EP4334481A1 - Procédé d'utilisation de gaz de synthèse pour améliorer l'impact environnemental de la réduction de minerai de fer dans des hauts fourneaux - Google Patents
Procédé d'utilisation de gaz de synthèse pour améliorer l'impact environnemental de la réduction de minerai de fer dans des hauts fourneauxInfo
- Publication number
- EP4334481A1 EP4334481A1 EP22727766.2A EP22727766A EP4334481A1 EP 4334481 A1 EP4334481 A1 EP 4334481A1 EP 22727766 A EP22727766 A EP 22727766A EP 4334481 A1 EP4334481 A1 EP 4334481A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reduction
- synthesis gas
- produced
- sct
- cpo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 101
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 80
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 55
- 230000007613 environmental effect Effects 0.000 title abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 47
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 37
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical class [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 131
- 239000000571 coke Substances 0.000 claims description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 239000003153 chemical reaction reagent Substances 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000003345 natural gas Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- 238000001311 chemical methods and process Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 claims description 2
- 230000004151 fermentation Effects 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 abstract description 11
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 92
- 229910002092 carbon dioxide Inorganic materials 0.000 description 55
- 238000006722 reduction reaction Methods 0.000 description 48
- 239000002817 coal dust Substances 0.000 description 20
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229910000805 Pig iron Inorganic materials 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000004449 solid propellant Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000002453 autothermal reforming Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007348 radical reaction Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 3⁄4 Chemical compound 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/001—Injecting additional fuel or reducing agents
-
- 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
- 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
- C21B7/00—Blast furnaces
- C21B7/002—Evacuating and treating of exhaust gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/001—Injecting additional fuel or reducing agents
- C21B2005/005—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
- C21B2100/22—Increasing the gas reduction potential of recycled exhaust gases by reforming
-
- 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
Definitions
- the present invention relates to a process for the reduction of iron ore in a blast furnace using synthesis gases produced by Catalytic Partial Oxidation (CPO), in order to reduce CO2 emissions.
- CPO Catalytic Partial Oxidation
- the product obtained in the BF is a pig iron with a high carbon content which is subsequently converted into steel in the Basic Oxygen Furnace (BOF).
- BOF Basic Oxygen Furnace
- the reduction of iron ores in the BF typically requires a coke consumption of 450 - 700 kg per ton of produced hot metal ⁇ Ton of Hot Metal - THM), an amount that by burning provides approximately the 75% of the total energy consumption required for the conversion of iron ores into steel with the combined BF and BOF processes.
- coke amount can also be reduced below 400 kg/THM if its use is combined with the use of pulverized and/or micronized coal, as occurs in the most recent steelmaking technologies.
- the coke oven that produces the coke from coal also produces a coke oven gas (COG), which contains hydrogen, light hydrocarbons but also pollutants such as polyaromatic hydrocarbons, various nitrogen and sulphur compounds as well as liquid and/or solid particles that can be dispersed into the atmosphere if not properly captured, and that are usually referred to as particulate matter.
- COG coke oven gas
- the processes for the reduction of iron ore in the BF produce a blast furnace gas (BFG), whose main components are CH 4 , CO, CO 2 , 3 ⁇ 4, H 2 O, N 2 as well as smaller amounts of aromatic hydrocarbons, sulphur compounds, particulate matter, ammonia compounds and NOx.
- BFG blast furnace gas
- the process for the reduction of iron ore in the BF produces large amounts of CO 2 , e.g. 1.7 tonnes of CO 2 /THM.
- an object of the present invention is to provide a process solution for the reduction of iron ore in a BF that improves its energy efficiency and reduces the carbon dioxide emissions.
- an aspect of the present invention relates to an environmentally friendly process for the reduction of iron ores in a BF for the production of iron and/or iron-carbon compounds, comprising the combustion of coke, and the utilization into said BF of synthesis gas produced from a hydrocarbon stream by means of a short contact time catalytic partial oxidation process.
- the process for the reduction of iron ore in a BF furnace for the production of iron and/or iron-carbon compounds is carried out by combustion of coke produced in a coke oven upstream of the blast furnace, and is characterized in that synthesis gas produced with a short contact time catalytic partial oxidation process (SCT-CPO) integrated with said process for the reduction of iron ore is also introduced into said blast furnace, wherein said SCT-CPO process uses a gaseous hydrocarbon stream, an oxidizing agent selected from one or more of oxygen, enriched air and air, and optionally hydrogen and/or steam.
- SCT-CPO catalytic partial oxidation process
- the hydrocarbon stream comprises BFG and COG recycled from said blast furnace and said coke oven, respectively.
- 'hydrocarbon gases' is meant as natural gas, gases from chemical processes, refinery gases and gases produced by the fermentation of biomass, also known as 'biogas'.
- synthesis gas in the process for the reduction of iron ore in the blast furnace allows a reduction in the amount of coke used in the blast furnace.
- coke oven gas and blast furnace gas to produce synthesis gas allows a further reduction in pollutant emissions related to the production and use of coke, as well as an improvement in the overall energy efficiency of the process for the reduction of iron ore and the reduction of CO2 emissions.
- FIG. 1 is a diagram of a process according to a first embodiment of the invention
- Fig. 2 is a diagram of a process according to a second embodiment of the invention
- Fig. 3 is a diagram of a process according to a third embodiment of the invention.
- Processes for the reduction of iron ore in blast furnaces typically produce pig iron, which is then converted into steel in oxygen converters.
- air, or oxygen-enriched air, preheated in a unit 70 is blown through the line 72.
- This oxidizing current reacts with the coke produced in the coke oven 10 integrated with the blast furnace, producing a carbon monoxide -rich gas at a high temperature (approx. 1900°C) that reduces iron ore.
- the process for the reduction of iron ore in a blast furnace for the production of iron and/or iron-carbon compounds by burning coke is implemented by replacing a portion of the coke produced in the coke oven upstream of the blast furnace with synthesis gas produced with a short contact time catalytic partial oxidation process that uses a hydrocarbon gas stream, an oxidizing agent selected from one or more of oxygen, enriched air and air and optionally hydrogen and/or steam.
- the process for the reduction of iron ores in a BF for the production of iron and/or iron-carbon compounds by coke combustion is implemented by replacing a portion of the coke produced in the coking plant upstream of the blast furnace with synthesis gas produced with a short contact time catalytic partial oxidation process using an oxidizing agent selected from oxygen, enriched air and air, and a gaseous hydrocarbon stream comprising BF gas and coke oven gas recycled from said BF and from said coke oven, respectively, thereby carrying out partial recycling of carbon atoms, and optionally from other hydrocarbon gases and steam.
- an oxidizing agent selected from oxygen, enriched air and air
- a gaseous hydrocarbon stream comprising BF gas and coke oven gas recycled from said BF and from said coke oven, respectively, thereby carrying out partial recycling of carbon atoms, and optionally from other hydrocarbon gases and steam.
- synthesis gas is produced by various technologies, such as Steam Reforming (SR), Non-Catalytic Partial Oxidation (POx) and AutoThermal Reforming (ATR).
- SR Steam Reforming
- POx Non-Catalytic Partial Oxidation
- ATR AutoThermal Reforming
- GHR Gas Heated Reforming
- Synthesis gas is used in many chemical processes, such as the synthesis of methanol and its derivatives, the synthesis of ammonia and urea, the synthesis of liquid hydrocarbons using the Fischer-Tropsch process and the production of hydrogen.
- synthesis gas production technologies mentioned above in fact use catalysts that require relevant amounts of steam in the reagent mixture, expressed as a steam to carbon ratio (S/C) in the hydrocarbon feedstock, in order not to be deactivated. These technologies therefore produce 'wef synthesis gas mixtures, the composition of which would have a negative impact on the efficiency of the BF.
- S/C steam to carbon ratio
- SCT-CPO technology is also described in the following scientific literature documents: a) "Issues in 3 ⁇ 4 and synthesis gas technologies for refinery, GTL and small and distributed industrial needs"; Basini, Luca, Catalysis Today, 106 (1-4), p.34, Oct 2005; b) "Fuel rich catalytic combustion: Principles and technological developments in short contact time (SCT) catalytic processes”; Basini, L.; Catalysis Today, 117(4), 384-393; DOI: 10.1016/j.cattod.2006.06.043 Published: Oct. 15, 2006; c) "Natural Gas Catalytic Partial Oxidation: A Way to Syngas and Bulk Chemicals Production / IntechOpen”; G.
- SCT-CPO short contact time catalytic partial oxidation
- CPO Catalytic Partial Oxidation
- the production of synthesis gas must take into account the parameters of moisture content and reducing capacity. In particular, it must contain low percentages of steam, which inhibits the reduction processes of iron ores, and a clear prevalence of partial oxidation products (CO, Fh) over the total oxidation products (CO2 , H2O) of hydrocarbons.
- the process of the invention thus constitutes an innovative solution suitable not only to reduce the production and use of coke with synthesis gas but also to use coke oven and BF gas to produce a synthesis gas with an optimal composition for the reduction of iron ore.
- This dual benefit is made possible by producing synthesis gas using the SCT-CPO process.
- the SCT-CPO process makes it possible to produce a synthesis gas suitable for the reduction processes that take place in the BF using different hydrocarbon sources such as: i) natural gas, ii) purge gas from refining processes and some chemical and petrochemical processes, iii) biogas produced from biomass.
- Figure 1 schematically shows an integrated iron ore reduction process according to a first embodiment of the invention.
- the integrated process comprises a coking plant 10, an iron ore feed 20, coke and iron ore sintering 30 and pelletizing 40 units, a BF 50 and a CPO catalytic partial oxidation reactor 60 for the production of synthesis gas.
- the SCT-CPO reactor 60 produces synthesis gas using hydrocarbon gases of various compositions, e.g. natural gas (NG), coke oven gas fed via the line 12, BF gas fed via the line 52 and one or more air streams, oxygen-enriched air and oxygen.
- NG natural gas
- coke oven gas fed via the line 12
- BF gas fed via the line 52
- air streams oxygen-enriched air and oxygen.
- the SCT-CPO reactor produces synthesis gas which is introduced into the BF 50 through one or more tube lines 62 located above a line 72 feeding a high temperature oxidant mixture from a unit 70.
- synthesis gas produced in this way makes it possible to reduce the production and use of coke and related polluting emissions, to reduce polluting emissions containing nitrogen, sulphur and carbon compounds and to reduce CO2 emissions.
- the production of synthesis gas with the SCT-CPO process takes place at pressures higher than those of the BF, so that the synthesis gas can be sent directly, without undergoing cooling and purification processes, and therefore at high temperature, into the BF via the line 62.
- the SCT-CPO process uses operating conditions characterized by low steam to carbon ratios (S/C) in the feed, which only the SCT-CPO catalytic technology allows the use of without promoting the formation of by-products consisting of unsaturated hydrocarbons, which could be transformed through radical reactions, giving rise to aromatic and polyaromatic compounds and possibly carbon residues.
- S/C steam to carbon ratios
- the operating conditions under which the SCT-CPO reactors will be used are as follows: pressures higher than those of the BF; preferably between 2 and 15 bar g , more preferably between 2.5 and 10 bar g , even more preferably between 3 and 8 bar g ; temperatures of the reagent mixtures between 100 and 600°C and preferably between 250 and 450°C; ratio O2/C (v/v) (moles of oxidant 02/moles of carbon C) in the reagent mixture between 0.30 and 0.70 v/v and preferably between 0.50 and 0.65 v/v;
- S/C ratio between 0 and 1.5 v/v and preferably between 0 and 0.5 v/v.
- the SCT-CPO reactors used in this application allow low pressure drops of between 5 and 0.5 kg/cm 2 .
- the v/v percentages of BFG in the mixture of hydrocarbon reagents used for the production of synthesis gas are between 0 and 60%, preferably between 15 and 50%.
- the v/v percentages of COG in the mixture of hydrocarbon reagents are between 0 and 60%, preferably between 15 and 50%.
- the sum of the v/v percentages of BFG and COG in the mixture of hydrocarbon reagents are between 0 and 80%, and preferably between 15 and 60%.
- the presence of hydrogen in the reagent mixture in particular that contained in the COG and BFG, strongly inhibits all the radical reactions that lead to the formation of carbon residues, both in the areas of heat shielding and pre -heating of the reagents, which separate the reagent mixing zone from the catalytic reaction zone, and in the catalytic bed where the heterogeneous catalytic processes for the production of synthesis gas take place.
- the hydrogen contained in the coke oven gas is used to carry out hydrogenation and hydro- desulphurisation reactions of the coke oven gas stream before being fed to the SCT-CPO reactor.
- the process of the invention provides for the integration, or replacement, of the processes used to produce oxygen by cryogenic distillation (Air Separation Unit - ASU) and Vacuum Pressure Swing Adsorption (VPSA) with an electrolysis process in which oxygen and hydrogen produced by water electrolysis are both used.
- Oxygen is fed to the SCT-CPO reactor and Hydrogen is added to the synthesis gas produced by the SCT-CPO reactor before being sent to the BF.
- Fig. 3 shows the electrolyzer 90, which can either be of polymer electrolyte membrane (PEM) or alkaline water (AE) type.
- PEM polymer electrolyte membrane
- AE alkaline water
- the water is supplied in liquid form.
- SOEC Solid Oxide Electrolyzer Cell
- water is fed into the steam phase and it is also possible to co-fuel CO2 in addition to steam and co-produce carbon monoxide, as well as hydrogen and oxygen.
- oxygen is fed to the SCT-CPO reactor while hydrogen and carbon monoxide are added to the synthesis gas produced before it is sent to the BF.
- electrolyzers in the iron ore reduction process is particularly advantageous when a surplus of electrical energy from various primary energy sources, including renewables, is available.
- Table 2 shows the input and output compositions to an CPO reactor operating at a Gas Hourly Space Velocity (GHSV) of 80,000 hours 1 (NL/hour of reagents/L of catalyst) using a catalyst consisting of spheroidal pellets of a-AEO ⁇ on which species of Rh (0.5% by weight) are deposited in the upper part of the catalytic bed and of Rh-Ni (0.5 and 2.5% by weight respectively) in the final part of the catalytic bed where the oxygen has been consumed by the hydrocarbon oxidation reactions.
- the SCT-CPO reactor produces from natural gas (NG), O2 , and steam a synthesis gas suitable for use in a BF. This synthesis gas is produced at a pressure of 2.5 bar g and a temperature of 950°C. It has an R-value of > 7.5 v/v and a moisture content of approximately 8% v/v.
- the reduction in the quantity of coke and coal dust used avoids the emission of 327,500 - 376,500 tonnes of CO2 per year, which is partly offset by CO2 emissions linked to the production and use of synthesis gas from natural gas (305,100 tonnes of CO2 ), which, however, does not contribute to NOx, SOx, aromatic and poly-aromatic and particulate emissions. Overall, therefore, the reduction in CO2 is between 22,300 and 71,400 tonnes per year.
- Table 5 shows the input and output compositions to a SCT-CPO reactor operating at a gas hourly space velocity (GHSV) of 80,000 hours 1 (NL/hour of reagents/L of catalyst) using a catalyst consisting of spheroidal pellets of 01-AI2O3 on which species of Rh (0.5% by weight) are deposited in the upper part of the catalytic bed and of Rh-Ni (0.5 and 2.5% by weight respectively) in the final part of the catalytic bed where the oxygen has been consumed by the hydrocarbon oxidation reactions.
- the SCT-CPO reactor produces from NG, O2, steam a synthesis gas suitable for use in a BF. This synthesis gas is produced at a pressure of 2.5 bar g and a T of 950°C. It has an R value > 7.5 v/v, a moisture content of approximately 8% v/v. Twice the amount of hydrogen is added to this synthesis gas with respect to the oxygen produced by the water electrolysis process.
- GHSV gas hourly space velocity
- the reduction of coke and coal dust use avoids the emission of between 342,600 and 393,000 tonnes of CO2 per year, which will be partly offset by CO2 emissions linked to the production and use of synthesis gas from natural gas (226,600 tonnes of CO2 ), which in any case does not contribute to NOx, SOx, aromatic and poly-aromatic and particulate emissions. Overall, therefore, the reduction in CO2 emissions is between 116,100 and 167,400 tonnes per year.
- This example describes an integrated synthesis gas production process using a SCT-CPO process fed with biogas and Oxygen and its use in the reduction of iron ore in a BF.
- Table 6 shows the inlet and outlet compositions to a SCT-CPO reactor producing synthesis gas containing 45% v/v CO2 , O2 in the absence of steam in the reagent mixture.
- the synthesis gas is suitable for use in a BF.
- the reactor operates at a gas hourly space velocity (GHSV) of 80,000 hours 1 (NF/hour of reagents/F of catalyst) using a catalyst consisting of spheroidal pellets of a-AF O3 on which species of Rh (0.5% by weight) are deposited in the upper part of the catalytic bed and of Rh- Ni species (0.5 and 2.5% by weight respectively) in the final part of the catalytic bed where the oxygen has been consumed by the hydrocarbon oxidation reactions.
- biogas can clearly complement the use of other gaseous hydrocarbon sources such as natural gas and coke oven and BFG (see examples 5 and 6) and enable the production of a synthesis gas with a lower vapour content and higher reducing power R.
- biogas does not contribute to NOx, SOx, aromatic and poly-aromatic and particulate emissions and to CO2 emissions.
- This example describes an integrated process for producing synthesis gas using a catalytic partial oxidation (CPO) process fed with biogas with 45% v/v CO2, oxygen and hydrogen produced in an electrolysis process, and its use in the reduction of iron ore in a BF.
- CPO catalytic partial oxidation
- Table 7 shows the inlet and outlet compositions of a CPO reactor fed with biogas containing 45% v/v CO2, O2 and in the absence of steam in the reagent mixture.
- the synthesis gas produced is suitable for use in a BF.
- the reactor operates at a gas hourly space velocity (GHSV) of 80,000 hours 1 (NF/hour of reagents/F of catalyst) using a catalyst consisting of spheroidal pellets of a-AF O3 on which species of Rh (0.5% by weight) are deposited in the upper part of the catalytic bed and of Rh- Ni, in quantities of 0.5 and 2.5% by weight respectively, in the final part of the catalytic bed, where the oxygen has been consumed by the hydrocarbon oxidation reactions.
- the synthesis gas is produced at a pressure of 2.5 kg/cm 2 at a temperature of 950°C.
- biogas can clearly complement the use of other gaseous hydrocarbon sources such as natural gas and coke oven and BF gases (see examples 5 and 6) and allow the production of a synthesis gas with a lower steam content and a higher reducing power R.
- Table 7
- CO2 emissions the reduction of the amount of coke used, and of coal dust, avoids the emission of 335,000 to 385,300 tonnes of CO2 per year. Furthermore, the use of biogas does not contribute to NOx, SOx, aromatic hydrocarbons and polycondensed aromatic hydrocarbons emissions, or to CO2 emissions.
- Table 8 shows the inlet and outlet compositions for a SCT-CPO reactor fed with the mixture defined above, with a reduced amount of steam.
- the synthesis gas produced is suitable for use in a BF.
- the reactor operates at a gas hourly space velocity (GHSV) of 95,000 hours 1 (NL/hour of reagents/L of catalyst), using a catalyst consisting of spheroidal pellets of a-AF O3 on which Rh species (0.8% by weight) are deposited in the upper part of the catalytic bed and Rh-Ni species (0.5 and 3.5% by weight respectively) in the final part of the catalytic bed, where the oxygen has been consumed by the hydrocarbon oxidation reactions.
- GHSV gas hourly space velocity
- Synthesis gas is produced at a pressure of 2.5 kg/cm 2 and a temperature of 950°C. It has an R- value of > 7.5 v/v and a moisture content of less than 7% v/v.
- CO2 emissions the reduction of coke and coal dust used avoids emissions of between 251,300 and 289,000 tonnes of CO2 per year, which are however partly offset by CO2 emissions related to the production and use of synthesis gas from natural gas (135,600 tonnes of CO2 ) ⁇ However, this does not contribute to emissions of NOx, SOx, aromatic hydrocarbons, polycondensed aromatic hydrocarbons and particulates.
- Table 9 shows the inlet and outlet compositions for a SCT-CPO reactor fed with the mixture defined above, with a reduced amount of steam.
- the volume of hydrogen co-produced through the electrolysis of water with oxygen is added to the synthesis gas thus produced.
- the synthesis gas produced is suitable for use in a BF.
- the reactor operates at a gas hourly space velocity (GHSV) of 95,000 hours 1 (NL/hour of reagents/L of catalyst), using a catalyst consisting of spheroidal pellets of a-AF O3 on which Rh (0.5% by weight) and Ir species (0.5% by weight) are deposited in the upper part of the catalytic bed and Ir-Ni species (0.5 and 3.5% by weight respectively) in the final part of the catalytic bed, where the oxygen has been consumed by the hydrocarbon oxidation reactions.
- the synthesis gas is produced at a pressure of 2.5 kg/cm 2 at a temperature of 950°C, has an R- value > 7.5 v/v and a moisture content of the order of 7% v/v.
- This saving in a plant with a production of 2.35 million tonnes of metal per year, corresponds to a reduction in production and use of between 91,700 and 105,400 tonnes of coke and coal dust per year and of the associated pollutant emissions of NOx, SOx, aromatic hydrocarbons, polycondensed aromatic hydrocarbons and particulates.
- CO2 emissions the lower consumption of coke and coal dust avoids emissions of between 296,900 and 341,500 tonnes of CO2 per year, which are partly offset by CO2 emissions linked to the production and use of synthesis gas from natural gas (135,600 tonnes of CO2). This, however, does not contribute to emissions of NOx, SOx, aromatic hydrocarbons, polycondensed aromatic hydrocarbons and particulate matter.
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- Chemical & Material Sciences (AREA)
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- Manufacture Of Iron (AREA)
Abstract
L'invention concerne un procédé de réduction de minerai de fer dans des BF, permettant la production de composés de fer et/ou de fer-carbone à faible impact environnemental. Un gaz de synthèse produit à partir d'un courant d'hydrocarbures, à l'aide d'un procédé d'oxydation partielle catalytique à court temps de contact (SCT-CPO) intégré au procédé de réduction du minerai de fer, est également utilisé dans les BF.
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Application Number | Priority Date | Filing Date | Title |
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IT102021000011189A IT202100011189A1 (it) | 2021-05-03 | 2021-05-03 | Processo a basso impatto ambientale per la riduzione di minerali ferrosi in altoforno impiegante gas di sintesi |
PCT/EP2022/061672 WO2022233769A1 (fr) | 2021-05-03 | 2022-05-02 | Procédé d'utilisation de gaz de synthèse pour améliorer l'impact environnemental de la réduction de minerai de fer dans des hauts fourneaux |
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EP4334481A1 true EP4334481A1 (fr) | 2024-03-13 |
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EP22727766.2A Pending EP4334481A1 (fr) | 2021-05-03 | 2022-05-02 | Procédé d'utilisation de gaz de synthèse pour améliorer l'impact environnemental de la réduction de minerai de fer dans des hauts fourneaux |
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AU (1) | AU2022268546A1 (fr) |
CA (1) | CA3218702A1 (fr) |
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IT1272532B (it) | 1993-08-27 | 1997-06-23 | Snam Progetti | Processo di ossidazione parziale catalitica del gas naturale per ottenere gas di sintesi e formaldeide |
IT1283585B1 (it) | 1996-04-11 | 1998-04-22 | Snam Progetti | Apparecchiatura per effettuare reazioni di ossidazione parziale |
ITMI20021133A1 (it) | 2002-05-24 | 2003-11-24 | Snam Progetti | Procedimento per reazioni di ossidazione parziale catalitica |
ITMI20031739A1 (it) | 2003-09-11 | 2005-03-12 | Enitecnologie Spa | Procedimento di ossidazione parziale catalitica per |
ITMI20041860A1 (it) | 2004-09-30 | 2004-12-30 | Eni Spa | Apparecchiatura per nebulizzare una corrente liquida con una corrente disperdente gassosa e miscelare il prodotto nebulizzato con un'ulteriore corrente gassosa adatta in apparecchiature per effettuare ossidazioni parziali catalitiche e relativo proce |
ITMI20052002A1 (it) | 2005-10-21 | 2007-04-22 | Eni Spa | Dispositivo per miscelare fluidi inserito o combinato ad un reattore |
KR20070067830A (ko) * | 2005-12-23 | 2007-06-29 | 재단법인 포항산업과학연구원 | 석탄과 철광석을 이용한 수소와 선철 생산 방법 |
ITMI20072209A1 (it) | 2007-11-21 | 2009-05-22 | Eni Spa | Procedimento migliorato per la produzione di gas di sintesi a partire da idrocarburi ossigenati ricavati da biomasse |
ITMI20072228A1 (it) | 2007-11-23 | 2009-05-24 | Eni Spa | Procedimento per produrre gas di sintesi e idrogeno a partire da idrocarburi liquidi e gassosi |
US8050369B2 (en) | 2008-04-14 | 2011-11-01 | Telefonaktiebolaget Lm Ericsson (Publ) | System and method of receiving and processing multicommunication signals |
IT1398292B1 (it) | 2009-12-16 | 2013-02-22 | Eni Spa | Processo per la produzione di idrogeno a partire da idrocarburi liquidi, idrocarburi gassosi e/o composti ossigenati anche derivanti da biomasse |
CN102782161A (zh) * | 2010-03-02 | 2012-11-14 | 杰富意钢铁株式会社 | 高炉的操作方法、炼钢厂的操作方法和含氧化碳气体的利用方法 |
IT1400492B1 (it) | 2010-06-03 | 2013-06-11 | Eni Spa | Sistema catalitico per processi di ossidazione parziale catalitica a basso tempo di contatto |
JP6019893B2 (ja) * | 2012-07-31 | 2016-11-02 | Jfeスチール株式会社 | 高炉の操業方法 |
WO2016016256A1 (fr) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Procédé intégré d'oxydation catalytique partielle à temps de contact court/reformage autotherme (sct-cpo/atr) pour la production de gaz de synthèse |
WO2016016251A1 (fr) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Procédé de production sct-cpo/sr intégré pour la production de gaz de synthèse |
WO2016016257A1 (fr) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Procédé intégré d'oxydation catalytique partielle à temps de contact court pour la production de gaz de synthèse |
WO2016016253A1 (fr) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Procédé intégré de reformage par oxydation catalytique partielle/chauffé au gaz à temps de contact court pour la production de gaz de synthèse |
CN106139838B (zh) * | 2016-07-12 | 2019-04-16 | 李智信 | 用回收co2在钢铁厂研制可循环再生能源系列产品的技术 |
FI3853196T3 (fi) | 2018-09-19 | 2024-02-01 | Eni Spa | Menetelmä metanolin valmistamiseksi kaasumaisista hiilivedyistä |
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WO2022233769A1 (fr) | 2022-11-10 |
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