AU2008327918A1 - Process for production of elemental iron - Google Patents
Process for production of elemental iron Download PDFInfo
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- AU2008327918A1 AU2008327918A1 AU2008327918A AU2008327918A AU2008327918A1 AU 2008327918 A1 AU2008327918 A1 AU 2008327918A1 AU 2008327918 A AU2008327918 A AU 2008327918A AU 2008327918 A AU2008327918 A AU 2008327918A AU 2008327918 A1 AU2008327918 A1 AU 2008327918A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
- C01B3/54—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids including a catalytic reaction
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/86—Carbon dioxide sequestration
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0969—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
- C21B2100/28—Increasing the gas reduction potential of recycled exhaust gases by separation
- C21B2100/282—Increasing the gas reduction potential of recycled exhaust gases by separation of carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/40—Gas purification of exhaust gases to be recirculated or used in other metallurgical processes
- C21B2100/42—Sulphur removal
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
- C21B2100/62—Energy conversion other than by heat exchange, e.g. by use of exhaust gas in energy production
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C2100/00—Exhaust gas
- C21C2100/06—Energy from waste gas used in other processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
Description
WO 2009/065843 PCT/EP2008/065797 PROCESS FOR PRODUCTION OF ELEMENTAL IRON Field of the invention The invention is directed to a process to prepare elemental iron by contacting an iron ore feed with a reducing gas comprising synthesis gas, wherein the 5 reducing gas is prepared by a partial oxidation process. Background of the invention Direct reduction of iron (DRI) generates metallic iron in a solid form by removing oxygen from the iron ore by using a reduction gas that can be provided from the 10 synthesis gas obtained by gasification of carbonaceous feedstock. Industrially applied DRI processes include MIDREX, HyL and FINMET, as described in "Development of Reduction Process for the Steel Production" by M. Gojic and S. Kozuh, Kem. Ind. 55 (1) 1-10 (2006). 15 EP-A-0916739 describes a process wherein the reducing gas for the DRI process is obtained by gasification of a coal slurry. The reducing gas fed to the DRI includes a recycle gas stream that has exited the DRI, and wherein acid gases have been removed from the recycle gas stream. 20 US-A-5871560 describes a process wherein synthesis gas is mixed with an off-gas produced in a DRI process to be used as a reduction gas and wherein H 2 S is fed to the reducing gas. US-A-2740706, as filed in 1951, describes a process 25 to for reducing metal oxides by contacting with a reducing gas. In its examples the reducing gas is prepared by partial oxidation of natural gas in admixture with carbon dioxide to obtain a reducing gas having two to three times as much volumes of carbon monoxide for 30 each volume of hydrogen. The reason, according to this publication, to add carbon dioxide to the natural gas is to achieve such high contents of carbon monoxide. Coal is WO 2009/065843 PCT/EP2008/065797 -2 mentioned as a possible feedstock instead of natural gas. In this process sulphur is removed from the reducing gas by contacting the gas with sponge iron. The so-called entrained-flow gasification process for 5 coal as described in "Gasification" by C. Higman and M. van der Burgt, 2003, Elsevier Science, Chapter 5.3, pages 109-128 was developed after 1970 (see page 5 of this reference). It is an object of the present invention to provide a 10 process that has a higher efficiency than the above described processes. Summary of the Invention The above object is achieved by the present invention by the following process. Process to prepare elemental 15 iron by contacting an iron ore feed with a reducing gas to obtain iron and an off-gas, wherein the reducing gas is prepared by performing the following steps (a) partially oxidizing a mixture consisting of a sulphur containing solid carbonaceous fuel and gaseous CO 2 as 20 carrier medium with oxygen, by supplying an oxygen containing gas and the solid carbonaceous fuel to a burner, thereby obtaining a gas comprising H 2 , CO, CO 2 and
H
2 S; (b) removing CO 2 and H 2 S from the gas obtained in 25 step (a) to obtain the reducing gas comprising H 2 and CO and a first stream comprising CO 2 and H 2 S; (c) reducing the content of H 2 S in the first stream comprising CO 2 and H 2 S obtained in step (b) in a liquid redox type process and 30 (d) recycling at least part of the CO 2 obtained in step (c) to step (a). Applicants found that by recycling part of the CO 2 to step (a) a more efficient process is obtained. A further advantage of the present invention is that, for a given WO 2009/065843 PCT/EP2008/065797 -3 amount of carbonaceous fuel to be partially oxidised in the gasification reactor, a smaller reactor volume can be used, resulting in lower equipment expenses, as compared to a situation wherein no CO 2 is present in step (a). A 5 further advantage is that the removal of CO 2 and H 2 S is performed in one step, namely step (b), while in the process of US-A-2740706 this removal takes place in two steps. The separation of H 2 S from the first stream comprising CO 2 and H 2 S by means of a liquid redox process 10 is much more efficient than removing H 2 S the entire effluent of step (a) as in the process of US-A-2740706. Detailed description of the invention In the DRI process an iron ore feed is contacted with the reducing gas comprising H 2 and CO to obtain elemental 15 iron and an off-gas. Exemplary DRI processes are those mentioned earlier. In a typical DRI process the iron ore feed is usually in the form of pellets or in the lump form or a combination of the two. The iron ore is supplied to a 20 heated furnace or to a set of reactors through which it descends by gravity at superatmospheric pressure, e.g., 1.5-12 bar. Iron ore feed is reduced in the said furnace or set of reactors by the action of counterflowing reducing gas that has high H 2 and CO contents. Process 25 specifics of the DRI processes are described for example in "Kirk-Othmer Encyclopedia of Chemical Technology", fourth edition, volume 14, John Wiley & Sons, 1985, pages 855-872. The reducing gas is used to remove oxygen from the 30 iron oxide comprised within the iron ore feed. The reducing process can be illustrated by the following reaction, where H 2 0 and CO 2 are obtained as by-products: Fe 2
O
3 + H 2 - 2Fe + 3H 2 0 Fe 2
O
3 + CO - 2Fe + CO 2 WO 2009/065843 PCT/EP2008/065797 -4 Preferably the reducing gas has H 2 /CO ratio of at least 0.5. It is also preferred that the reducing gas has a "gas quality" of at least 10. The gas quality is defined as a ratio of reductants to oxidants, as demonstrated by 5 the following equation: Gas quality = (mol% H 2 + mol% CO) / (mol% H 2 0 + mol% C0 2 ) Iron obtained from the DRI process is cooled and carbonized by means of the counterflowing gasses in the lower portion of the shaft furnace according to the 10 following reaction: 3Fe + CO + H 2 -- Fe 3 C + H 2 0 3Fe + CH 4 -- Fe 3 C + 2H 2 By means of this process it is possible to manufacture for example so-called cold DRI products, hot briquetted 15 iron, or hot direct reduction iron. The off-gas obtained by the DRI process is the spent reducing gas exiting the furnace. The off-gas can be cleaned by scrubbing and CO 2 removal and is preferably recycled to be used as the reducing gas. Preferably the 20 off-gas is treated before the re-use as reducing gas to satisfy the requirement for reducing gas as described above. In step (a) of the process according to the invention a mixture consisting of a sulphur containing solid 25 carbonaceous fuel and CO 2 with oxygen containing gas is partially oxidized, thereby obtaining a gas comprising
H
2 , CO, CO 2 and H 2
S
The partial oxidation may be performed by any process known. Preferably the partial oxidation is performed by 30 means of the so-called entrained-flow gasification process as described in "Gasification" by C. Higman and M. van der Burgt, 2003, Elsevier Science, Chapter 5.3, pages 109-128. More preferably step (a) is performed in an entrained-flow gasifier process wherein the reaction WO 2009/065843 PCT/EP2008/065797 -5 between the mixture of carbonaceous fuel and CO 2 with oxygen containing gas takes place in a gasification reactor provided with one or more burners. In such a process an oxygen containing gas and a solid carbonaceous 5 fuel are supplied to a burner. CO 2 is used as carrier medium to transport the fuel to the burner. One or more burners can be provided in the gasification reactor. The burner can be a single burner directed downward at the top of a vertically elongated reactor. Preferably the 10 gasification reactor will have substantially horizontal firing burners in diametrically opposing positions. The burner is preferably a co-annular burner with a passage for an oxygen containing gas and a passage for the fuel and the carrier gas. Partial oxidation of the 15 carbonaceous fuel occurs at a relatively high temperature in the range of 1000 0 C to 2000 0 C and at a pressure in a range of from about 1-70 bar. Preferably the pressure is between 10 and 70 bar, more preferably between 30 and 60 bar. The gas is cooled with either direct quenching 20 with water, direct quenching with the off-gas, direct quenching with the part of the gas obtained in either steps (a) or (b), by indirect heat exchange against evaporating water or combination of such cooling steps. Slag and other molten solids are suitably discharged from 25 the gasification reactor at the lower end of the said reactor. The term solid carbonaceous fuel may be any carbonaceous fuel in solid form. Examples of solid carbonaceous fuels are coal, coke from coal, petroleum 30 coke, soot, biomass and particulate solids derived from oil shale, tar sands and pitch. Preferably the solid carbonaceous fuel is chosen from the group of coal, petroleum coke, peat and solid biomass. Coal is particularly preferred, and may be of any type and 35 sulphur content, including lignite, sub-bituminous, WO 2009/065843 PCT/EP2008/065797 -6 bituminous and anthracite. Although in many DRI processes natural gas is used as a fuel, coal is an interesting choice for a fuel source because of its abundance. Coal is preferably supplied to the burner in form of fine 5 particulates. The term fine particulates is intended to include at least pulverized particulates having a particle size distribution so that at least about 90% by weight of the material is less than 90 pm and moisture content is typically between 2 and 12% by weight, and 10 preferably less than about 8%, more preferably less than 5% by weight. Preferably coal is supplied in admixture with CO 2 as a carrier medium. Gaseous CO 2 containing carrier medium contains preferably at least 80%, more preferably at least 95% 15 Co 2 . CO 2 can be separated from the reducing gas and from the off-gas of the DRI process. It has been found that by using CO 2 as obtained in step (c) in step (a), as the carrier medium, a more efficient process is obtained. Preferably, the CO 2 containing carrier gas supplied 20 in step (a) is supplied to the burner at a velocity of less than 20 m/s, preferably from 5 to 15 m/s, more preferably from 7 to 12 m/s. Further it is preferred that the CO 2 and the carbonaceous fuel are supplied at a density of from 300 to 600 kg/m 3 , preferably from 350 to 25 500 kg/m 3 , more preferably from 375 to 475 kg/m 3 . In a preferred embodiment of the process according to the present invention, the weight ratio of CO 2 to the carbonaceous fuel in step (a) is in the range from 0.12 0.49, preferably below 0.40, more preferably below 0.30, 30 even more preferably below 0.20 and most preferably between 0.12-0.20 on a dry basis. It has been found according to the present invention that using the relatively low weight ratio of CO 2 to the carbonaceous fuel in step (a) less oxygen is consumed WO 2009/065843 PCT/EP2008/065797 -7 during gasification. The oxygen containing gas comprises substantially pure O2 or air. Preferably it contains at least 90% by volume oxygen, with nitrogen, carbon dioxide and argon being permissible as impurities. Substantially 5 pure oxygen is preferred, such as prepared by an air separation unit (ASU). Steam may be present in the oxygen containing gas as supplied to the burner to act as moderator gas. The ratio between oxygen and steam is preferably from 0 to 0.3 parts by volume of steam per 10 part by volume of oxygen. When the downstream DRI process requires a high CO to H 2 ratio it is advantageous to use
CO
2 instead of steam as a moderator gas. This CO 2 is preferably CO 2 as obtained in step (c). A mixture of the fuel and oxygen from the oxygen containing stream is then 15 reacted in a reaction zone in the gasification reactor. The gaseous stream obtained in step (a) comprises mainly H 2 and CO, which are the main components of the synthesis gas, and can further comprise other components such as CO 2 , H 2 S, HCN and COS. The gaseous stream 20 obtained in step (a) suitably comprises from 1 to 10 mol% C0 2 , preferably from 4.5 to 7.5 mol% CO 2 on a dry basis when performing the process according to the present invention. The gaseous stream obtained in step (a) is preferably 25 subjected to a dry solids removal and wet scrubbing. The dry solids removal unit may be of any type, including the cyclone type. The dry solid material is discharged from the dry solids removal unit to be further processed prior to disposal. 30 In order to remove the particulate matter, for example soot particles, the gaseous stream obtained in step (a) is contacted with a scrubbing liquid in a soot scrubber. The gaseous stream exiting the gasifier is generally at elevated temperature and at elevated WO 2009/065843 PCT/EP2008/065797 -8 pressure. To avoid additional cooling and/or depressurising steps, the scrubbing step in the soot scrubber is preferably performed at elevated temperature and/or at elevated pressure. Preferably, the temperature 5 at which the reducing gas is contacted with scrubbing liquid is in the range of from 120 to 160 'C, more preferably from 130 to 150 0 C. Preferably, the pressure at which the gaseous stream obtained in step (a) is contacted with scrubbing liquid is in the range of from 10 20 to 80 bara, more preferably from 20 to 60 bara. The process further comprises step (b) of removing
CO
2 and H 2 S from the gas obtained in step (a) thereby obtaining the reducing gas comprising H 2 and CO and a first stream comprising CO 2 and H 2
S
15 Removing CO 2 and H 2 S is performed in a, hereafter referred to, CO 2 recovery system. The CO 2 recovery system is preferably a combined C0 2
/H
2 S removal system. Preferably C0 2
/H
2 S removal is performed by absorption using so-called physical and/or chemical solvent process. 20 The CO 2 recovery is performed on the gaseous stream obtained in step (a). The off-gas of the DRI contacting process is suitably also subjected to the same or a different CO 2 recovery system to obtain a recycle reducing gas comprising CO and H 2 and a second stream 25 comprising CO 2 and possibly H 2 S. In case the CO 2 recovery system is the same, the second stream and the first stream are the same and will be referred to as the first stream. It is preferred to remove at least 80 vol%, 30 preferably at least 90 vol%, more preferably at least 95 vol% and at most 99.5 vol%, of the CO 2 present in the gaseous stream obtained in step (a).
WO 2009/065843 PCT/EP2008/065797 -9 Absorption processes are characterized by washing the synthesis gas with a liquid solvent, which selectively removes the acid components (mainly CO 2 and
H
2 S) from the gas. The laden solvent is regenerated, 5 releasing the acid components and recirculated to the absorber. The washing or absorption process takes place in a column, which is usually fitted with for example packing or trays. On an industrial scale there are chiefly two categories of absorbent solvents, depending 10 on the mechanism to absorb the acidic components: chemical solvents and physical solvents. Reference is made to the absorption process as described in chapters 8.2.1 and 8.2.2 of "Gasification"(already referred to), page 298-309, and Perry, Chemical Engineerings' Handbook, 15 Chapter 14, Gas Absorption. Chemical solvents which have proved to be industrially useful are primary, secondary and/or tertiary alkanolamines. The most frequently used amines are derived from ethanolamine, especially monoethanol 20 amine (MEA), diethanolamine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA) and methyldiethanolamine (MDEA). Physical solvents which have proved to be industrially suitable are cyclo-tetramethylenesulfone and 25 its derivatives, aliphatic acid amides, N-methylpyrrolidone, N-alkylated pyrrolidones and the corresponding piperidones, methanol, ethanol and mixtures of dialkylethers of polyethylene glycols. A well-known commercial process uses an aqueous 30 mixture of a chemical solvent, especially DIPA and/or MDEA, and a physical solvent, especially cyclotetramethylene-sulfone also referred to as sulfolane. Such systems show good absorption capacity and good selectivity against moderate investment costs and WO 2009/065843 PCT/EP2008/065797 - 10 operational costs. They perform very well at high pressures, especially between 20 and 90 bara. Preferably the solvent comprises one or more compounds selected from the group of N-methylpyrrolidone 5 (NMP), dimethyl ether of polyethylene glycol (DMPEG), methanol or an amine such as di-isopropanol amine (DIPA) or mixtures of amines with sulfolane. More preferably, the solvent comprises an amine and sulfolane. Preferably step (b) comprises one or more further 10 removal systems that may be guard or scrubbing units, either as back-up or support to the C0 2
/H
2 S removal system. These further removal systems are aimed at removing HCN and COS or other contaminants such as NH 3 ,
H
2 S, metals, carbonyls, hydrides or other trace 15 contaminants which may be comprised in the gas obtained in step (a). Preferably step (b) is performed by at least two steps wherein in a first step the gas obtained in step (a) is contacted with the HCN/COS hydrolysis 20 catalyst to convert HCN to NH 3 and COS to H 2 S, followed by removal of water and ammonia from the gas by cooling and/or scrubbing, and in a second step the gas obtained in said first step is contacted with a suitable solvent, which is selective for absorbing CO 2 and H 2 S as described 25 above. The process of contacting the gas obtained in step (a) with the HCN/COS hydrolysis catalyst to convert HCN to NH 3 and COS to H 2 S takes place by catalytic hydrolysis in the hydrolysis unit. Examples of a 30 suitable hydrolysis step are disclosed in WO-A-04105922. The hydrolysis zone can be a gas/solid contactor, preferably a fixed bed reactor. Catalysts for the hydrolysis of HCN and COS are known to those skilled in the art and include for example TiO 2 -based catalysts or WO 2009/065843 PCT/EP2008/065797 - 11 catalysts based on alumina and/or chromium-oxide. Preferred catalysts are TiO 2 -based catalysts. The process further comprises step (c) of reducing the content of H 2 S in the first stream comprising CO 2 and 5 H 2 S obtained in step (b). Preferably the CO 2 as obtained in step (c) has a sulphur content lower than 10 ppmv, more preferably between 5 and 10 ppmv. Step (c) is performed by means of a liquid redox type process. More preferably step (c) is performed by liquid redox type 10 process by contacting the stream of CO 2 and H 2 S obtained in step (b) with an aqueous reactant solution comprising iron (III) chelate of an organic acid or complex reactant system to produce elemental sulphur which is recovered as a by-product of the present process either prior to or 15 subsequent to regeneration of the reactant, as described in for example "Gas Purification" by A. Kohl and R. Nielsen, Gulf Publishing Company, fifth edition, pages 670-840, and more specifically pages 803-840. The reduction of H 2 S content in step (c) can also be 20 performed on a mixture of the first and second stream comprising
CO
2 and H 2
S
The process according to the invention further includes step (d) wherein at least part of the CO 2 obtained in step (c) is recycled to step (a). The CO 2 25 that is recycled to step (a) is isolated from the first and optional second stream comprising CO 2 and H 2
S
The reducing gas obtained in step (b) is directed to an expander wherein the pressure of the reducing gas is reduced and power is generated. The reducing gas is then 30 heated in a gas heater before entering the furnace of the DRI process where it is contacted with iron ore feed to produce iron and the off-gas. The off-gas of the DRI contacting process can be subjected to the CO 2 recovery as described above, thereby WO 2009/065843 PCT/EP2008/065797 - 12 obtaining a recycle reducing gas comprising CO and H 2 and a second stream comprising CO 2 and H 2 S. The recycle reducing gas comprising CO and H 2 can be recycled to the furnace of the DRI process. The CO 2 from the first and 5 second streams comprising CO 2 and H 2 S is preferably used in step (a) as a carrier medium to carry the coal to the burner. Excess CO 2 is preferably stored in subsurface reservoirs or more preferably a part of the CO 2 as obtained in step (c) is used for one of the processes 10 comprising enhanced oil recovery, CO 2 sequestration or coal bed methane extraction. A part of the CO 2 can be injected into the subterranean zone to obtain a desired pressure in said subterranean zone such to enhance the recovery of a hydrocarbon containing stream as produced 15 from said subterranean zone. A part of the reducing gas obtained in step (c) is preferably used as a fuel in a gas turbine to generate power. Brief description of the drawings Figure 1 schematically shows a process scheme for a 20 process according to the present invention. Detailed description of the drawings In the process scheme of Figure 1 a sulphur containing solid carbonaceous fuel (1), preferably coal as fine particulates, is mixed with the CO 2 containing 25 carrier gas (2) and fed to a burner of a gasification reactor (4) where it is contacted with an oxygen containing gas (3) to obtain the reducing gas comprising
H
2 and CO (5) and slag (4a). The reducing gas (5) is treated in a dry solids removal unit (6). The dry solid 30 material is discharged from the dry-solids removal unit (6) via line (6a). Stream (7), free of solids, enters a C0 2
/H
2 S removal system (8) where the removal of acid gases such as C0 2 , H 2 S, and any other contaminants as WO 2009/065843 PCT/EP2008/065797 - 13 HCN, COS takes place. After exiting the C0 2
/H
2 S removal system (8), the cleaned reducing gas (13) is expanded in an expander (14) whereby power (15) is produced to be used in the current process or in a separate process. The 5 reducing gas exiting the expander via line (16) is further heated in a heater (17) and is directed as a stream (18) to a DRI furnace (19) where it is used as a reducing gas to be contacted with the iron ore (20). The resulting iron is discharged via stream (21). The off-gas 10 (22) of the DRI furnace (19) is directed to a CO 2 removal system (23) wherein CO 2 is separated thereby obtaining a second stream comprising CO 2 and H 2 S (24) and a recycle reducing gas comprising CO and H 2 (35). The recycle reducing gas comprising CO and H 2 (35) is recycled to the 15 DRI furnace (19) via heater (17), by combining stream (35) with stream (16). In case the sulphur content of the second stream comprising CO 2 and H 2 S (24) is more than 10 ppmv, the said stream (24) is directed as stream (25) to a liquid redox process type unit (10) where it joins the 20 first stream comprising CO 2 and H 2 S (9) exiting the C0 2
/H
2 S removal system (8). Gas treatment can take place in separate systems (8) and (23), or it can take place in a single system. The sulphur obtained in the liquid redox process type unit (10) is discharged via stream (11) 25 while the CO 2 exits the liquid redox process type unit (10) as stream (29). A part (30) of stream (29) can be directed to any other suitable process where CO 2 is used via the stream (32). Another part of the stream (29) is used as carrier gas (2) for carrying the carbonaceous 30 feed (1) to the gasifier (4). In case that sulphur content of the stream (24) is less than 10 ppmv, the gas stream (24) may by-pass the liquid redox process type unit (10) as stream (31). This stream may also find use as the above stream (32) or as carrier gas (2).
Claims (11)
1. Process to prepare elemental iron by contacting an iron ore feed with a reducing gas to obtain iron and an off-gas, wherein the reducing gas is prepared by performing the following steps 5 (a) partially oxidizing a mixture consisting of a sulphur containing solid carbonaceous fuel and gaseous CO 2 as carrier medium with oxygen, by supplying an oxygen containing gas and the solid carbonaceous fuel to a burner, thereby obtaining a gas comprising H 2 , CO, CO 2 10 and H 2 S; (b) removing CO 2 and H 2 S from the gas obtained in step (a) to obtain the reducing gas comprising H 2 and CO and a first stream comprising CO 2 and H 2 S; (c) reducing the content of H 2 S in the first stream 15 comprising CO 2 and H 2 S obtained in step (b) in a liquid redox type process and (d) recycling at least part of the CO 2 obtained in step (c) to step (a).
2. Process according to claim 1, wherein 20 Co 2 and H 2 S are removed from the off-gas of the contacting process to obtain a recycle reducing gas comprising CO and H 2 and a second stream comprising CO 2 and H 2 S, and wherein the recycle reducing gas is used as reducing gas, and 25 wherein a mixture of the first and second stream comprising CO 2 and H 2 S is subjected to step (c).
3. Process according to any one of claims 1-2, wherein the weight ratio of CO 2 to the carbonaceous fuel in 30 step (a) is less than 0.5 on a dry basis. WO 2009/065843 PCT/EP2008/065797 - 15
4. Process according to any one of claims 1-3, wherein the solid carbonaceous fuel is chosen from the group of coal, petroleum coke, peat and solid biomass.
5. Process according to any one of claims 1-4, wherein 5 the gas obtained in step (a) also comprises HCN and COS and wherein step (b) is performed by (i) contacting the gas as obtained in step (a) with a HCN/COS hydrolysis catalyst to convert HCN to NH 3 and COS to H 2 S, followed by removal of water and ammonia from the 10 gas by cooling and/or scrubbing; (ii) contacting the gas obtained in step (i) with a suitable solvent, which is selective for absorbing CO 2 and H 2 S
6. Process according to claim 5, wherein the solvent 15 comprises one or more compounds selected from the group of N-methylpyrrolidone (NMP), dimethyl ether of polyethylene glycol (DMPEG), methanol or an amine such as di-isopropanol amine (DIPA) or mixtures of amines with sulfolane. 20
7. Process according to claim 6 wherein the solvent comprises an amine and sulfolane.
8. Process according to any one of claims 1-7, wherein step (c) is performed by liquid redox type process by contacting the stream of CO 2 and H 2 S obtained in step (b) 25 with an aqueous reactant solution comprising iron (III) chelate of an organic acid or complex reactant system to produce elemental sulphur which is recovered as a by product of the present process either prior to or subsequent to regeneration of the reactant. 30
9. Process according to any one of claims 1-8, wherein a part of the CO 2 as obtained in step (c) is used for one of the following processes being enhanced oil recovery, CO 2 sequestration or coal bed methane extraction. WO 2009/065843 PCT/EP2008/065797 - 16
10. Process according to claim 9, wherein a part of the CO 2 is injected into the subterranean zone to obtain a desired pressure in said subterranean zone such to enhance the recovery of a hydrocarbon containing stream 5 as produced from said subterranean zone.
11. Process according to any one of claims 1-10, wherein part of the reducing gas obtained in step (b) is used as a fuel in a gas turbine to generate power.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07121142 | 2007-11-20 | ||
EP07121142.9 | 2007-11-20 | ||
PCT/EP2008/065797 WO2009065843A2 (en) | 2007-11-20 | 2008-11-19 | Process for production of elemental iron |
Publications (1)
Publication Number | Publication Date |
---|---|
AU2008327918A1 true AU2008327918A1 (en) | 2009-05-28 |
Family
ID=39271080
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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AU2008327918A Abandoned AU2008327918A1 (en) | 2007-11-20 | 2008-11-19 | Process for production of elemental iron |
Country Status (6)
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US (1) | US20090133535A1 (en) |
EP (1) | EP2209922A2 (en) |
JP (1) | JP2011503363A (en) |
AU (1) | AU2008327918A1 (en) |
WO (1) | WO2009065843A2 (en) |
ZA (1) | ZA201002945B (en) |
Families Citing this family (5)
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WO2010020655A1 (en) * | 2008-08-21 | 2010-02-25 | Shell Internationale Research Maatschappij B.V. | Improved process for production of elemental iron |
AT508522B1 (en) * | 2009-07-31 | 2011-04-15 | Siemens Vai Metals Tech Gmbh | REFORMERGAS-BASED REDUCTION PROCESS WITH REDUCED NOX EMISSION |
US8518356B2 (en) * | 2010-07-27 | 2013-08-27 | Air Products And Chemicals, Inc. | Method and apparatus for adjustably treating a sour gas |
US20150306541A1 (en) * | 2014-03-21 | 2015-10-29 | Joseph Naumovitz | Methods for treating furnace offgas |
CN108014598B (en) * | 2016-11-02 | 2020-05-12 | 中国石油化工股份有限公司 | Non-methane alkane in low-temperature methanol washing tail gas of crushed coal is removed and C is recovered2+Hydrocarbon system and method |
Family Cites Families (6)
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US2740706A (en) * | 1951-10-10 | 1956-04-03 | Texaco Development Corp | Method of reducing metal oxides |
BE791243A (en) * | 1971-12-23 | 1973-05-10 | Texaco Development Corp | PROCESS FOR PRODUCING A REDUCING GAS MIXTURE |
US3868817A (en) * | 1973-12-27 | 1975-03-04 | Texaco Inc | Gas turbine process utilizing purified fuel gas |
USH825H (en) * | 1988-05-20 | 1990-10-02 | Exxon Production Research Company | Process for conditioning a high carbon dioxide content natural gas stream for gas sweetening |
AT402825B (en) * | 1994-06-23 | 1997-09-25 | Voest Alpine Ind Anlagen | METHOD FOR DIRECTLY REDUCING IRON-OXIDATING MATERIAL |
US6149859A (en) * | 1997-11-03 | 2000-11-21 | Texaco Inc. | Gasification plant for direct reduction reactors |
-
2008
- 2008-11-19 JP JP2010534459A patent/JP2011503363A/en active Pending
- 2008-11-19 EP EP20080851362 patent/EP2209922A2/en not_active Withdrawn
- 2008-11-19 AU AU2008327918A patent/AU2008327918A1/en not_active Abandoned
- 2008-11-19 WO PCT/EP2008/065797 patent/WO2009065843A2/en active Application Filing
- 2008-11-20 US US12/275,041 patent/US20090133535A1/en not_active Abandoned
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- 2010-04-28 ZA ZA2010/02945A patent/ZA201002945B/en unknown
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US20090133535A1 (en) | 2009-05-28 |
WO2009065843A3 (en) | 2009-07-09 |
EP2209922A2 (en) | 2010-07-28 |
JP2011503363A (en) | 2011-01-27 |
WO2009065843A2 (en) | 2009-05-28 |
ZA201002945B (en) | 2010-12-29 |
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