• 专利附录
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    • 专利摘要:
    The invention relates to a process for the reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen. The gas stream containing both hydrocarbon and hydrogen is separated into a hydrogen-rich fraction and into a hydrocarbon-rich fraction. Subsequently, at least one subset of the hydrocarbon-rich fraction is subjected to at least one operation from the group oxidation with technically pure oxygen, reforming by means of C 0 2 and H 2 O. Then it is at least introduced as part of a reducing gas into a reduction unit containing the metal oxides. In this case, the hydrocarbon content is adjusted by the at least one operation from the group mentioned so that the hydrocarbon content in the reducing gas when entering the reduction unit is less than 12% by volume. The invention also relates to a device for carrying out such a method.
    公开号:AT510955A4
    申请号:T785/2011
    申请日:2011-05-30
    公开日:2012-08-15
    发明作者:Christian Dipl Ing Boehm；Robert Dipl Ing Millner
    申请人:Siemens Vai Metals Tech Gmbh；
    IPC主号:
    专利说明:

    • · · • ·*· • · 1
    2011P11617AT
    Reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen
    Field of Technology 5
    The present invention relates to a process for the reduction of metal oxides, preferably iron oxides, using a gas stream containing both hydrocarbon and hydrogen. It also relates to a device for carrying out such a method. 10
    State of the art
    Coke oven gas is produced in the production of coke in integrated steelworks or stand-alone production plants and has previously been used, for example, to support the calorific value of the blast furnace blast furnace gases prior to their use in blast furnaces, as fuel gas in slab impact or roller hearth furnaces, and for power generation in power plants. It contains as main constituents both hydrocarbons - for example one or more hydrocarbons CnH2n + 2. where n = 1 or 2 or 3 or 4; but mainly 20 methane, ie n = 1 - as well as hydrogen. Coke oven gas is also used in some integrated smelters to produce technically pure hydrogen, for example for use in annealing furnaces. Typical resulting compositions of coke oven gas in integrated smelters are as follows 2
    2011P11617AT KOG analysis (dry): h2 [vol%] 65 62.1 n2 [vol%] 2.5 incl. In balance CO [vol%] 6 6.2 CH4 [vol%] 22 21.4 cnHm [vol% ] 3 incl. In remainder co2 [vol%] 1.5 incl. In remainder h2o [vol%] saturated incl. In remainder h2s [g / Nm *] 0.35 na Tar lg / Nm3] 5 n.a. Dust Ig / Nm9] 5 n.a. Remainder [vol%] - 10.3
    Although the coke oven gas for a reduction of metal oxides in general and iron oxides in particular well usable components such as hydrogen and carbon monoxide, but can be used due to the hydrocarbon content only limited for the reduction of metal oxides, especially iron oxides, a reduction aggregate, as a result of Introduction of coke oven gas into the reduction unit of highly endothermic hydrocarbon reactions. For example, hydrocarbon CH4 CH4 2 H2 + C Cracking Δ H2ee = +74.86 [kJ / mol] 3 Fe + CH4 * Fe3C + 2 H2 carburization ΔH ^ a = + 99.7 [kJ / mol] 25 the reduction temperature too strong would decrease, which in turn would severely limit the productivity of the reduction unit.
    Summary of the invention 30
    Technical task
    It is an object of the present invention to provide a process which utilizes a hydrocarbon as well as hydrogen. " It is also possible to use a gas stream containing a reduction of metal oxides. It is also an object to provide an apparatus for carrying out such a method. 5 Technical solution
    This object is achieved by a
    Method of reducing metal oxides using both
    Hydrocarbon as well as hydrogen-containing gas stream, which is characterized in that the gas stream containing both hydrocarbon and hydrogen is separated into a hydrogen-rich fraction and into a hydrocarbon-rich fraction, and subsequently at least a subset of the hydrocarbon-rich fraction of at least one operation from the group - oxidation with technically pure oxygen, - is subjected to reforming by means of CO 2 and H 2 O 20, and then at least introduced as a constituent of a reducing gas into a reduction unit containing the metal oxides, wherein the hydrocarbon content by the at least one operation from said group is adjusted so that the hydrocarbon content in the reducing gas when entering the
    Reduction unit is less than 12% by volume, preferably less than 10% by volume, more preferably less than 8% by volume.
    Metal oxides may be, for example, iron oxides, or oxides of nickel, copper, lead, cobalt.
    The reduction of the metal oxides is preferably carried out to substantially metallized metal - that is, a degree of metallization of greater than or equal to 90%, preferably greater than or equal to 92% -, for example sponge iron. • ft • ft • ft • ft • ft • ft • ft • ft • ft • ft • ft • ft • ft ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••
    2011P11617AT
    Advantageous Effects of the Invention
    The gas stream containing both hydrocarbon and hydrogen may contain one or two or more types of hydrocarbon. For example, it contains lower saturated hydrocarbons CnH ^, where n = 1, ie methane, or n = 2, ie ethane, or n = 3, that is propane, or n = 4, ie butane or isobutane. It may also contain lower, mono- or polyunsaturated hydrocarbons, where, for example, CnH2n > for example, ethene. It may also contain aromatic hydrocarbons, such as benzene or toluene. In the gas stream containing both hydrocarbon and hydrogen may also be one or more types of hydrocarbon having the general formula CnHm be included, where m may be m = n, 15 m = 2n, m = 2n + 2.
    According to the invention, the gas stream containing both hydrocarbon and hydrogen is separated into a hydrogen-rich fraction and into a hydrocarbon-rich fraction. It contains the
    Hydrocarbon rich fraction not only hydrocarbons but also other components such as argon, nitrogen, carbon monoxide, carbon dioxide and water vapor. The term hydrocarbon rich refers to the fact that this fraction has a higher content of hydrocarbon as compared to the gas stream containing both hydrocarbon and hydrogen.
    The hydrogen-rich fraction not only contains hydrogen.
    The term hydrogen-rich refers to the fact that this fraction has a higher content of hydrogen compared to the gas stream containing both hydrocarbon and hydrogen.
    Subsequent to the separation, at least a subset of the hydrocarbon-rich fraction obtained during the separation is at least one operation from the group
    2011P11617AT 5 - Oxidation with technically pure oxygen, - Reforming with C02 and H20. It can also be subjected to a combination of these two operations. In a combination, it is preferable to first partially oxidise with technically pure oxygen for the purpose of increasing the temperature and then to reform with CO 2 and H 2 O, for example in an autothermal reformer. In an autothermal reformer no firing of the reformer is needed, which is why no supply of fuel gas to the autothermal reformer is necessary. This saves 10 construction costs and reduces the exhaust gases of the reformer.
    In this case, not the entire amount of hydrocarbons is oxidized in the oxidation, but only a portion of the molar amount of hydrocarbons - which is referred to in this application as partial oxidation. 15 In this case, not the entire amount of substance of the
    Hydrocarbons reformed, but a predominant part of the molar amount of hydrocarbons.
    By the above operations alone or in combination, the content of the hydrocarbons decreases. 20
    After at least a subset of the hydrocarbon-rich fraction obtained in the separation has been subjected to at least one operation from the said group, it is introduced at least as a constituent of a reducing gas into a reduction aggregate 25 containing the metal oxides - this is, of course, meant to mean that in the case of Operations received product is initiated.
    At least as a constituent of a reducing gas means that the reducing gas may also contain other constituents which may be mixed in before a mixture obtained during the mixing is introduced as a reducing gas into the reduction aggregate.
    According to the invention, the hydrocarbon content of the subset is adjusted by the at least one operation from the said group in such a way that the hydrocarbon content in the reducing gas upon entry into the ····· 6
    2011P11617AT
    Reduction unit below 12% by volume, preferably below 10% by volume, more preferably below 8% by volume, but above 1% by volume, preferably above 2% by volume, particularly preferably above 3% by volume. The mentioned limits are included.
    The higher the hydrocarbon content in the reducing gas when entering the reduction unit, the higher the reduction temperature - in the case of reduction shafts as a reduction unit also called the Bustlegastemperatur - must be set, or the lower the productivity of the system. In the case of a hydrocarbon content set according to the invention, the reduction temperature does not decrease so much as a result of lower endothermic reactions of the hydrocarbons that the
    Productivity of the reduction unit decreases below an economically acceptable level.
    The lower limit for the hydrocarbon content is determined, for example, in the reduction of iron oxides by the required Kohlenstoffgehait -15 carbon bonded as Fe3C or elemental carbon - in the reduced product for the steel plant - there, for example, an electric arc furnace. As the carbon content in the reduced product increases, the energy required for the subsequent treatment in the electric arc furnace decreases. A hydrocarbon content in the reducing gas entering the reduction unit in the region 20 of the lower limit is used, for example, for producing a minimum content of carbon in a sponge iron, in particular in the form of Fe 3 C, or such a hydrocarbon content is possibly required for temperature control in the reduction unit , In addition, for example, in the production of sponge iron, 25 hot briquetting plants - HBI plants, HBI stands for hot briquetted iron - as are common in DR plants - DR stands for direct reduction - also certain minimum briquetting temperatures - preferably> 650eC to avoid increased Maintenance costs and obtaining product densities > 5 g / cm3 which can not be achieved by excessive cooling of the DRI in the reduction unit due to 30 endothermic reactions.
    In a preferred embodiment, the gas stream containing both hydrocarbon and hydrogen is coke oven gas. 2011P11617AT 7
    Preferably, therefore, because coke oven gas accumulates in an integrated steelworks usually anyway or used in a stand-alone coking plant only for power generation or flared without use.
    By the inventive method, it can be used for efficient iron production 5; the resulting material use has a higher efficiency than, for example, a use for power generation.
    Under an integrated steelworks is a steelmaking route which among other things consists of coking plant, sinter plant and blast furnace to understand.
    The gas stream containing both hydrocarbon and hydrogen may also be gas produced in a coal gasifier.
    According to a preferred embodiment, the separation of the gas stream containing both hydrocarbon and hydrogen into a hydrogen-rich fraction 15 and into a hydrocarbon-rich fraction by at least one operation from the group - pressure swing adsorption, - membrane separation. 20 The pressure swing adsorption takes place, for example, in a PSA or VPSA system, where PSA stands for Pressure Swing Adsorption, and VPSA for Vacuum Pressure Swing Adsorption. Preferably, prior to pressure swing adsorption, a pre-purification of the gas stream, for example in a pre-cleaning device for the separation of tar and dust by means of 25 tar filters made of fibers or adsorbents. Due to the different adsorption, both a hydrocarbon and hydrogen-containing gas stream such as coke oven gas with a suitable design of the size of Druckwechseladsorptions systems and by operating with appropriately designed cycle times by a PSA plant or a VPSA plant in a hydrogen-rich fraction and in a Separated hydrocarbon-rich fraction. The hydrogen falls on the product side without practically significant pressure loss. The hydrocarbon - rich fraction falls under very low pressure or under * «2011P11617AT 8
    Vacuum and is then compressed to the pressure required in the following steps.
    In membrane separation, the separation is due to the different 5 permeability of a membrane. Hydrogen falls concentrated on the low pressure side of the membrane.
    According to a preferred embodiment, at least a portion of the at least one subset of the hydrocarbon-rich fraction 10 which has been subjected to at least one operation from the group oxidation with technically pure oxygen, reforming by means of CO 2 and H 2 O, is mixed with an additional reducing gas 15, before the resulting mixture of these two components is introduced as a reducing gas into the metal oxide-containing reduction aggregate. In this case, the reducing gas introduced into the reduction unit containing the metal oxides is generated by the mixing of two components, the one component being obtained by oxidation and / or reforming of at least one subset of the hydrocarbon-rich fraction. 25
    In such a procedure, other gases with reduction potential can be used materially for the reduction of metal oxides by being admixed as an additional reducing gas. In an apparatus for carrying out such a method according to the invention are corresponding feed lines for the introduction of additional reducing gases to the proportion or optionally the entire amount of the hydrocarbon-rich fraction, the at least one operation from the group
    2011P11617AT θ
    - oxidation with technically pure oxygen, - reforming by means of C02 and H2O, was present. In a preferred embodiment, the mixing ratio of the two components is set as a function of a temperature specification for the mixture. In this way, it is ensured that the reducing gas is in the process area for the reduction of metal oxides and economically favorable temperature range. By adjusting the temperature 10, the reaction rate in the reduction reactor -
    Kinetics - optimally adjusted. Furthermore, the efficiency of the reduction gas preheating can be optimized.
    Corresponding devices for controlling the mixing ratio and 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 method according to the invention.
    According to a preferred embodiment, the two components 20 are mixed after the additive reducing gas has been heated in a gas furnace. This allows an improved temperature adjustment for the reducing gas. The temperature for the reducing gas should preferably be in the range 780-1050 ° C, depending on the H2 / CO ratio in the reducing gas. According to a preferred embodiment, top gas is withdrawn from the reduction unit, and the additional reduction gas is recovered at least partially by mixing dedusted top gas largely freed from CO 2 and at least one further gas. In this way, the reductants (CO and H2) still contained in the top gas are utilized again for the reduction of the 30 metal oxides.
    Advantageously, the at least one further gas comprises the hydrogen-rich hydrofluorocarbon obtained in the separation of the gas stream containing both hydrocarbon and hydrogen, preferably coke oven gas, with Μ 10
    2011P11617AT
    Fraction. In this way, the reduction potential contained in this fraction for the reduction of metal oxides is exploited; exploited mainly because the reduction rate - kinetics - is generally faster over hydrogen: 5 3 Fe 2 O 3 + H 2 Fe 3+ + H 2 O 2 = 292 = -2.72 [kJ / mol]
    Fe304 + H2 3 Fe0 + H20 ΔΗ29Β = +59.83 [kJ / mol]
    FeO + 3H2 Fe + 2H2 + H20 ΔΗ298 = +29.60 [kJ / mol] 10 Advantageously, the gas furnace is operated with a fuel gas consisting at least partly of at least one gas from the group - Tailgas resulting from the removal of CO 2 from the top gas Gas containing both hydrocarbons and hydrogen, preferably coke oven gas, hydrogen-rich fraction obtained by separating from both the hydrocarbon and hydrogen-containing gas stream, preferably coke oven gas, by separation of both hydrocarbon and hydrogen-containing gas Gas stream, preferably coke oven gas obtained
    Hydrocarbon - rich fraction.
    In this way, these gases are used in the process for the reduction of metal oxides 25, which increases its cost-effectiveness. When using hydrogen-rich gases for underfiring the gas furnace, the CO 2 emission can be kept correspondingly low.
    Individual, several or all of the corresponding fuel gas supply lines to the gas oven are provided in an apparatus for carrying out the method according to the invention: a tail gas feed line for feeding tail gas resulting from the removal of CO2 from the top gas, which proceeds from the CO 2 removal process.
    • I • I 11
    2011P11617AT - a Topgaszuleitung for supplying Topgas, emanating from a top gas from the reduction unit derived Topgasableitung. a fuel gas feed line for feeding both hydrocarbon and 5 hydrogen-containing gas stream emanating from a supply line for a gas stream containing both hydrocarbon and hydrogen, which itself into a device for separating a gas stream containing both hydrocarbon and hydrogen into a hydrogen-rich fraction and into a hydrocarbon-rich fraction 10 opens. a fuel gas feed line for feeding gas stream containing both hydrocarbon and hydrogen, preferably coke oven gas, to a hydrogen-rich fraction obtained from a device for separating a gas stream containing both hydrocarbon and hydrogen into a hydrogen-rich fraction and into a gas-rich fraction A hydrocarbon-rich fraction, 20 or from a hydrogen-rich fraction effluent, which itself originates from a gas-stream separation apparatus comprising both hydrocarbon and hydrogen in a hydrogen-rich fraction and a hydrocarbon-rich fraction, - a fuel gas feed line of hydrocarbon-rich hydrogen-rich fraction 30 obtained from separation of the gas stream containing both hydrocarbon and hydrogen, preferably coke-oven gas, starting from a feed line for the hydrocarbon ff - rich hydrogen-rich fraction, which itself from a device for separating a gas stream containing both hydrocarbon and hydrogen in • ··· * · · 4 * *
    Or a device for separating a gas stream containing both hydrocarbon and hydrogen into a hydrogen-rich fraction and into a hydrocarbon-rich fraction.
    Advantageously, the reduction unit is a reduction shaft, and a first portion of the hydrocarbon-rich fraction is introduced directly into the reduction pit, and a second portion of the hydrocarbon-rich fraction is entrained prior to its introduction into the reduction pit of at least one group oxidation operation technically pure oxygen, 20 - reforming by means of CO 2 and H 2 O, and then introduced at least as a constituent of a reducing gas into a reduction aggregate containing the metal oxides, the hydrocarbon content 25 being adjusted by the at least one operation from the said group such that the Hydrocarbon content in the reducing gas when entering the reduction unit is less than 12% by volume, preferably less than 10% by volume, particularly preferably less than 8% by volume.
    The first subset can thus be used for carburizing the metal produced in the reduction unit; For example, it can be used for carburizing metallic iron. 30
    ♦ ·· 13
    2011P11617AT
    Advantageously, before the reforming by means of CO 2 and H 2 O, at least one CO 2 and / or H 2 0 -containing gas stream is added to the hydrocarbon-rich fraction. This can be, for example, steam, Taiigas from a CO 2 removal process - for example, from the removal of CO 2 5 from the top gas top gas from the reduction shaft, or crucible gas. It can also be added to water.
    In this way, these gases are used in the process of reducing the metal oxides, which increases its cost-effectiveness and reduces the environmental emissions 10, since CO 2 is converted back into CO.
    Corresponding supply lines for the supply of one or more of these gases, which emanate from such gas-producing devices or lines carrying such gases, are present in a device for carrying out the method according to the invention. H2S is also enriched in the hydrocarbon-rich fraction. Therefore, according to a preferred embodiment desulfurization of the hydrocarbon-rich fraction is carried out before it is subjected to at least one operation from the group oxidation with technically pure oxygen, reforming by means of CO 2 and H 2 O or. As a result, the sulfur content in the largely metallized metal can be reduced. In a device for carrying out a process according to the invention, a desulphurisation device is then present in a feed line for the hydrocarbon-rich fraction 3, before, viewed in the flow direction, this into an aggregate for carrying out an operation from the group oxidation with technically pure oxygen - Reforming using C02 and H20, opens. ··· * ♦ · * «« «« i «• * • φ • # · * ··· t ♦ · · * • * * * • · * * * 2011P11617AE 14
    The process according to the invention has the following advantages: efficient use of coke oven gas for the reduction of metal oxides, especially for the reduction of iron oxides for sponge iron production, an advantage over the thermal utilization of coke oven gas which has hitherto been achieved according to the prior art, compared with the use of natural gas Reduction of metal oxides, especially for the reduction of iron oxides for sponge iron production, high economic advantages over natural gas, as the coke oven gas is produced at lower prices - very environmentally friendly method, especially by low CO 2 and NO x, 10 emissions, as in some embodiments, a very hydrogen-rich gas can be used for reduction, and on the other hand, by using low-carbon gases in the reformer and / or gas furnace their emissions can be further reduced. - In addition, some of the CO2 emissions in the reformer can be converted back into 15 CO and subsequently used for reduction.
    The specific carbon emission factor for coke oven gas is 43.7 kg CO2 / GJ fuel, while for natural gas it is 55.7 kg CO2 / GJ fuel. The use of coke oven gas is thus much more environmentally friendly than the use of natural gas. 20
    A further subject of the present application is an apparatus for carrying out the process according to the invention with a reduction unit for the reduction of metal oxides, with a device for separating a gas stream containing both hydrocarbon and hydrogen into a hydrogen-rich fraction and into a hydrocarbon-rich fraction one from this springing up
    Feed line for the hydrocarbon - rich fraction, which opens into an aggregate for carrying out a group 30 operation - oxidation with technically pure oxygen, - reforming by means of CO 2 and H 2 O, and one or more feed lines for the introduction of at least one gas stream from the group
    Hydrocarbon - rich fraction, - in the aggregate for carrying out oxidation with technical grade. English:. German: v3.espacenet.com/textdoc gas stream obtained in pure oxygen, gas stream obtained in the unit for carrying out reforming by means of CO 2 and H 2 O 5, into the reduction unit.
    Preferably, the apparatus for separating a gas stream containing both hydrocarbon and hydrogen into a hydrogen-rich fraction and into a hydrocarbon-rich hydrogen-rich fraction is an apparatus for separating coke oven gas into a hydrogen-rich fraction and a hydrocarbon-rich hydrogen-rich fraction. Preferably, the apparatus for separating a gas stream containing both hydrocarbon and hydrogen into a hydrogen-rich fraction and a hydrocarbon-rich fraction is one of the group - pressure swing adsorption apparatus, 20 - membrane separation apparatus.
    Preferably, the one or more introduction lines open into the reduction unit, wherein before the mouth of at least one of the introduction lines into the reduction unit
    Additional reducing gas line for supplying additional reducing gas to the reduction unit 30 opens into this discharge line.
    Preferably, a gas furnace is present in the additional reducing gas line before the mouth of the additional reducing gas line in the introduction line.
    2011P11617A1 •••• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • ft · ft · ft ft • «
    Preferably x introduction lines are present, wherein x is greater than or equal to 2, of which at a maximum of x-1 introduction lines, that before the mouth of at least one of the introduction lines into the reduction unit a 5 additional reduction gas line for supplying additional reducing gas to the reduction unit in this introduction leads.
    In this way, at least one introduction line is present, into which no additional Reduktionsgasieitung opens. Thus, a portion of the hydrocarbon-rich fraction may be introduced directly into the reduction well without being mixed with supplemental reducing gas; this subset can be used, for example, for carburizing the metal produced in the reduction unit; For example, it can be used for carburizing metallic iron. According to one embodiment, the reduction unit is a reduction shaft, for example a fixed-bed reduction shaft for carrying out a MIDREX® or HYL® reduction method.
    In one embodiment, the reduction aggregate is a fluidized bed cascade.
    Brief description of the drawings
    The invention will be explained with reference to embodiments based on the following schematic and exemplary figures.
    FIG. 1 shows an apparatus for carrying out a process according to the invention, in which coke-oven gas is separated into a hydrogen-rich fraction and a hydrocarbon-rich fraction, and the latter is subjected to oxidation before being introduced into a reduction shaft as part of a reducing gas.
    FIG. 2 shows an apparatus and process analogous to FIG. 1, with the difference that the hydrocarbon-rich fraction of a reactor has a high viscosity
    Reforming is subjected by means of C02 and H20 before it is introduced as part of a reducing gas in a reduction shaft.
    FIG. 3 shows an apparatus and method according to the invention, which differs from FIG. 1 mainly in that a
    Fluidized bed cascade is present as a reduction unit, and as a device for separating Koksofengas instead of a device for pressure swing adsorption there is a device for membrane separation. FIG. 4 shows an apparatus and method according to the invention, which differs from FIG. 1 mainly in that a fluidized-bed cascade is present as a reduction unit, and there is a device for membrane separation instead of a device for pressure swing adsorption as a device for separating coke oven gas. 15
    Description of the embodiments
    FIG. 1 shows an apparatus for carrying out a method according to the invention. This comprises as a reduction unit for the reduction of 20 Metalioxiden a reduction shaft 1 containing iron ore, ie iron oxides. It also comprises an apparatus for separating a gas stream containing both hydrocarbon and hydrogen, in this case a PSA or a VPSA plant 2 by means of pressure swing adsorption, into a hydrogen-rich fraction and into a hydrocarbon-rich fraction. In the present example, the gas stream containing both hydrocarbon and hydrogen is coke oven gas. From the PSA or VPSA plant 2, a feed line for the hydrocarbon-rich fraction 3, which empties into an aggregate for carrying out an oxidation with technically pure oxygen 4, originates. In this unit for carrying out an oxidation with technically pure oxygen 4, the hydrocarbon-rich fraction is partially oxidized; that is, it is not the entire amount of substance oxidized, but only a portion of the molar amount of the hydrocarbon-rich fraction. By way of an introduction line 5 for introducing the gas stream obtained in the unit for the performance of oxidation with technically pure oxygen 4, + · · «** ** ** ** ** ** ** ** ** ** ** ** ** ** This is introduced as a component of a reducing gas into the reduction shaft 1. In the partial oxidation, the hydrocarbon content is adjusted so that the hydrocarbon content in the reducing gas entering the reduction shaft is less than 12% by volume. 5
    The gas stream obtained in the aggregate for carrying out oxidation with technically pure oxygen 4 is mixed with an additional reducing gas, the resulting mixture is introduced as a reducing gas into the reduction shaft 1. The two components of the reducing gas 10 are mixed after the additive reducing gas is heated in a gas furnace 6. The additional reducing gas is mixed via an additional reducing gas line 7 for supplying additional reducing gas to the reduction unit 1, which reducing gas line 7 opens into the discharge line 5. Thus, both the gas stream obtained in the unit for carrying out oxidation with technically pure oxygen 4 and the additional reducing gas are introduced into the reduction shaft 1 via the introduction line 5, namely as a mixture which is called reducing gas. The temperature specification of the additional reduction gas which is heated in the gas furnace 6 is set as a function of a temperature specification for the mixture. The gas furnace 6 is disposed in the auxiliary reducing gas pipe 7.
    From the reduction shaft 1 Topgas is derived via a Topgasableitung 8. The additional reducing gas is in the example shown by 25 mixture of dedusted - a gas scrubber 9 is present in the top gas discharge 8 - and largely exempt from C02 - a C02 Entfemungsanlage 10 is present in the top gas 8 - top gas and another gas won. The additional gas is the hydrogen-rich fraction obtained in the separation of the coke oven gas. 30
    The gas furnace 6 is operated with a fuel gas. The fuel gas is burned while supplying air through an opening into the gas burner air supply line 11. The fuel gas consists of the gases from the group - tail gas accumulating in the removal of CO 2 from the top gas,
    2011P11617AT 19
    • v ·· * * - top gas, - coke oven gas, - hydrogen-rich fraction obtained by separation of coke oven gas.
    For supplying these gases in the gas burner 6 are 5 - a Tailgaszuleitung 12 for supplying in the removal of CO 2 from the
    Topgas accumulating tail gas present, which emanates from the C02-Removungsaniage 10 and opens into the gas burner, - a Topgaszuleitung 13 for supplying Topgas present, which emanates from the top gas from the reduction unit top 10 derived gas 8 and flows into the gas burner, - a Koksofengaszuieitung 14 for the supply of coke oven gas, which emanates from a feed line for coke oven gas 15 and flows into the top gas feed line 13,
    a hydrogen fraction feed line 16 branches off from a hydrogen fraction discharge 17 emanating from the PSA 15 or VPSA plant 2 and flows into the coke oven gas feed line 14.
    So that additional reduction gas can be obtained by mixing dedusted and largely freed from C02 top gas and the hydrogen-rich fraction obtained in the separation of the coke oven gas, both the hydrogen fraction outlet 17 and the top gas 8 lead into the additional reduction gas line. 7
    The feed line for coke oven gas 15 emanates from a source of coke oven gas, not shown, and flows into the PSA or VPSA system 2. 25 In the apparatus shown in FIG. 1, two discharge lines opening into the reduction shaft 1 are present. The initiating line 5, called the first initiating line, has already been discussed. Another feed line, called the second feed line 18, branches off from the feed line for the hydrocarbon-rich fraction 3 and ends in the reduction well. Through this second introduction line 18, a subset of the hydrocarbon-rich fraction can be introduced directly into the reduction shaft. This subset can thus be used to carburize the metallic iron produced in the reduction shaft 1, in this case sponge iron. A refrigerant gas line for supplying refrigerant gas in 4 4 44 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 5 4 5 4 4 5 4 4 4 4 5 6 8 8 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 4 4 4 4 4 f * * · · * 2011Ρ11617ΑΤ 20 the reduction shaft 1 is not shown for reasons of clarity; In principle, for the purpose of carburizing, a subset of the hydrocarbon-rich fraction could also be mixed with the cooling gas via a corresponding branch from the feed line for the hydrocarbon-rich fraction 3, which opens into the cooling gas line.
    In the tar filter device 19 arranged in the feed line for coke oven gas 19, tar is removed from the coke oven gas. In the burner 20, the additional reduction gas can be partially oxidized with the supply of technically pure oxygen, if this is desired to increase the temperature.
    For the sake of clarity, the illustration of device parts which are not essential to the present invention has been omitted, for example, the illustration of various compressors, bypass lines, gasometers, gas coolers, flare chimneys.
    In FIG. 2, with an apparatus and procedure otherwise analogous, the hydrocarbon-rich fraction is subjected to reforming by means of CO 2 and H 2 O instead of a partial oxidation before it is introduced into a reduction shaft as part of a reducing gas. The same system parts and method steps to Figure 1 are not described here largely again, the reference numerals for the same system parts are not registered for better clarity. The reforming takes place in an aggregate for carrying out a reforming by means of CO 2 and H 2 O, here a reformer 21, into which the feed line for the hydrocarbon-rich fraction 3 discharges. Exhaust gas from the reformer 21 is used via a heat exchanger 22 to heat the hydrocarbon-rich fraction before entering the reformer 30 21. A plurality of feed lines 23a, 23b, which open into the feed line for the hydrocarbon-rich fraction 3, are admixed with a plurality of CO 2 -containing gas streams before entry into the reformer 21 into the hydrocarbon-rich fraction. About feed line 23a tail gas from the COr
    2011P11617AT 21
    Entfemungsanlage 10 admixed; the feed line 23a rises from the tail gas feed line 12. Via feed line 23b, top gas is admixed. Via a water feed line 24, which opens into the feed line for the hydrocarbon-rich fraction 3, the hydrocarbon-rich fraction is added to the reformer 21 steam and / or water before entering 5.
    The reformer 21 can be fired with top gas, coke oven gas or with the hydrocarbon-rich fraction; appropriate opening into the reformer 21 lines are not shown for clarity. 10 via a branch line 29, which branches off from the second inlet line 18 and opens into the first inlet line 5, the hydrocarbon content in the reducing gas on entering the reduction shaft 1 can be influenced by supply of hydrocarbon-rich fraction. In FIG. 3, the reduction unit is a fluidized bed cascade 25 from which top gas is withdrawn from its last fluidized bed reactor 26, viewed in the direction of flow of the reducing gas. the top gas line is like the top gas line in Figure 1 provided with the reference numeral 8. The introduction line 5, which is shown opening into the reduction shaft 1 in FIG. 1, is illustrated in FIG. 3 in an analogous manner in the first fluidized bed reactor 27 seen in the flow direction of the reduction gas. As a device for separating coke oven gas is - instead of as in Figure 1 a device for pressure swing adsorption - a device for membrane separation 28 before. Via a branch from the feed line for the hydrocarbon-rich fraction 3, hydrocarbon-rich fraction can be fed into the first feed line 5, which offers a possibility for influencing the hydrocarbon content in the reducing gas.
    FIG. 4 differs from FIG. 2 by the same changes, by which FIG. 3 differs from FIG. In addition, in Figure 1, in contrast to Figure 2, no heat exchanger 22 is present.
    Although the invention has been illustrated and described in detail by the preferred embodiments, the invention is not limited by the invention. * · «* • ···» ··· * · »» · # ♦ «·« · 22
    And other variations can be deduced therefrom by those skilled in the art without departing from the scope of the invention. # # # # # # # # # # # # Fr # fr # fr # fr # fr # fr # fr fr # fr frfr fr 2011P11617AT List of Reference Numbers 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23a, 23b 24 25 26 · # M frfrfrfr fr # * fr fr • # ♦ · ♦ ·· * fr * fr 9 # fr * fr fr • fr ·· II · 23
    Reduction shaft PSA or VPSA system Supply line for the hydrocarbon-rich fraction
    Aggregate for performing oxidation with technically pure oxygen (first) gas furnace inlet line
    Additional reducing gas line to
    Supply of additional reducing gas to the reduction unit 1
    Topgasableitung
    Gas scrubber C02 removal unit
    air supply
    Tailgaszuleitung
    Topgaszuleitung
    Koksofengaszuleitung
    Feed line for coke oven gas
    Hydrogen fraction supply line
    Hydrogen fraction outlet Second inlet line
    Teerfiltereinrichtung
    burner
    Reformer heat exchanger
    Zuspeisleitung
    Water Zuspeisleitung
    Fluidized bed cascade
    Last fluidized bed reactor
    1P11617AT 24
    First fluidized bed reactor Membrane separation device Branch pipe
    权利要求:
    Claims (20)
    [1]
    Claims 1. A process for the reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen, characterized in that the gas stream containing both hydrocarbon and hydrogen is converted into a hydrogen-rich fraction and into a hydrocarbon-rich fraction And at least one subset of the hydrocarbon-rich fraction is subsequently subjected to at least one operation from the group oxidation with technically pure oxygen, reforming by means of CO 2 and H 2 O 15, and then at least as a constituent of a reducing gas into a metal oxide-containing fraction The reduction unit is initiated, wherein the hydrocarbon content is adjusted by the at least one operation from said group, 20 that the hydrocarbon content in the reducing gas when entering the reduction unit below 12 vol%, preferably unte r is 10% by volume, more preferably less than 8% by volume.
    [2]
    2. The method according to claim 1, characterized in that the gas stream containing both hydrocarbon and hydrogen is coke oven gas.
    [3]
    A process according to claim 1, characterized in that the gas stream containing both hydrocarbon and hydrogen is gas produced in a coal gasifier. 30
    [4]
    4. The method according to any one of claims 1 to 3, characterized in that the separation of the gas stream containing both hydrocarbon and hydrogen in a hydrogen-rich fraction and in a hydrocarbon-rich fraction by at least one operation from the group - pressure swing adsorption, - membrane separation he follows.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that at least a portion of at least a subset of the hydrocarbon-rich fraction was subjected to at least one operation from the group - oxidation with technically pure oxygen, - reforming by means of CO2 and H20 , is mixed with an additional reducing gas before the resulting mixture of these two components is introduced as a reducing gas into the metal oxide-containing reduction aggregate
    [6]
    6. The method according to claim 5, characterized in that the mixing ratio of the two components is set in dependence on a temperature specification for the mixture.
    [7]
    7. The method according to claim 5 or 6, characterized in that the two components are mixed after the additional reducing gas has been heated in a gas oven.
    [8]
    8. The method according to any one of claims 5 to 7, wherein is deducted from the reduction unit top gas, characterized in that ··· e * »· *

    27 2011P11617AT the additional reduction gas is at least partially obtained by mixing dedusted and largely free of C02 top gas and at least one other gas.
    [9]
    9. Process according to claim 8, characterized in that the at least one additional gas comprises the hydrogen-rich fraction obtained in the separation of the gas stream containing both hydrocarbon and hydrogen, preferably coke-oven gas.
    [10]
    10. The method according to claim 8 or 9, characterized in that the gas furnace is operated with a fuel gas, at least partially from at least one gas from the group - in the removal of CO 2 from the top gas accumulating tail gas, -Topgas, 15 - both Hydrocarbon as well as hydrogen-containing gas stream, preferably coke-oven gas, hydrogen-rich fraction obtained by separation of the gas stream containing both hydrocarbon and hydrogen, preferably coke oven gas, obtained by separation of the gas stream containing both hydrocarbon and hydrogen, preferably coke oven gas Hydrocarbon - rich fraction. 25
    [11]
    11. The method according to any one of claims 1 to 10, wherein the reduction unit is a reduction shaft, characterized in that the reduction unit is a reduction shaft, characterized in that a first subset of the hydrocarbon-rich fraction is introduced directly into the reduction shaft, ♦ »··· ··

    And a second subset of the hydrocarbon-rich fraction 5 is subjected to at least one operation from the group oxidation with technically pure oxygen, reforming by means of CO 2 and H 2 O before being introduced into the reduction shaft, and then at least as a constituent of a reducing gas a reduction aggregate containing the metal oxides is introduced, the hydrocarbon content being adjusted by the at least one operation from the said group, such that the hydrocarbon content in the reduction gas entering the reduction unit is less than 12% by volume, preferably less than 10% by volume. , more preferably below 8% by volume.
    [12]
    12. The method according to any one of claims 1 to 11, characterized in that the hydrocarbon-rich fraction before reforming by means of C02 and H20 at least one C02 and / or H20-containing gas stream is added.
    [13]
    13. A device for carrying out a method according to any one of claims 1 to 25, comprising a reduction unit for the reduction of metal oxides, with a device for separating a gas stream containing both hydrocarbon and hydrogen into a hydrogen-rich fraction and into a hydrocarbon-rich fraction, 30 having a hydrocarbon-rich fraction feedstock therefrom which is converted into an aggregate for performing an operation from the group consisting of oxidation with technically pure oxygen, β ······· ··· ······ * ·············· *. ············································································································································································································································································ gas stream obtained for the purpose of oxidation with technically pure oxygen, gas stream obtained in the aggregate for carrying out reforming by means of CO 2 and H 2 O 10, into the reduction aggregate.
    [14]
    14. The apparatus according to claim 13, characterized in that the device for separating a gas stream containing both hydrocarbon and hydrogen 15 in a hydrogen-rich fraction and in a hydrocarbon-rich fraction, a device for separating coke oven gas into a hydrogen-rich fraction and into a hydrocarbon -rich faction is.
    [15]
    15. The apparatus of claim 13 or 14, characterized in that the device for separating a gas stream containing both hydrocarbon and hydrogen in a hydrogen-rich fraction and in a hydrocarbon fraction, a device from the group 25 - device for pressure swing adsorption - device for membrane separation , is.
    [16]
    16. Device according to one of claims 13 to 15, wherein the 30 one or more introduction lines open into the reduction unit, characterized in that before the mouth of at least one of the introduction lines into the reduction unit a ·· eeeeaa ♦ · • ee * e • e • Additional fuel gas line for supplying additional reducing gas to the reduction unit opens into this discharge line.
    [17]
    17. The apparatus according to claim 16, characterized in that before the 5 mouth of the additional reducing gas line in the introduction line, a gas furnace in the additional reducing gas line is present.
    [18]
    18. Device according to one of claims 16 to 17, characterized in that x inlet lines present, wherein x is greater than or equal to 2, of which 10 at a maximum x-1 introduction lines applies that before the mouth of at least one of the introduction lines into the reduction unit an additional reducing gas line for supplying additional reducing gas to the reduction unit opens into this Einieitungsleitung.
    [19]
    19. Device according to one of claims 13 to 18, characterized in that the reduction unit is a reduction shaft.
    [20]
    20. An apparatus for carrying out a method according to any one of claims 13 to 18, characterized in that the reduction unit is a 20 fluidized bed cascade.
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    同族专利:
    公开号 | 公开日
    EP2714942A1|2014-04-09|
    CN103562412A|2014-02-05|
    WO2012163628A1|2012-12-06|
    RU2013157801A|2015-07-10|
    CA2837611A1|2012-12-06|
    US20140083252A1|2014-03-27|
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    TW201307578A|2013-02-16|
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    EP2714942B1|2015-03-18|
    UA111488C2|2016-05-10|
    KR20140048898A|2014-04-24|
    TWI565806B|2017-01-11|
    BR112013030747A2|2016-12-06|
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    KR101890788B1|2018-08-22|
    AU2012265081B2|2016-09-08|
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    CN101891150B|2010-07-09|2011-12-07|太原重工股份有限公司|Reborner for reforming coke-oven gas|US9970071B2|2014-09-23|2018-05-15|Midrex Technologies, Inc.|Method for reducing iron oxide to metallic iron using coke oven gas|
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    法律状态:
    2016-06-15| PC| Change of the owner|Owner name: PRIMETALS TECHNOLOGIES AUSTRIA GMBH, AT Effective date: 20160415 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA785/2011A|AT510955B1|2011-05-30|2011-05-30|REDUCTION OF METAL OXIDES USING A BOTH HYDROCARBONS AND HYDROGEN CONTAINING GAS STREAM|ATA785/2011A| AT510955B1|2011-05-30|2011-05-30|REDUCTION OF METAL OXIDES USING A BOTH HYDROCARBONS AND HYDROGEN CONTAINING GAS STREAM|
    PCT/EP2012/058360| WO2012163628A1|2011-05-30|2012-05-07|Reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen|
    BR112013030747A| BR112013030747A2|2011-05-30|2012-05-07|metal oxide reduction using a gas stream containing both hydrocarbons and hydrogen|
    UAA201313791A| UA111488C2|2011-05-30|2012-05-07|process for reducing metal oxides using a coke gas and a device for carrying out such a process|
    RU2013157801/02A| RU2013157801A|2011-05-30|2012-05-07|REDUCTION OF METAL OXIDES USING A GAS FLOW CONTAINING AS A HYDROCARBON AND HYDROGEN|
    CA2837611A| CA2837611A1|2011-05-30|2012-05-07|Reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen|
    US14/123,020| US20140083252A1|2011-05-30|2012-05-07|Reduction of metal oxides using gas stream containing both hydrocarbon and hydrogen|
    KR1020137035070A| KR101890788B1|2011-05-30|2012-05-07|Reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen|
    CN201280026155.1A| CN103562412B|2011-05-30|2012-05-07|Use not only hydrocarbonaceous but also the method for hydrogeneous air-flow reducing metal oxide|
    EP12722096.0A| EP2714942B1|2011-05-30|2012-05-07|Reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen|
    AU2012265081A| AU2012265081B2|2011-05-30|2012-05-07|Reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen|
    TW101118933A| TWI565806B|2011-05-30|2012-05-28|Reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen|
    ZA2013/08896A| ZA201308896B|2011-05-30|2013-11-26|Reduction of metal oxides using a gas stream containing both hydrocarbon and hydrogen|
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