Patent Grant
9797026
The present invention relates to a process for the reduction of metal oxides to form metalized material by contact with hot reducing gas, which is produced at least partially by catalytic reformation of a mixture of
By way of example, FIG. 1 of WO2006135984 describes a process for the reduction of metal oxides to form metalized material by contact with hot reducing gas, which is produced by catalytic reformation of a mixture of natural gas with the top gas taken from the reduction unit, wherein the fuel gas for burners which provide the heat for the endothermal reformation processes which take place during the reformation is obtained from a partial quantity of the top gas produced during the reduction of metal oxides to form metalized material and from natural gas. Owing to ever more stringent statutory environmental regulations, it is desirable to separate CO2 in order to produce a concentrated CO2 flow from the off-gases produced during the processes, with the possibility of subsequent sequestration of the CO2 flow, before the off-gases treated in this way are released into the environment. In the case of a process as shown in WO2006135984, the fuel gas for the reformer is combusted with air as the oxygen source, for which reason the combustion off-gas contains a large quantity of nitrogen. Correspondingly, downstream plants for removing CO2 from the combustion off-gas have to have large dimensions. Additionally, substantially only chemical absorption processes are suitable for removing CO2 from the combustion off-gas, and these are distinguished by a large plant size and a high consumption of energy, which is supplied, for example, using steam.
According to various embodiments, a process can be provided which makes it possible to avoid the presence of CO2 in the combustion off-gas using smaller plants—with correspondingly lower levels of consumption—and makes other CO2 removal processes possible, and also an apparatus for carrying out the process.
According to an embodiment, in a process for the reduction of metal oxides to form metalized material by contact with hot reducing gas, the reducing gas is produced at least partially by catalytic reformation of a mixture of—a gas containing carbon dioxide (CO2) and/or steam (H2O) with—gaseous hydrocarbons, wherein the heat for the endothermal reformation processes which take place during the reformation is provided at least partially by the combustion of a fuel gas, and the combustion off-gas produced in the process is drawn off, wherein the fuel gas is obtained at least partially from a partial quantity of the top gas produced during the reduction of metal oxides to form metalized material, and wherein the partial quantity of the top gas, from which the fuel gas is obtained, is firstly subjected to dedusting and then to a CO conversion reaction, and the conversion gas obtained during the CO conversion reaction is subjected to CO2 removal after cooling, and the CO2-depleted conversion gas produced in the process is used at least as a component of the fuel gas.
According to a further embodiment, the gas containing carbon dioxide (CO2) and/or steam (H2O) can be top gas from the process for the reduction of metal oxides. According to a further embodiment, the gas containing carbon dioxide (CO2) and/or steam (H2O) can be export gas from a smelting reduction process or syngas from a coal gasification process. According to a further embodiment, gaseous hydrocarbons can be admixed to the CO2-depleted conversion gas in order to obtain fuel gas. According to a further embodiment, the dedusting may take place in dry form or in wet form.
According to another embodiment, an apparatus for carrying out the process as described above, may have a reduction unit for the reduction of metal oxides to form metalized material, and a reformer for carrying out catalytic reformation of a mixture of—a gas containing carbon dioxide (CO2) and/or steam (H2O) with—gaseous hydrocarbons, wherein the reformer is provided with a mixture supply line for supplying the mixture, and wherein the reformer is provided with burners, which are connected to an oxygen supply line, for providing heat by the combustion of fuel gas, having a drawing-off line for drawing off combustion off-gas from the reformer, having a reducing gas supply line for hot reducing gas from the reformer into the reduction unit, having a discharge line for discharging top gas from the reduction unit, wherein the burners are connected to the discharge line via a connection line which branches off from the discharge line, and wherein a dedusting apparatus is present at least in the discharge line between the reduction unit and the connection line which branches off from it, or in the connection line, wherein a CO conversion reactor, a gas cooling apparatus and a CO2 removal apparatus are present in succession, as seen from the discharge line, in the connection line, between the dedusting device which may be present and the burners.
According to a further embodiment of the apparatus, a hydrocarbon feed line for gaseous hydrocarbons may issue into the connection line. According to a further embodiment of the apparatus, the hydrocarbon feed line for gaseous hydrocarbons may issue into the connection line downstream from the CO2 removal apparatus, as seen from the discharge line. According to a further embodiment of the apparatus, the dedusting apparatus can be a dry-dedusting apparatus. According to a further embodiment of the apparatus, the dedusting apparatus can be a wet-dedusting apparatus. According to a further embodiment of the apparatus, a gas heating apparatus can be present in the connection line between the wet-dedusting apparatus and the CO conversion reactor. According to a further embodiment of the apparatus, the reduction unit can be a fluidized bed cascade. According to a further embodiment of the apparatus, the reduction unit can be a fixed-bed reduction shaft.
In the text which follows, the various embodiments are explained in more detail with reference to a plurality of schematic figures.
As stated above, according to various embodiments, in a process for the reduction of metal oxides to form metalized material by contact with hot reducing gas, the reducing gas is produced at least partially by catalytic reformation of a mixture of
The metal oxides are preferably iron oxides. However, according to the Richardson-Jeffes diagram, nickel, copper, lead and cobalt can furthermore also be reduced, for example.
The reducing gas is produced at least partially by catalytic reformation of a mixture of
This reformation takes place by at least partial conversion of the gaseous hydrocarbons with H2O and CO2 to form hydrogen (H2) and carbon monoxide (CO). The substances H2O and/or CO2 required for the reformation can be added to the mixture for reformation in each case individually or together, and/or the H2O and/or CO2 present in the gas containing carbon dioxide CO2 and/or steam H2O is used. It is preferable to add at least H2O—as steam—to the mixture.
Gaseous hydrocarbons are to be understood as meaning, for example, natural gas, methane, propane, syngas from coal gasification or coke furnace gas. The term “gaseous hydrocarbons” includes both the possibility that only one compound, for example pure propane, is present, and also the possibility that a mixture of a plurality of compounds is present, for example a mixture of propane and methane.
The gas containing carbon dioxide CO2 and/or steam H2O is, for example, top gas from the process according to various embodiments for the reduction of metal oxides. In this case, top gas is to be understood as meaning the gas which is discharged from the reduction unit in which the metal oxides are reduced to form metalized material. Before the reformation, the top gas may also be cleaned, for example by the separation of dust and/or water carried along.
The gas containing carbon dioxide CO2 and/or steam H2O can also be, for example, export gas from a different process for the reduction of metal oxides, for example a smelting reduction process, or syngas from a coal gasification process, for example a Lurgi fixed-bed gasifier or Siemens entrained-flow gasifier.
With preference, the gas is top gas from the process according to various embodiments for the reduction of metal oxides.
Table 1 shows a typical composition of top gas from a direct reduction process:
In the gas containing carbon dioxide CO2 and/or steam H2O, the lower limit for the carbon dioxide CO2 content is 0% by volume, preferably 5% by volume, particularly preferably 15% by volume, and the upper limit for the carbon dioxide CO2 content is 25% by volume, preferably 30% by volume, particularly preferably 40% by volume.
In the gas containing carbon dioxide CO2 and/or steam H2O, the lower limit for the steam H2O content is 0% by volume, preferably 10% by volume, and the upper limit for the steam H2O content is 20% by volume, preferably 55% by volume.
The catalytic reformation produces a reducing gas which contains principally H2 and CO as reducing constituents. It is known that such reformation involves an endothermal reaction, and for this reason heat is supplied to the reformer, for example by the combustion of fuel gas with oxygen, in burners associated with the reformer. By way of example, the oxygen is provided by the supply of air, the supply of a different oxygen-containing gas mixture or the supply of technically pure oxygen.
In order to increase the efficiency of the process as a whole, the fuel gas is obtained at least partially from a partial quantity of the top gas produced during the reduction of metal oxides to form metalized material. This top gas also contains combustible constituents, for example CO and H2, which are used in the burners of the reformer to produce the heat required for the reformation.
According to various embodiments, the partial quantity of the top gas, from which the fuel gas is obtained, is subjected to a CO conversion reaction (also referred to as a CO shift reaction or water gas shift reaction). This known reaction serves to simultaneously reduce the CO content in the top gas and increase the H2 content, with CO2 being formed simultaneously.
CO+H2OCO2+H2ΔH0R 298=−41.2 kJ/mol
After the CO conversion reaction, according to various embodiments the CO2 and H2O contents are cooled and removed in a CO2 removal plant, before they are used as fuel gas. Here, the CO2 is already efficiently separated before the combustion. Accordingly, the effort required to remove CO2 from the combustion off-gas can be reduced.
By virtue of these measures, a fuel gas containing principally hydrogen H2 as combustible component is supplied to the burners of the reformer. This has the advantage that less CO2 is produced as a result of combustion in the burners, since the proportion of CO components which generate CO2 during the combustion in the fuel gas is low.
The CO conversion reaction preferably takes place on the basis of high-temperature or crude-gas conversion processes, since neither of these processes is overly sensitive to the presence of hydrogen sulfide (H2S) in the gas flow to be treated.
The CO conversion reaction is an exothermal reaction, but can also be an isothermal reaction and in this case can be used, for example, for producing steam. Depending on the CO conversion process, an inlet temperature of 160-450° C., preferably 300-450° C. in the case of a high-temperature CO conversion process, has to be complied with for operation of the CO conversion reactor. If the top gas is washed when wet before the CO conversion reaction, it is necessary to carry out heating to such temperatures after the wet wash owing to the associated drop in temperature. If the top gas is dedusted when dry before the CO conversion reaction, the temperature of the top gas can equally be employed for the subsequent CO conversion reaction.
According to various embodiments, the CO conversion reaction is followed by cooling and separation of CO2 and H2O from the flow of the conversion gas obtained during the CO conversion reaction. Since the flow of the conversion gas contains only a small amount of nitrogen compared to the combustion off-gas, and the CO2 is accordingly present in more concentrated form than in the combustion off-gas, and because the CO2 is removed before the combustion, the gas volume to be subjected to CO2 removal is less than in the case of the removal of CO2 from combustion off-gas. Accordingly, the removal is less complex. CO2 does not make a contribution to the calorific value of the fuel gas. In conventional processes for the use of top gas—which already contains CO2 after the reduction of the metal oxides—in the fuel gas, it is therefore often necessary to admix gaseous hydrocarbons, for example natural gas, in order to increase the calorific value of the fuel gas to an extent required to achieve the required flame temperature in the reformer. Since, according to various embodiments, the CO2 is removed before the combustion—and owing to the associated increase in the calorific value of the fuel gas—it is generally possible to dispense with such an admixture of gaseous hydrocarbons. It is of course also possible to admix gaseous hydrocarbons if required.
Such an admixture can be carried out such that gaseous hydrocarbons are admixed to the CO2-depleted conversion gas in order to produce fuel gas.
If nothing is admixed to the CO2-depleted conversion gas before it is used as fuel gas, the CO2-depleted conversion gas is the fuel gas. If something is admixed to the CO2-depleted conversion gas, for example gaseous hydrocarbons, this is a component of the fuel gas.
A further advantage of various embodiments is that the combustion off-gas can be used extremely effectively as seal gas after possible separation of water. A seal gas is defined as a noncombustible and inert gas for sealing off the outlet of process gas and for providing an inert atmosphere over a material. Seal gas is used, for example, for the charging of raw materials and in the shaft discharge of a reduction shaft, or for hot conveyors. The gas obtained after possible separation of water from the combustion off-gas in the process according to various embodiments contains, as main constituent, nitrogen and barely any CO2. By contrast, combustion off-gas produced according to a process as shown in FIG. 1 of WO2006135984 contains 18 to 20% by volume CO2, which can lead to reoxidation and thus to product impairment on contact with product from the reduction process, for example hot DRI (direct reduced iron), for example in the shaft discharge of a reduction shaft or in hot conveyors. When the combustion off-gas produced according to various embodiments is used as seal gas, a risk of this nature does not arise.
Owing to the high temperature of the conversion gas produced, it is necessary in the process according to various embodiments for the conversion gas to be cooled before the CO2 removal in order to obtain a temperature required for the CO2 removal, preferably from 30-60° C. Steam which is introduced during the conversion reaction, but is unconverted, is preferably also removed from the conversion gas by condensation.
Furthermore, it is necessary to dedust the partial quantity of the top gas, from which fuel gas is obtained, before the CO conversion reaction, in order to keep the outlay in terms of maintenance resulting from deposits and damage to plant components low, to ensure high availability of the plant and also to comply with the environmental regulations regarding the dust content of gases released into the environment. The dedusting can take place in wet or dry form. The advantage of dry dedusting is that the heat content can be used for the purpose of carrying out the CO conversion reaction at the required temperature. The outlet temperature of top gas from a reduction unit is typically in the range of 250-500° C. For optimum temperature control for the subsequent process steps, it may be necessary to adjust the temperature a bit more by cooling, heating or evaporation of water. The heat content is advantageously used to produce steam, which is needed in order to carry out the CO conversion reaction. It is also advantageous if the steam needed in order to carry out the CO conversion reaction is obtained at other stations of the process according to various embodiments.
In the event of wet dedusting, it may be necessary for the top gas flow to be heated before the CO conversion reaction is carried out, in order to ensure that the temperature of the gas flow required for the CO conversion reaction is obtained.
The dedusting can take place in a manner such that all of the top gas is dedusted, and after this dedusting a partial quantity is branched off in order to obtain fuel gas, or the dedusting can take place after the partial quantity has been branched off in order to obtain fuel gas.
By way of example, the CO2 produced during the CO2 removal can be compressed, condensed and/or sequestered, in order to lower the CO2 emissions of the process which are emitted to the environmental atmosphere.
According to yet another embodiment, an apparatus for carrying out the process, may have a reduction unit for the reduction of metal oxides to form metalized material,
a reformer for carrying out catalytic reformation of a mixture of
The gaseous hydrocarbons are typically natural gas, methane or propane.
According to one embodiment, a hydrocarbon feed line for gaseous hydrocarbons issues into the connection line, as a result of which it is possible, if required, to admix gaseous hydrocarbons, in order to obtain a fuel gas with the desired calorific value.
In this case, the hydrocarbon feed line for gaseous hydrocarbons can issue into the connection line downstream from the CO2 removal apparatus, as seen from the discharge line.
According to one embodiment, the dedusting apparatus is a dry-dedusting apparatus, for example a cyclone, a hot-gas filter or a bag filter.
According to another embodiment, the dedusting apparatus is a wet-dedusting apparatus.
It is also possible for more than one dedusting apparatus to be present. These can be arranged, for example, both in the discharge line between the reduction unit and the connection line which branches off from it and in the connection line.
According to one embodiment, in this case, by way of example, a wet-dedusting apparatus is arranged in the discharge line between the reduction unit and the connection line which branches off from it, and a dry-dedusting apparatus is arranged in the connection line.
In this case, a gas heating apparatus is preferably present in the connection line between the wet-dedusting apparatus and the CO conversion reactor.
In
The drawing-off line 10 comprises an apparatus 11 for cooling the combustion off-gas and for removing water from the combustion off-gas. Cooling and removal of water take place in the same apparatus. The drawing-off line 10 leads into a chimney, through which the combustion off-gas can be released into the environment.
Steam, which can be used for the CO conversion, can also be produced by the apparatus 11 or by further process waste heat, for example from top gas or the conversion gas after the CO conversion.
The burners 8a, 8b, 8c are provided with apparatuses for supplying fuel gas, represented by the connection line 12 which branches off from the discharge line 5. Fuel gas is fed to the burners 8a, 8b, 8c through the connection line 12.
The oxygen required for the combustion of the fuel gas is supplied to the burners 8a, 8b, 8c via the oxygen supply line 13 for supplying oxygen—in this case by means of the supply of air. The air is fed into the oxygen supply line by means of a blower 14.
The drawing-off line 10 is provided with an apparatus for heating the air guided in the oxygen supply line 13, in this case a recuperator 15 for indirect heat exchange between the air in the oxygen supply line 13 and the combustion off-gas in the drawing-off line 10.
Furthermore, the drawing-off line 10 is provided with an apparatus for heating the mixture of top gas and gaseous hydrocarbons in the mixture supply line 6, in this case a recuperator 16 for indirect heat exchange between the mixture of top gas and gaseous hydrocarbons in the mixture supply line 6 and the combustion off-gas in the drawing-off line 10.
A dedusting apparatus 18, in this case a wet-dedusting apparatus, is present in the discharge line 5 between the reduction unit 1 and the point at which the connection line 12 branches off.
A gas heating apparatus 19, in this case a recuperator for indirect heat exchange, a CO conversion reactor 20, a gas cooling apparatus 21 and a CO2 removal apparatus 22 are present in succession in the connection line 12, as seen from the point at which the latter branches off from the discharge line 5.
Here, a steam supply line 23 issues into the connection line 12 upstream from the CO conversion reactor 20, as seen from the point at which said connection line branches off from the discharge line 5.
The discharge of steam which has been produced from the CO conversion reactor 20 is indicated by a dashed arrow which proceeds from the latter. The discharge of condensate from the gas cooling apparatus 21 is indicated by an arrow which proceeds from the latter. The discharge of a CO2-rich gas flow from the CO2 removal apparatus 22 is indicated by a dashed arrow which proceeds from the latter. By way of example, the CO2-rich gas flow can be sequestered.
A hydrocarbon feed line 24 for gaseous hydrocarbons issues into the connection line 12 downstream from the CO2 removal apparatus 22, as seen from the discharge line.
As indicated by an arrow, the metal oxides 3 reduced in the reduction unit 1 are removed from the reduction unit 1.
The top gas produced during the reduction is discharged out of the reduction unit through the discharge line 5. After dedusting in the dedusting apparatus 18, a partial quantity of the top gas is guided in the connection line 12 to the burners 8a, 8b, 8c, said top gas firstly being heated in the gas heating apparatus 19 to a temperature required for the CO conversion reactor 20 to function and, after steam has been supplied via the steam supply line 23, being subjected to the CO conversion reaction in the CO conversion reactor 20. The product obtained in the process, referred to as conversion gas, is cooled in the gas cooling apparatus 21 and steam carried along is removed therefrom by condensation, and CO2 is then removed therefrom in the CO2 removal apparatus 22. The CO2-depleted product of this step, referred to as CO2-depleted conversion gas, is used as fuel gas in the burners 8a, 8b, 8c after gaseous hydrocarbons have been admixed through the hydrocarbon feed line 24. The oxygen required for combustion is supplied via the oxygen supply line 13 in the form of air compressed by means of the blower 14.
Hot reducing gas is produced in the reformer 4 by reforming a mixture of top gas and gaseous hydrocarbons, and is fed to the reduction unit via the reducing gas supply line 9.
Since no temperature loss occurs in the dedusting apparatus 26, no gas heating apparatus 19 is needed to ensure that the temperature required for the CO conversion reactor is obtained. For greater clarity, only the apparatus parts which appear in addition in
Instead,
Since no temperature loss occurs in the dedusting apparatus 27, no gas heating apparatus 19 is needed to ensure that the temperature required for the CO conversion reactor is obtained. For greater clarity, only the apparatus parts which appear in addition in
| Number | Date | Country | Kind |
|---|---|---|---|
| A1217/2009 | Jul 2009 | AT | national |
The present application is a divisional under 37 C.F.R. §1.53(b) of prior U.S. patent application Ser. No. 13/387,895, filed Mar. 16, 2012, which in turn is a U.S.C. §371 National Phase conversion of PCT/EP2010/060130, filed Jul. 14, 2010, which claims priority of Austrian Patent Application No. A1217/2009, filed Jul. 31, 2009. The contents of each of these applications are incorporated in full by reference herein.
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| Entry |
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| International Search Report dated Oct. 27, 2010, issued in corresponding international application No. PCT/EP2010/060130. |
| Russian Federation Decision of Grant dated May 20, 2014 issued in Russian Patent Application No. 2012107479/02(011287). |
| Number | Date | Country | |
|---|---|---|---|
| 20150329930 A1 | Nov 2015 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13387895 | US | |
| Child | 14811037 | US |
