399 are stated to be directed to a unified process for producing high purity synthesis gas from carbon-containing materials. More specifically, insofar as the mode of operation of the unified process to which the teachings of U.S. Patent No.
4,272,399 are directed is concerned, a metal-oxygen containing material, which can be characterized as a heat and oxygen carrier and which can be referred to generally as an oxidant, is used as the transfer agent of oxygen and heat for oxidatively gasifying carbon-containing material. Continuing, steam, carbon dioxide, synthesis gas or mixtures thereof are employed to fluidize and transport the oxidant through an up-flow, co-current system.
Thus, in accordance with the mode of operation of the subject unified process, synthesis gas is first oxidized and heated by the oxidant to form water and carbon dioxide in an oxidant reducing zone prior to contact of the oxidant and gases with the carbon-containing material in a gasifying zone. In addition, the carbon-containing materials are oxidized to predominately carbon monoxide and hydrogen in a manner such that the nitrogen contained in the air does not contaminate the product synthesis gas.
Furthermore, the gasification of the carbon-containing material is accomplished by the alternate oxidation and reduction of a fluidized oxidant. Then, after such gasification, the reduced oxidant, which may be in the form of the elemental metal or lower oxidized state is re-oxidized in an oxidizing zone and the cycle is then repeated.
[0012] Regarding further the hybrid combustion-gasification technologies of the advanced clean fossil fuel technologies to which reference has been had above previously wherein various forms of hot solids processes are employed, attention is next directed herein, by way of exemplification and not limitation, to U.S. Patent No.
7,083,658, which issued on August 1, 2006 to ALSTOM Technology Ltd., which is incorporated herein by reference. The teachings of U.S. Patent No. 7,083,658 are considered to be representative of an exemplification of a further development in the continuing evolution of hybrid combustion-gasification technologies of the type wherein hot solids processes are employed. To this end, in accordance with the teachings thereof, the teachings of U.S.
Patent No. 7,083,658 are stated to be directed to apparatus utilizing fossil fuels, biomass, petroleum coke, or any other carbon bearing fuel to produce hydrogen for power generation, which minimizes or eliminates the release of carbon dioxide (C02).
More specifically, insofar as the mode of operation of the apparatus to which the teachings of U.S. Patent No. 7,083,658 are directed is concerned, a gasifier is provided for producing a gas product from a carbonaceous fuel, which comprises a first chemical process loop including an exothermic oxidizer reactor and an endothermic reducer reactor.
Continuing, the exothermic oxidizer reactor has a CaS inlet, a hot air inlet and a CaSO4/waste gas outlet. Whereas, the endothermic reducer reactor has a CaSO4 inlet in fluid communication with the exothermic oxidizer reactor CaSO4/waste gas outlet, a CaS/gas product outlet in fluid communication with the exothermic oxidizer reactor CaS
inlet, and a materials inlet for receiving the carbonaceous fuel. Moreover, CaS is oxidized in air in the exothermic oxidizer reactor to form hot CaSO4, which is discharged to the endothermic reducer reactor. Furthermore, hot CaSO4 and carbonaceous fuel that is received in the endothermic reducer reactor undergo an endothermic reaction utilizing the heat content of the CaSO4 with the carbonaceous fuel stripping the oxygen from the CaS04 to form CaS and the gas product. Thereafter, the CaS is discharged to the exothermic oxidizer reactor, and with the gas product being discharged from the first chemical process loop.
[0013] It is, therefore, an object of the present invention to provide a hot solids process.
[0014] It is also an object of the present invention to provide such a hot solids process that is capable of generating an output.
[0015] It is another object of the present invention to provide such a hot solids process that is capable of generating such an output that is designed to be suitable for use as an input to a petrochemical process.
[0016] It is still another object of the present invention to provide such a hot solids process that is designed to employ a portion of the otherwise normally unusable product output, which is produced from such a petrochemical process, for purposes of generating in accordance with the present invention the output from the hot solids process of the present invention that is designed to be suitable for use as an input to such a petrochemical process.
[0017] Yet another object of the present invention is to provide such a hot solids process that is relatively inexpensive to provide, is relatively uncomplicated to employ, and is characterized by its great versatility insofar as the applicability thereof to petrochemical processes is concerned.

SUMMARY OF THE INVENTION

[0018] In accordance with the present invention a hot solids process is provided, which is capable of generating a predetermined output that is designed to be suitable for use as an input to a petrochemical process. To this end, the mode of operation, in accordance with the present invention of such a hot solids process, is such that preferably a portion of the otherwise normally unusable product output, which is produced from such a petrochemical process, is designed to be employed as an input to the hot solids process of the present invention for purposes of generating in accordance with the present invention the predetermined output from the hot solids process of the present invention, which is designed to be suitable for use as an input to said petrochemical process.
[0019] Continuing, in accordance with the present invention the mode of operation of the hot solids process of the present invention is such that preferably a limestone based sorbent, such as, by way of exemplification and not limitation, CaS, is designed to be combusted in an oxidizing reactor, such oxidizing reactor preferably, by way of exemplification and not limitation, being a circulating bed reactor, which is designed to be selected from a group of reactors that includes a fixed bed reactor, a bubbling bed reactor, a circulating bed reactor, a transport reactor, and an entrained bed reactor, in order to thereby produce hot CaSO4 from the combustion of such limestone based sorbent. This hot CaSO4 is then in turn designed to be employed in a reducing reactor, such reducing reactor preferably, by way of exemplification and not limitation, being a circulating bed reactor, which is designed to be selected from a group of reactors that includes a fixed bed reactor, a bubbling bed reactor, a circulating bed reactor, a transport reactor, and an entrained bed reactor, for purposes of generating the predetermined output, which is designed to be suitable for use as an input to a petrochemical process.
[0020] With further regard to the mode of operation of the hot solids process of the present invention, the inputs to the oxidizing reactor, which is employed in accordance with the mode of operation of the hot solids process of the present invention, when the fuel that is designed to be combusted in accordance therewith comprises a carbonaceous fuel, such as, preferably a portion of the otherwise normally unusable product output, which is produced from a petrochemical process, and wherein a portion of such otherwise normally unusable product output, which is produced from a petrochemical process, and which more particularly comprises petcoke and/or oil residuals that are known to be otherwise produced as normally unusable product outputs from a petrochemical process, and when the predetermined output that is being generated in accordance with the preferred mode of operation of the hot solids process of the present invention is designed to be suitable for use as an input to a petrochemical process, include CaS and air, and the outputs from such an oxidizing reactor in such a case include ash, CaSO4, and N2. Whereas, the inputs to the reducing reactor, which is employed in accordance with the mode of operation of the hot solids process of the present invention, when the fuel that is designed to be combusted in accordance therewith comprises a carbonaceous fuel, such as, preferably a portion of the otherwise normally unusable product output, which is produced from a petrochemical process, and wherein a portion of such otherwise normally unusable product output, which is produced from a petrochemical process, and which more particularly comprises petcoke and/or oil residuals that are known to be otherwise produced as normally unusable product outputs from a petrochemical process, and when the predetermined output that is being generated in accordance with the preferred mode of operation of the hot solids process of the present invention is designed to be suitable for use as an input to a petrochemical process, include the carbonaceous fuel, CaCO3, steam, and CaSO4, and the output from such a reducing reactor in such a case is designed to be the predetermined output, which is being generated in accordance with the preferred mode of operation of the hot solids process of the present invention such that the predetermined output generated from the hot solids process of the present invention is suitable for use as an input to a petrochemical process.
BRIEF DESCRIPTION OF THE DRAWINGS

[00211 Figure 1 of the drawing is a schematic diagram of a preferred embodiment of the mode of operation of a hot solids process that functions in accordance with the present invention to generate a predetermined output, which is suitable for use as an input to a petrochemical process, the latter petrochemical process also being schematically depicted as well in Figure 1.

DETAILED DESCRIPTION
[0022] Referring now to Figure 1 of the drawing, there is depicted therein a schematic diagram of a hot solids process, generally denoted by the reference numeral 10 in Figure 1 of the drawing, that is designed to be operable in accordance with the present invention for purposes of generating a predetermined output, such as, by way of exemplification and not limitation, H2 or syngas and steam, and with the latter predetermined output being denoted by the arrow 12 in Figure 1 of the drawing.
The predetermined output 12 from the hot solids process 10 is designed in accordance with the present invention to be suitable for use as an input to a petrochemical process, the latter petrochemical process being denoted generally by the reference numeral 14 in Figure 1 of the drawing. To this end, the mode of operation, in accordance with the present invention of the hot solids process 10, is such that preferably a portion of the otherwise normally unusable product output, denoted by the reference numeral 16 in Figure 1 of the drawing, which is produced from the petrochemical process 14, is designed to be utilized as an input to the hot solids process 10 of the present invention for purposes of generating in accordance with the present invention the predetermined output 12 from the hot solids process 10 of the present invention that is designed to be suitable for use as an input to the petrochemical process, which is schematically depicted at 14 in Figure 1 of the drawing.
The remainder, which is denoted by the reference numeral 17 in Figure 1 of the drawing, of the otherwise normally unusable product output 16 that is produced from the petrochemical process 14, which is schematically depicted in Figure 1 of the drawing, is designed so as to be capable of being discharged from the petrochemical process 14 in any conventional manner, which is deemed to be suitable for use for such a purpose.
[0023] Continuing, the hot solids process of the present invention in accordance with the preferred mode of operation thereof is designed to utilize air; a carbonaceous fuel, such as, by way of exemplification and not limitation, the portion of the otherwise normally unusable product output, which is 16 from a petrochemical process, such as, the petrochemical process that is schematically depicted at 14 in Figure 1 of the drawing, and wherein such a portion of the otherwise normally unusable product output 16, which is produced from the petrochemical process 14, and which preferably comprises petcoke and/or oil residuals that are known to be producible as an otherwise normally unusable product output from a petrochemical process, such as, the petrochemical process 14 that is schematically depicted in Figure 1 of the drawing; a source of calcium (e.g., calcium oxide); and steam to effect therewith the generation of the predetermined output 12, which is designed to be suitable for use as an input to a petrochemical process, such as, the petrochemical process that is schematically depicted at 14 in Figure 1 of the drawing.
[0024] With further reference to Figure 1 of the drawing, a reducing reactor, denoted generally by the reference numeral 18 in Figure 1 of the drawing, selected from a group of reactors that includes a fixed bed reactor, a bubbling bed reactor, a circulating bed reactor, a transport reactor and an entrained bed reactor and preferably comprising a circulating bed reactor, and an oxidizing reactor, denoted generally by the reference numeral 20 in Figure 1 of the drawing, selected from a group of reactors that includes a fixed bed reactor, a bubbling bed reactor, a circulating bed reactor, a transport reactor and an entrained bed reactor and preferably comprising a circulating bed reactor, are each designed to be employed in the hot solids process 10 of the present invention, in accordance with the preferred mode of operation thereof. Continuing, in accordance with the preferred embodiment of the hot solids process 10 of the present invention, the carbonaceous fuel, such as, by way of exemplification and not limitation, the portion of the otherwise normally unusable product output 16 that is produced from the petrochemical process, which is schematically depicted at 14 in Figure 1 of the drawing, that is designed to be supplied from the petrochemical process 14 as an input to the reducing reactor 18, is designed to be burned in the reducing reactor 18 preferably using air indirectly. To this end, a source of calcium (i.e., calcium oxide), and with the latter source of calcium being denoted by the arrow 22 in Figure 1 of the drawing, which is designed to be added, in accordance with the preferred mode of operation of the hot solids process 10 of the present invention, is also supplied, by way of exemplification and not limitation, as an input to the reducing reactor 18. However, such source of calcium 22 could equally well be supplied elsewhere in the hot solids process 10 of the present invention other than as an input to the reducing reactor 18, without departing from the essence of the present invention. Such source of calcium 22, which may be selected from the group including of limestone (CaCO3) or lime (CaO) or gypsum or the spent bed material from a circulating bed boiler, by way of exemplification and not limitation, preferably comprises limestone (CaCO3). With further reference thereto, such limestone (CaCO3) 22, which is added in accordance with the preferred mode of operation of the hot solids process 10 of the present invention, is designed to be operative to capture in the reducing reactor 18 the sulfur (S), which is contained in the carbonaceous fuel 16, such as to thereby produce calcium sulfide (CaS) therefrom in the reducing reactor 18.
[00251 Continuing, such calcium sulfide (CaS), as denoted by the arrow 24 in Figure 1 of the drawing, is then made to exit from the reducing reactor 18 as an output therefrom, whereupon such calcium sulfide (CaS) 24 is designed to be supplied as an input to the oxidizing reactor 20. In the oxidizing reactor 20, this calcium sulfide (CaS) 24 is designed to be burned in a heat liberation reaction with air, and with the latter air being denoted by the arrow 26 in Figure 1 of the drawing, which is designed to be supplied as an input to the oxidizing reactor 20, such as to thereby effect the production therefrom of calcium sulfate (CaSO4) in the oxidizing reactor 20. This calcium sulfate (CaSO4), as is denoted by the arrow 28 in Figure 1 of the drawing, is then designed to be made to exit as an output from the oxidizing reactor 20, whereupon this calcium sulfate (CaSO4) 28 is designed to be cycled to the reducing reactor 18 as an input thereto for purposes of thereby producing therefrom the supply of oxygen and of heat that is required both in order to burn the carbonaceous fuel 16 and in order to reduce the calcium sulfate (CaSO4) 28 to calcium sulfide (CaS) 24 in the reducing reactor 18, such as to thereby permit a continuous recycling thereof to be had. With further regard thereto, in accordance with the preferred mode of operation of the hot solids process 10 of the present invention that is depicted in Figure 1 of the drawing, steam, and with the latter steam being denoted by the arrow 30 in Figure 1 of the drawing, is preferably also supplied as an input to the reducing reactor 18.
[00261 Referring once again to Figure 1 of the drawing, the burning of the carbonaceous fuel 16 in the reducing reactor 18 is designed to be such that the predetermined output 12 is thus capable of being generated in the reducing reactor 18, and with the carbon and the hydrogen contained in the carbonaceous fuel 16 being converted, in the course of such burning of the carbonaceous fuel 16 to a product gas, such as, H2 or syngas, in a suitable form such that such product gas, with the possible addition thereto of steam is capable of being made to function as the predetermined output 12 from the hot solids process 10 of the present invention, in accordance with the preferred mode of operation thereof, which is designed to be suitable for use as an input to a petrochemical process, such as, by way of exemplification and not limitation, the predetermined process, which is schematically depicted at 14 in Figure 1 of the drawing.
In addition, as is indicated in Figure 1 of the drawing by the arrow that is denoted therein by the reference numeral 32, the nitrogen (N2), which remains from the oxidation of the calcium sulfide (CaS) 24 that takes place in the oxidizing reactor 20, is designed to be made to exit through an outlet (not shown in the interest of maintaining clarity of illustration in the drawing) with which the oxidizing reactor 20 is designed to be suitably provided for this purpose.
[0027] For purposes of completing the description of the nature of the construction and of the mode of operation in accordance with the present invention of both the hot solids process 10 and the petrochemical process 14, which are schematically depicted in Figure 1 of the drawing, reference will once again be had herein to Figure 1 of the drawing. To this end, in accordance with the mode of operation of the present invention the hot solids process 10 is suitably constructed so as to be capable of generating a predetermined output 12, such as, by way of exemplification and not limitation, steam and H2 or syngas, that is designed to be suitable for use as an input to a petrochemical process, such as, for example, the petrochemical process, which is schematically depicted in Figure 1 of the drawing.
[0028] With further reference to the petrochemical process, which is schematically depicted at 14 in Figure 1 of the drawing, in accordance with the conventional mode of operation of such petrochemical processes, crude, which is denoted by the arrow 34 in Figure 1 of the drawing, is designed to be supplied as an input to the petrochemical process 14. Continuing with the discussion of the mode of operation thereof, the crude 34 and the input 12, the latter being produced as an output from the hot solids process 10 of the present invention, are designed to be supplied as inputs to the petrochemical process 14 such that in accordance with conventional practice the crude 34 and the input 12, which are supplied as inputs to the petrochemical process 14, are designed to be converted in known fashion through operation of the petrochemical process 14 so as to thereby produce both a usable product output, the latter usable product output being denoted by the arrow 36 in Figure 1 of the drawing,, that commonly consists of one or more of the following: diesel fuel, gasoline, etc., and an otherwise normally unusable product output 16 to which reference has been had herein previously.
With further regard thereto, in accordance with the present invention a portion of the otherwise normally unusable product output 16, which preferably comprises, by way of exemplification and not limitation, petcoke and/or oil residuals, from the petrochemical process that is depicted at 14 in Figure 1 of the drawing, is designed to be employed in accordance with the present invention as an input to the hot solids process 10 for purposes of effecting, in accordance with the present invention, the production within the hot solids process 10 of the predetermined output 12 that is designed to be suitable for purposes of being employed as the input 12 to the petrochemical process, which is schematically depicted at 14 in Figure 1 of the drawing. The remainder of the otherwise normally unusable product output, such remainder being depicted in Figure 1 of the drawing by the arrow that is denoted therein by the reference numeral 17, which is produced from the petrochemical process 14 that is schematically depicted in Figure 1 of the drawing, is suitably designed such as to be capable of being discharged from the petrochemical process 14 in any conventional manner, which is deemed to be suitable for use for such a purpose.
[0029] While the embodiments of the present invention described hereinbefore included a calcium oxide, the invention contemplates that the oxide may include a metal oxide, for example, formed of iron such as FeO.
[0030] While a preferred embodiment of the present invention has been shown and described in the instant application, it is to be understood that various modifications and substitutions, some of which have been alluded to in the instant application, may be made thereto without departing from the spirit and scope of the present invention, as the present invention is set forth in the claims that are appended hereto.
Accordingly, it is to be further understood that the present invention, as the present invention has been shown and described in the instant application, has been shown and described therein by way of illustration only, and not by way of limitation.

Claims (13)

1. A hot solids process capable of generating a predetermined output suitable for use as an input to a petrochemical process comprising:
providing a first reactor capable of operating as a reducing reactor;
providing a second reactor capable of operating as an oxidizing reactor;
supplying both a sulfur containing carbonaceous fuel and a source of calcium as inputs to the first reactor;
supplying air as an input to the second reactor;
effecting with the source of calcium the capture in the first reactor of the sulfur in the sulfur containing carbonaceous fuel so as to thereby produce CaS
in the first reactor;
effecting the discharge as an output from the first reactor of the CaS
produced in the first reactor;
supplying as an input to the second reactor the CaS discharged as an output from the first reactor;
effecting the production of CaSO4 in the second reactor from the CaS
supplied as an input to the second reactor;
effecting the discharge as an output from the second reactor of the CaSO4 produced in the second reactor;
supplying the CaSO4 discharged as an output from the second reactor as an input to the first reactor;
effecting in the first reactor the generation of a predetermined output suitable for use as an input to a petrochemical process by virtue of the utilization of the CaSO4 supplied to the first reactor from the second reactor both as an oxygen source and as a heat source;
connecting in operative relation to the hot solids process a petrochemical process operable for purposes of producing a usable product output as well as an otherwise normally unusable product output;

effecting the discharge as an output from the first reactor of the predetermined output suitable for use as an input to a petrochemical process produced in the first reactor;
and supplying as an input to the petrochemical process the predetermined output suitable for use as an input to a petrochemical process that is discharged as an output from the first reactor.
2. The hot solids process as claimed in claim 1 further comprising selecting as the first reactor a circulating bed reactor capable of operating as a reducing reactor, and selecting as the second reactor a circulating bed reactor capable of operating as an oxidizing reactor.
3. The hot solids process as claimed in claim 1 further comprising selecting a portion of the otherwise normally unusable product output from the petrochemical process for use as the sulfur containing carbonaceous fuel in the hot solids process.
4. The hot solids process as claimed in claim 3 further comprising supplying as an input to the first reactor of the hot solids process the portion of the otherwise normally unusable product output from the petrochemical process selected for use as the sulfur containing carbonaceous fuel in the hot solids process.
5. The hot solids process as claimed in claim 4 wherein the portion of the otherwise normally unusable product output from the petrochemical process supplied as an input to the first reactor of the hot solids process for use as the sulfur containing carbonaceous fuel in the hot solids process comprises petcoke.
6. The hot solids process as claimed in claim 3 wherein the portion of the otherwise normally unusable product output from the petrochemical process supplied as an input to the first reactor of the hot solids process for use as the sulfur containing carbonaceous fuel in the hot solids process comprises residual oils.
7. The hot solids process as claimed in claim 1 further comprising selecting CaCO3 for use as the source of calcium supplied as an input to the first reactor of the hot solids process.
8. The hot solids process as claimed in claim 1 wherein the predetermined output suitable for use as an input to a petrochemical process that is supplied as an input to the petrochemical process from the first reactor of the hot solids process comprises H2.
9. The hot solids process as claimed in claim 8 wherein the predetermined output suitable for use as an input to a petrochemical process that is supplied as an input to the petrochemical process from the first reactor of the hot solids process further comprises steam.
10. The hot solids process as claimed in claim 1 wherein the predetermined output suitable for use as an input to a petrochemical process that is supplied as an input to the petrochemical process from the first reactor of the hot solids process comprises syngas.
11. The hot solids process as claimed in claim 10 wherein the predetermined output suitable for use as an input to a petrochemical process that is supplied as an input to the petrochemical process from the first reactor of the hot solids process further comprises steam.
12. A hot solids process capable of generating a predetermined output suitable for use as an input to a petrochemical process comprising:
providing a first reactor capable of operating as a reducing reactor;
providing a second reactor capable of operating as an oxidizing reactor;
supplying both a sulfur containing carbonaceous fuel and an oxide as inputs to the first reactor;
supplying air as an input to the second reactor;
effecting with the oxide the capture in the first reactor of the sulfur in the sulfur containing carbonaceous fuel;
effecting the production of an oxide in the second reactor;
effecting the discharge as an output from the second reactor of the oxide produced in the second reactor;
supplying the oxide discharged as an output from the second reactor as an input to the first reactor;
effecting in the first reactor the generation of a predetermined output suitable for use as an input to a petrochemical process by virtue of the utilization of the oxide supplied to the first reactor from the second reactor both as an oxygen source and as a heat source;
connecting in operative relation to the hot solids process a petrochemical process operable for purposes of producing a usable product output as well as an otherwise normally unusable product output;
effecting the discharge as an output from the first reactor of the predetermined output suitable for use as an input to a petrochemical process produced in the first reactor;
and supplying as an input to the petrochemical process the predetermined output suitable for use as an input to a petrochemical process that is discharged as an output from the first reactor.
13. The hot solids process as claimed in claim 12 wherein the oxide is one of a calcium oxide and metal oxide.
CA2757824A 2009-03-31 2010-03-30 A hot solids process having an output suitable for the input to a petrochemical process Expired - Fee Related CA2757824C (en)

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US16504209P 2009-03-31 2009-03-31
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US61/165,094 2009-03-31
US61/165,069 2009-03-31
US12/749,238 US20100288678A1 (en) 2009-03-31 2010-03-29 Hot solids process having an output suitable for the input to a petrochemical process
US12/749,238 2010-03-29
PCT/US2010/029179 WO2010117772A2 (en) 2009-03-31 2010-03-30 A hot solids process having an output suitable for the input to a petrochemical process

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DE2624302C2 (en) * 1976-05-31 1987-04-23 Metallgesellschaft Ag, 6000 Frankfurt Methods for carrying out exothermic processes
GB2039293B (en) * 1979-01-09 1982-11-17 Exxon Research Engineering Co Conversion of fuel to reducing and/or synthesis gas
US4272399A (en) * 1979-09-21 1981-06-09 Monsanto Company Conversion of carbon-containing materials to synthesis gas
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US5533471A (en) * 1994-08-17 1996-07-09 A. Ahlstrom Corporation fluidized bed reactor and method of operation thereof
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US7083658B2 (en) * 2003-05-29 2006-08-01 Alstom Technology Ltd Hot solids gasifier with CO2 removal and hydrogen production
US20070000177A1 (en) * 2005-07-01 2007-01-04 Hippo Edwin J Mild catalytic steam gasification process

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WO2010117772A3 (en) 2011-04-07
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EP2414486A2 (en) 2012-02-08
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