US20140083252A1 - Reduction of metal oxides using gas stream containing both hydrocarbon and hydrogen - Google Patents

Reduction of metal oxides using gas stream containing both hydrocarbon and hydrogen Download PDF

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Publication number
US20140083252A1
US20140083252A1 US14/123,020 US201214123020A US2014083252A1 US 20140083252 A1 US20140083252 A1 US 20140083252A1 US 201214123020 A US201214123020 A US 201214123020A US 2014083252 A1 US2014083252 A1 US 2014083252A1
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gas
reducing
hydrocarbon
rich fraction
volume
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English (en)
Inventor
Christian Boehm
Robert Millner
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Primetals Technologies Austria GmbH
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Siemens VAI Metals Technologies GmbH Austria
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Publication of US20140083252A1 publication Critical patent/US20140083252A1/en
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/06—Making pig-iron in the blast furnace using top gas in the blast furnace process
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • 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
    • 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
    • C21B2100/24—Increasing the gas reduction potential of recycled exhaust gases by shift reactions
    • 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
    • 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
    • C21B2100/44—Removing particles, e.g. by scrubbing, dedusting
    • 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
    • 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
    • C21C2100/02—Treatment of the exhaust gas
    • 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
    • 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
    • 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
    • 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
    • Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
    • 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
    • Y02P10/25—Process efficiency

Definitions

  • Described below are a process for reducing metal oxides, such as iron oxides, using a gas stream containing both hydrocarbon and hydrogen and a device for carrying out such a process.
  • Coke oven gas is formed when coke is generated in integrated smelting works or stand-alone production plants and is used to date, for example, for reinforcing the heating value of the blast furnace top gases before use thereof in recuperators, as fuel gas in slab reheating furnaces or roller hearth furnaces, and for electricity generation in power plants.
  • coke oven gas is also used for generating technically pure hydrogen, for example for use in annealing furnaces.
  • Typical coke oven gas compositions formed in integrated smelting works are as follows
  • the coke oven gas contains components such as hydrogen and carbon monoxide which are readily usable for reducing metal oxides in general, and iron oxides in particular, on account of the hydrocarbon content, it can only be used with restrictions for reducing metal oxides, especially iron oxides, in a reducing unit, since, as a consequence of highly endothermic reactions of the hydrocarbons proceeding on the introduction of coke oven gas into the reducing unit, for example hydrocarbon CH 4
  • the reduction temperature would decrease too greatly, which in turn would greatly restrict the productivity of the reducing unit.
  • Described below are a process which permits the use of a gas stream containing hydrocarbon and hydrogen for reducing metal oxides and a device for carrying out such a process.
  • This process for reducing metal oxides uses a gas stream containing not only hydrocarbon but also hydrogen, which is characterized in that the gas stream containing not only hydrocarbon but also hydrogen is separated into a hydrogen-rich fraction and a hydrocarbon-rich fraction, and subsequently at least a subquantity of the hydrocarbon-rich fraction is subjected to at least one operation of the group
  • Metal oxides can be, for example, iron oxides, or oxides of nickel, copper, lead, cobalt.
  • the reduction of the metal oxides proceeds to form extensively metalized metal—that is to say the degree of metalization is greater than or equal to 90%, which may be greater than or equal to 92%, for example sponge iron.
  • the gas stream containing not only hydrocarbon but also hydrogen can contain one or two or more types of hydrocarbon.
  • C n H 2n applies, for example ethene.
  • C n H 2n applies, for example ethene.
  • aromatic hydrocarbons such as benzene or toluene.
  • one or more types of hydrocarbon having the general formula C n H m can also be present, wherein m can be
  • the gas stream containing not only hydrocarbon but also hydrogen is separated into a hydrogen-rich fraction and a hydrocarbon-rich fraction.
  • the hydrocarbon-rich fraction contains not only hydrocarbons, but also further components such as argon, nitrogen, carbon monoxide, carbon dioxide and steam.
  • the term hydrocarbon-rich relates to the fact that this fraction, compared with the gas stream containing not only hydrocarbon but also hydrogen, has a higher content of hydrocarbon.
  • the hydrogen-rich fraction contains not only hydrogen.
  • hydrogen-rich relates to the fact that this fraction, compared with the gas stream containing not only hydrocarbon but also hydrogen, has a higher content of hydrogen.
  • partial oxidation may be performed first using technically pure oxygen for the purpose of temperature elevation, and subsequently reforming is performed using CO 2 and H 2 O, for example in an autothermal reformer.
  • the reformer does not need to be fired, because no feed line of fuel gas to the autothermal reformer is necessary. This saves expenditure on construction and reduces the exhaust gases of the reformer.
  • the total amount of hydrocarbons is not oxidized, but only a part of the amount of hydrocarbons—in the context of this application, this is also termed partial oxidation.
  • the total amount of hydrocarbons is not reformed, but a predominant part of the amount of hydrocarbons.
  • the hydrocarbon-rich fraction obtained in the separation After at least a subquantity of the hydrocarbon-rich fraction obtained in the separation has been subjected to at least one operation of the group, it is introduced at least as a component of a reducing gas into a reducing unit containing the metal oxides—this means of course that the product obtained in the operation or operations is introduced.
  • the reducing gas can also contain other components which may optionally be added before a mixture obtained in the addition is introduced as reducing gas into the reducing unit.
  • the hydrocarbon content of the subquantity is set by the at least one operation of the group in such a manner that the hydrocarbon content in the reducing gas, on entry into the reducing unit, is less than 12% by volume, such as less than 10% by volume, particularly less than 8% by volume, but greater than 1% by volume, desirably greater than 2% by volume, particularly desirably greater than 3% by volume. These limits are included herein.
  • the lower limit of the hydrocarbon content is determined, for example, in the reduction of iron oxides, by the required carbon content—carbon bound as Fe 3 C or elemental carbon—in the reduced product for the steelworks—there, for example, an electric arc furnace. With increasing carbon content in the reduced product, the energy requirement in the subsequent treatment in the electric arc furnace decreases.
  • a hydrocarbon content in the reducing gas on entry into the reducing unit in the range of the lower limit is used, for example, for generating a minimum content of carbon in a sponge iron, in particular in the form of Fe 3 C, or such a hydrocarbon content is necessary optionally for controlling the temperature in the reducing unit.
  • HBI hot briquetted iron
  • the gas stream containing not only hydrocarbon but also hydrogen is coke oven gas.
  • coke oven gas in an integrated smelting works, is usually formed in any case, or, in a stand-alone coking plant, is only used for electricity generation, or is flared off without being used. Using the process, it can be utilized for efficient iron production; the material utilization thereof achieved in this case has a higher efficiency than, for example, utilization for electricity generation.
  • An integrated smelting works is taken to mean a steel generation route which consists, inter alia, of coking plant, sintering plant and blast furnace.
  • the gas stream containing not only hydrocarbon but also hydrogen can also be gas generated in a coal gasifier.
  • the gas stream containing not only hydrocarbon but also hydrogen is separated into a hydrogen-rich fraction and a hydrocarbon-rich fraction by at least one operation of the group
  • the pressure-swing adsorption proceeds, for example, in a PSA or VPSA plant, wherein PSA means Pressure Swing Adsorption and VPSA means Vacuum Pressure Swing Adsorption. More desirably, a prepurification of the gas stream proceeds before the pressure-swing adsorption, for example in a prepurification appliance for separating off tar and dust using tar filters made of fibers or adsorption materials.
  • a gas stream containing not only hydrocarbon but also hydrogen, for example coke oven gas in the case of an appropriate design of the plant size of pressure-swing adsorption plants and by operation using correspondingly designed cycle times using a PSA plant or a VPSA plant can be separated into a hydrogen-rich fraction and a hydrocarbon-rich fraction.
  • the hydrogen is formed on the product side virtually without a significant pressure drop.
  • the hydrocarbon-rich fraction is formed at very low pressure or a vacuum and is then compressed to the required pressure subsequently in the process.
  • the separation proceeds on the basis of the differing permeability of a membrane. Hydrogen is produced in this case in the concentrated state on the low-pressure side of the membrane.
  • the reducing gas introduced into the reducing unit containing the metal oxides is generated by mixing two components, wherein the one component is obtained by oxidizing and/or reforming at least one subquantity of the hydrocarbon-rich fraction.
  • corresponding feed lines are present for introducing auxiliary reducing gases to the proportion of the hydrocarbon-rich fraction, or optionally to the total amount of the hydrocarbon-rich fraction, which has been subjected to at least one operation of the group
  • the mixing ratio of the two components is set in dependence on a preset temperature for the mixture. In this manner, it is ensured that the reducing gas is in the temperature region which is favorable in terms of the process and economics for reducing metal oxides.
  • the reaction rate in the reducing reactor—kinetics can be set optimally.
  • the efficiency of the reducing gas preheating can be optimized.
  • Corresponding devices for controlling the mixing ratio and also temperature measuring devices for measuring the temperature of the mixture and/or for measuring the temperatures of the components are present in a device for carrying out the process.
  • the two components are mixed after the auxiliary reducing gas has been heated in a gas furnace.
  • the temperature of the reducing gas may be in the range 780-1050° C., according to the H 2 /CO ratio in the reducing gas.
  • top gas is taken off from the reducing unit, and the auxiliary reducing gas is obtained at least in part by mixing top gas that is dedusted and substantially freed from CO 2 , and at least one further gas.
  • the reductants (CO and H 2 ) still present in the top gas are utilized again for reducing the metal oxides.
  • the at least one further gas includes the hydrogen-rich fraction obtained in the separation of the gas stream, such as coke oven gas, containing not only hydrocarbon but also hydrogen.
  • the reduction potential present in this fraction is also utilized for reducing metal oxide; utilized, especially in that the reduction rate—kinetics—is generally more rapid via hydrogen:
  • the gas furnace is operated with a fuel gas which at least in part includes at least one gas of the group
  • these gases are utilized in the process for reducing metal oxides, which increases the efficiency thereof.
  • hydrogen-rich gases are used for firing the gas furnace from below, the CO 2 emission can be kept correspondingly low.
  • the reducing unit is a reducing shaft and a first subquantity of the hydrocarbon-rich fraction is introduced directly into the reducing shaft, and a second subquantity of the hydrocarbon-rich fraction before introduction thereof into the reducing shaft is subjected to at least one operation of the group
  • the first subquantity can thus be utilized for carbonization of the metal generated in the reducing unit; for example, it can be utilized for carbonization of metallic iron.
  • the at least one gas stream containing CO 2 and/or H 2 O is added to the hydrocarbon-rich fraction before reforming using CO 2 and H 2 O.
  • this can be, for example, steam, tail gas from a CO 2 removal process—for example from the removal of CO 2 from the top gas—top gas from the reducing shaft, or converter gas. Water can also be added.
  • Corresponding feed lines for feeding one or more of these gases which exit from devices producing such gases or lines bearing such gases are present in a device for carrying out the process.
  • H 2 S is also enriched. According to an embodiment, therefore, desulfurization of the hydrocarbon-rich fraction is carried out before it is subjected to at least one operation of the group
  • the sulfur content can thereby be reduced in the largely metalized metal.
  • a desulfurization device is present, before—seen in the direction of flow—the feed line opens out into a unit for carrying out an operation of the group
  • coke oven gas The specific carbon emission factor in the case of coke oven gas is 43.7 kg of CO 2 /GJ of fuel, while in the case of natural gas it is 55.7 kg of CO 2 /GJ of fuel.
  • the use of coke oven gas is therefore considerably more environmentally friendly than the use of natural gas.
  • a further subject matter of the present application is a device for carrying out the process having a reducing unit for reducing metal oxides, having a device for separating a gas stream containing not only hydrocarbon but also hydrogen into a hydrogen-rich fraction and a hydrocarbon-rich fraction, having, arising therefrom, a feed line for the hydrocarbon-rich fraction which opens out into a unit for carrying out an operation of the group
  • the device for separating a gas stream containing not only hydrocarbon but also hydrogen into a hydrogen-rich fraction and a hydrocarbon-rich hydrogen-rich fraction may be a device for separating coke oven gas into a hydrogen-rich fraction and a hydrocarbon-rich fraction.
  • the device for separating a gas stream containing not only hydrocarbon but also hydrogen into a hydrogen-rich fraction and a hydrocarbon-rich fraction may be a device of the group
  • the one or more introduction lines may open out into the reducing unit, wherein upstream of the opening of at least one of the introduction lines into the reducing unit, an auxiliary reducing gas line for feeding auxiliary reducing gas to the reducing unit opens out into this introduction line.
  • a gas furnace may be present in the auxiliary reducing gas line.
  • x introduction lines are present, wherein x is greater than 2 or is equal to 2, of the at most x ⁇ 1 introduction lines it is true that, upstream of the opening of at least one of the introduction lines into the reducing unit, an auxiliary reducing gas line, for feeding auxiliary reducing gas to the reducing unit, opens out into this introduction line.
  • At least one introduction line is present into which no auxiliary reducing gas line opens out. Therefore, a subquantity of the hydrocarbon-rich fraction can be introduced directly into the reducing shaft without being mixed with auxiliary reducing gas; this subquantity can be used, for example, for carbonizing the metal generated in the reducing unit; for example it can be used for carbonizing metallic iron.
  • the reducing unit is a reducing shaft, for example a fixed-bed reducing shaft for carrying out a MIDREX® or HYL® reduction process.
  • the reducing unit is a fluidized-bed cascade.
  • FIG. 1 is block diagram of a device for carrying out a process in which coke oven gas is separated into a hydrogen-rich fraction and a hydrocarbon-rich fraction and the latter is subjected to an oxidation before it is introduced into a reducing shaft as part of a reducing gas.
  • FIG. 2 is block diagram of a device and procedure similar to FIG. 1 , with the difference that the hydrocarbon-rich fraction is subjected to reforming using CO 2 and H 2 O before it is introduced as part of a reducing gas into a reducing shaft.
  • FIG. 3 is block diagram of a device and procedure which chiefly differs from FIG. 1 in that a fluidized-bed cascade is present as reducing unit, and the device present for separating coke oven gas, instead of a device for pressure-swing adsorption, is a device for membrane separation.
  • FIG. 4 is block diagram of a device and procedure which chiefly differs from FIG. 1 in that a fluidized-bed cascade is present as reducing unit, and the device for separating coke oven gas, instead of a device for pressure-swing adsorption, is a device for membrane separation.
  • FIG. 1 shows a device for carrying out a process.
  • This includes, as a reducing unit for reducing metal oxides, a reducing shaft 1 which contains iron ore, that is to say iron oxides. It likewise includes a device for separating a gas stream containing not only hydrocarbon but also hydrogen, in this case a PSA or a VPSA plant 2 using pressure-swing adsorption, into a hydrogen-rich fraction and a hydrocarbon-rich fraction.
  • the gas stream containing not only hydrocarbon but also hydrogen is coke oven gas.
  • the hydrocarbon-rich fraction is partially oxidized; that is, the entire amount of substance is not oxidized, but only a part of the amount of substance of the hydrocarbon-rich fraction.
  • this gas stream is introduced as a component of a reducing gas into the reducing shaft 1 .
  • the hydrocarbon content is set in such a manner that the hydrocarbon content in the reducing gas is less than 12% by volume on entry into the reducing shaft.
  • the gas stream obtained in the unit for carrying out oxidation using technically pure oxygen 4 is mixed with an auxiliary reducing gas, the resultant mixture is introduced as reducing gas into the reducing shaft 1 .
  • the two components of the reducing gas are mixed after the auxiliary reducing gas has been heated in a gas furnace 6 .
  • the auxiliary reducing gas is added via an auxiliary reducing gas line 7 for feeding auxiliary reducing gas to the reducing unit 1 , which reducing gas line 7 opens out into the introduction line 5 .
  • Via the introduction line 5 therefore, not only the gas stream obtained in the unit for carrying out oxidation using technically pure oxygen 4 , but also the auxiliary reducing gas is introduced into the reducing shaft 1 , specifically as a mixture termed reducing gas.
  • the temperature preset of the auxiliary reducing gas which is heated in the gas furnace 6 is set in dependence on a temperature preset for the mixture.
  • the gas furnace 6 is arranged in the auxiliary reducing gas line 7 .
  • top gas is conducted away via a top gas outlet line 8 .
  • the auxiliary reducing gas in the example shown, is formed by mixing dedusted—a gas scrubber 9 is present in the top gas outlet line 8 —top gas that is largely freed from CO 2 —a CO 2 removal plant 10 is present in the top gas outlet line 8 —and a further gas.
  • the further gas is the hydrogen-rich fraction obtained in the separation of the coke oven gas.
  • the gas furnace 6 is operated using a fuel gas.
  • the fuel gas is burnt with feed of air through an air feed line 11 opening out into the gas burner.
  • the fuel gas contains gases of the group
  • auxiliary reducing gas can be obtained by mixing top gas that is dedusted and largely freed from CO 2 and the hydrogen-rich fraction obtained in the separation of the coke oven gas, not only the hydrogen fraction outlet line 17 but also the top gas outlet line 8 open out into the auxiliary reducing gas line 7 .
  • the feed line for coke oven gas 15 exits from a coke oven gas source that is not shown and opens out into the PSA or VPSA plant 2 .
  • introduction line 5 In the device shown in FIG. 1 , two introduction lines opening out into the reducing shaft 1 are present.
  • the introduction line 5 called first introduction line
  • a further introduction line, called second introduction line 18 branches off from the feed line for the hydrocarbon-rich fraction 3 and opens out into the reducing shaft.
  • second introduction line 18 a subquantity of the hydrocarbon-rich fraction can be introduced directly into the reducing shaft. This subquantity can thus be used for carbonizing the metallic iron, in this case sponge iron, generated in the reducing shaft 1 .
  • a cooling gas line for feeding cooling gas into the reducing shaft 1 is not shown for reasons of clarity; in principle, for the purpose of carbonization, a subquantity of the hydrocarbon-rich fraction could also be added to the cooling gas via a corresponding branch from the feed line for the hydrocarbon-rich fraction 3 which opens out into the cooling gas line.
  • the auxiliary reducing gas can be partially oxidized with feed of technically pure oxygen, if this is wanted for temperature elevation.
  • the hydrocarbon-rich fraction instead of a partial oxidation, is subjected to reforming using CO 2 and H 2 O before it is introduced as part of a reducing gas into a reducing shaft.
  • Plant parts and processes which are identical to FIG. 1 are not described again here for the most part, and the reference signs for the same plant parts, for better clarity, are not entered into the drawing.
  • the reforming takes place in a unit for carrying out reforming using CO 2 and H 2 O, here a reformer 21 , into which the feed line for the hydrocarbon-rich fraction 3 opens out. Off-gas from the reformer 21 is used via a heat exchanger 22 for heating the hydrocarbon-rich fraction before entering into the reformer 21 .
  • a plurality of feed lines 23 a, 23 b which open out into the feed line for the hydrocarbon-rich fraction 3 , before entry into the reformer 21 , a plurality of CO 2 -containing gas streams are added to the hydrocarbon-rich fraction.
  • feed line 23 a tail gas from the CO 2 removal plant 10 is added; the feed line 23 a arises from the tail gas feed line 12 .
  • feed line 23 b top gas is added.
  • a water feed line 24 which opens out into the feed line for the hydrocarbon-rich fraction 3 , before entry into the reformer 21 , steam and/or water is added to the hydrocarbon-rich fraction.
  • the reformer 21 can be fired using top gas, coke oven gas or with the hydrocarbon-rich fraction; corresponding lines opening out into the reformer 21 , for the sake of clarity, are not shown.
  • the hydrocarbon content in the reducing gas on entry into the reducing shaft 1 can be influenced via the feed of hydrocarbon-rich fraction.
  • the reducing unit is a fluidized-bed cascade 25 , from the last fluidized-bed reactor 26 of which, seen in the direction of flow of the reducing gas, top gas is taken off; the top gas line is given the reference sign 8 , as is the top gas line in FIG. 1 .
  • the introduction line 5 which in FIG. 1 is shown opening out into the reducing shaft 1 , is, in FIG. 3 , shown opening out into the first fluidized-bed reactor 27 , similarly seen in the direction of flow of the reducing gas.
  • a device for separating coke oven gas instead of, as in FIG. 1 , a device for pressure-swing adsorption—there is a device for membrane separation 28 .
  • hydrocarbon-rich fraction can be fed into the first introduction line 5 , which offers a possibility for influencing the hydrocarbon content in the reducing gas.
  • FIG. 4 differs from FIG. 2 by the same modifications by which FIG. 3 differs from FIG. 1 .
  • FIG. 1 in contrast to FIG. 2 , no heat exchanger 22 is present.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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US14/123,020 2011-05-30 2012-05-07 Reduction of metal oxides using gas stream containing both hydrocarbon and hydrogen Abandoned US20140083252A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ATA785/2011 2011-05-30
ATA785/2011A AT510955B1 (de) 2011-05-30 2011-05-30 Reduktion von metalloxiden unter verwendung eines sowohl kohlenwasserstoff als auch wasserstoff enthaltenden gasstromes
PCT/EP2012/058360 WO2012163628A1 (de) 2011-05-30 2012-05-07 Reduktion von metalloxiden unter verwendung eines sowohl kohlenwasserstoff als auch wasserstoff enthaltenden gasstromes

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US (1) US20140083252A1 (zh)
EP (1) EP2714942B1 (zh)
KR (1) KR101890788B1 (zh)
CN (1) CN103562412B (zh)
AT (1) AT510955B1 (zh)
AU (1) AU2012265081B2 (zh)
BR (1) BR112013030747A2 (zh)
CA (1) CA2837611A1 (zh)
RU (1) RU2013157801A (zh)
TW (1) TWI565806B (zh)
UA (1) UA111488C2 (zh)
WO (1) WO2012163628A1 (zh)
ZA (1) ZA201308896B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160083811A1 (en) * 2014-09-23 2016-03-24 Midrex Technologies, Inc. Method for reducing iron oxide to metallic iron using coke oven gas
SE2150126A1 (en) * 2021-02-03 2022-08-04 Hybrit Dev Ab Bleed-off gas recovery in a direct reduction process

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CA2837611A1 (en) 2012-12-06
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