US20150191803A1 - Blast-furnace-blow-in charcoal and method for producing same - Google Patents

Blast-furnace-blow-in charcoal and method for producing same Download PDF

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Publication number
US20150191803A1
US20150191803A1 US14/412,921 US201314412921A US2015191803A1 US 20150191803 A1 US20150191803 A1 US 20150191803A1 US 201314412921 A US201314412921 A US 201314412921A US 2015191803 A1 US2015191803 A1 US 2015191803A1
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United States
Prior art keywords
coal
blast furnace
oxygen
furnace injection
pyrolysis
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Abandoned
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US14/412,921
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English (en)
Inventor
Setsuo Omoto
Keiichi Nakagawa
Tsutomu Hamada
Masakazu Sakaguchi
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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Assigned to MITSUBISHI HEAVY INDUSTRIES, LTD. reassignment MITSUBISHI HEAVY INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAMADA, TSUTOMU, NAKAGAWA, KEIICHI, OMOTO, SETSUO, SAKAGUCHI, MASAKAZU
Publication of US20150191803A1 publication Critical patent/US20150191803A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/007—Conditions of the cokes or characterised by the cokes used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
    • C10B57/10—Drying
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/14—Features of low-temperature carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof
    • 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
    • C21B5/003—Injection of pulverulent coal

Definitions

  • the present invention relates to blast furnace injection coal and a method of manufacturing the same.
  • Blast furnace installations are designed to be capable of manufacturing pig iron from iron ore by charging raw materials such as iron ore, limestone, and coke into the blast furnace main unit through the top and blowing hot air and pulverized coal (PCI coal) as auxiliary fuel through the tuyeres on the lower lateral side.
  • PCI coal pulverized coal
  • coals have been proposed which are obtained by adding an oxidant such for example as KMn0 4 , H 2 O 2 , KClO 3 , or K 2 Cr 2 O 4 to pulverized coal in advance to improve the combustion efficiency so that generation of unburned carbon (soot) can be suppressed (see Patent Literature 1 listed below, for example).
  • an oxidant such for example as KMn0 4 , H 2 O 2 , KClO 3 , or K 2 Cr 2 O 4
  • Patent Literature 1 Japanese Patent Application Publication No. Hei 6-220510
  • Patent Literature 2 Japanese Patent Application Publication No. 2003-286511
  • Patent Literature 2 listed above requires operating the blast furnace with a large amount of oxygen constantly added into the hot air and therefore increases the running cost as well.
  • an object of the present invention is to provide blast furnace injection coal and a method of manufacturing the same which are capable of improving the combustion efficiency at a low cost and suppressing generation of unburned carbon (soot).
  • Blast furnace injection coal for solving the above-mentioned problems is blast furnace injection coal to be blown into a blast furnace main unit of a blast furnace installation through a tuyere, characterized in that an oxygen atom content ratio (dry base) is between 10 and 20% by weight, and an average pore size is between 10 and 50 nm.
  • Blast furnace injection coal according to a second aspect of the invention is the first aspect of the invention, characterized in that a pore volume is between 0.05 and 0.5 cm 3 /g.
  • Blast furnace injection coal according to a third aspect of the invention is the first or second aspect of the invention, characterized in that a specific surface area is between 1 and 100 m 2 /g.
  • a method of manufacturing blast furnace injection coal according to a fourth aspect of the invention for solving the above-mentioned problems is a method of manufacturing the blast furnace injection coal according to any one of the first to third aspect of the invention, characterized in that the method comprises: a drying step of heating subbituminous coal or brown coal to remove moisture; and a pyrolysis step of performing pyrolysis at a temperature between 460 and 590° C. on the coal dried in the drying step.
  • the method of manufacturing blast furnace injection coal according to a fifth aspect of the invention is the fourth aspect of the invention, characterized in that the method further comprises: a cooling step of cooling the coal subjected to the pyrolysis in the pyrolysis step to a temperature between 50 and 150° C.; and a partially oxidizing step of partially oxidizing the coal cooled in the cooling step by exposing the coal in an oxygen-containing atmosphere at a temperature between 50 and 150° C. to let the coal chemically adsorb oxygen.
  • the average pore size is 10 to 50 nm, that is, tar producing groups such as oxygen-containing functional groups (such as carboxyl groups, aldehyde groups, ester groups, and hydroxyl groups) desorb and greatly decrease, while the oxygen atom content ratio (dry base) is 10 to 20% by weight, that is, decomposition (decrease) of the main skeletons (combustion components mainly containing C, H, and O) is greatly suppressed.
  • oxygen-containing functional groups such as carboxyl groups, aldehyde groups, ester groups, and hydroxyl groups
  • the blast furnace injection coal when such blast furnace injection coal is blown into the blast furnace main unit through the tuyere together with hot air, the blast furnace injection coal can be completely combusted with almost no unburned carbon (soot) generated because many oxygen atoms are contained in the main skeletons and also because the large-sized pores allow the oxygen in the hot air to be easily spread to the inside and also significantly suppresses the production of tar. Accordingly, it is possible to improve the combustion efficiency at a low cost and suppress generation of unburned carbon (soot).
  • the blast furnace injection coals described above can be manufactured at a low cost.
  • FIG. 1 is a flowchart showing the procedure of a first embodiment of a method of manufacturing blast furnace injection coal according to the present invention.
  • FIG. 2 is a flowchart showing the procedure of a second embodiment of the method of manufacturing blast furnace injection coal according to the present invention.
  • FIG. 3 is a graph showing the relation between the temperature of subbituminous coal and the ratio of content of each of its oxygen-containing functional groups based on an infrared absorption spectrum of the subbituminous coal measured with its temperature is raised under a nitrogen-containing atmosphere.
  • FIG. 4 is a graph showing the relation between the ratios of unburned carbon collected after present invention coal, dried coal, and conventional coal are combusted, and the concentrations of residual oxygen (excess oxygen concentrations) in combustion exhaust gases after the combustion.
  • FIG. 5 is a graph showing the relation between the excess oxygen ratio and the combustion temperature of complete combustion of each of the present invention and the conventional coal.
  • a first embodiment of the blast furnace injection coal and the method of manufacturing the same according to the present invention will be described with reference to FIG. 1 .
  • the blast furnace injection coal according to this embodiment has an oxygen atom content ratio (dry base) of 10 to 18% by weight and an average pore size of 10 to 50 nm (nanometer) (preferably 20 to 50 nm (nanometer)).
  • the blast furnace injection coal according to this embodiment as mentioned above can be easily manufactured by: drying low-rank coal (oxygen atom content ratio (dry base): over 18% by weight, average pore size: 3 to 4 nm) 11 such as subbituminous coal or brown coal by heating it (at 110 to 200° C. ⁇ 0.5 to 1 hour) in a low oxygen atmosphere (oxygen concentration: 5% by volume or lower) to remove moisture (drying step S 11 ); performing pyrolysis on the resultant coal by heating it (at 460 to 590° C.
  • drying low-rank coal (oxygen atom content ratio (dry base): over 18% by weight, average pore size: 3 to 4 nm) 11 such as subbituminous coal or brown coal by heating it (at 110 to 200° C. ⁇ 0.5 to 1 hour) in a low oxygen atmosphere (oxygen concentration: 5% by volume or lower) to remove moisture (drying step S 11 ); performing pyrolysis on the resultant coal by heating it (at 460 to 590° C.
  • the average pore size is 10 to 50 nm, that is, tar producing groups such as oxygen-containing functional groups (such as carboxyl groups, aldehyde groups, ester groups, and hydroxyl groups) desorb and greatly decrease, while the oxygen atom content ratio (dry base) is 10 to 18% by weight, that is, decomposition (decrease) of the main skeletons (combustion components mainly containing C, H, and O) is greatly suppressed.
  • oxygen-containing functional groups such as carboxyl groups, aldehyde groups, ester groups, and hydroxyl groups
  • the blast furnace injection coal 12 when the blast furnace injection coal 12 is blown into a blast furnace main unit through each tuyere together with hot air, the blast furnace injection coal 12 can be completely combusted with almost no unburned carbon (soot) generated because many oxygen atoms are contained in the main skeletons and also because the large-sized pores allow the oxygen in the hot air to be easily spread to the inside and also significantly suppresses the production of tar.
  • the blast furnace injection coal 12 can improve the combustion efficiency and suppress generation of unburned carbon (soot) without adding an oxidant such as KMn0 4 , H 2 O 2 , KClO 3 , or K 2 Cr 2 O 4 or enriching the oxygen in the hot air.
  • an oxidant such as KMn0 4 , H 2 O 2 , KClO 3 , or K 2 Cr 2 O 4 or enriching the oxygen in the hot air.
  • the average pore size of the blast furnace injection coal 12 needs to be 10 to 50 nm (preferably 20 to 50 nm). This is because if the average pore size is smaller than 10 nm, the spreadability of the oxygen in the hot air to the inside will be deteriorated and the combustibility will be accordingly deteriorated, whereas if the average pore size is larger than 50 nm, the blast furnace injection coal 12 will easily crack into smaller sizes due to heat shock and the like, and will therefore crack into smaller sizes when blown into the blast furnace main unit, which leads to a situation where the blast furnace injection coal 12 passes through the inside of the blast furnace main unit with a gas stream and is discharged without combustion.
  • the oxygen atom content ratio (dry base) needs to be not smaller than 10% by weight as well. This is because it will be difficult to achieve complete combustion without adding an oxidant or enriching the oxygen in the hot air if the oxygen atom content ratio (dry base) is smaller than 10% by weight.
  • the pore volume is preferably 0.05 to 0.5 cm 3 /g and particularly preferably 0.1 to 0.2 cm 3 /g. This is because the surface area of contact (surface area of reaction) with the oxygen in the hot air will be small and the combustibility will possibly be deteriorated if the pore volume is smaller than 0.05 cm 3 /g, whereas large amounts of components will volatilize and the blast furnace injection coal 12 will be so porous that the combustion components may be excessively reduced if the pore volume is larger than 0.5 cm 3 /g.
  • the specific surface area is preferably 1 to 100 m 2 /g and particularly preferably 5 to 20 m 2 /g. This is because the surface area of contact (surface area of reaction) with the oxygen in the hot air will be small and the combustibility will possibly be deteriorated if the specific surface area is smaller than 1 m 2 /g, whereas large amounts of components will volatilize and the blast furnace injection coal 12 will be so porous that the combustion components may be excessively reduced if the specific surface area is larger than 100 m 2 /g.
  • the temperature of the pyrolysis in the pyrolysis step S 12 needs to be 460 to 590° C. (preferably 500 to 550° C.).
  • the tar producing groups such as oxygen-containing functional groups will fail to be desorbed sufficiently from the low-rank coal 11 and it will be extremely difficult to obtain an average pore size of 10 to 50 nm if the temperature is lower than 460° C.
  • the decomposition of the main skeletons (combustion components mainly containing C, H, and O) of the low-rank coal 11 will start to be remarkable, and large amounts of component will volatilize, which in turn excessively reduces the combustion components, if the temperature is higher than 590° C.
  • a second embodiment of the blast furnace injection coal and the method of manufacturing the same according to the present invention will be described with reference to FIG. 2 . Note that for portions similar to those in the foregoing embodiment, reference signs similar to the reference signs used in the description of the foregoing embodiment will be used, and their description overlapping the description in the foregoing embodiment will be omitted.
  • the blast furnace injection coal according to this embodiment has an oxygen atom content ratio (dry base) of 12 to 20% by weight and an average pore size of 10 to 50 nm (preferably 20 to 50 nm).
  • the blast furnace injection coal according to this embodiment as mentioned above can be easily manufactured by: drying the low-rank coal (oxygen atom content ratio (dry base): over 18% by weight) 11 in a similar way to the foregoing embodiment (drying step S 11 ); performing pyrolysis on the resultant coal in a similar way to the foregoing embodiment (pyrolysis step S 12 ); cooling the resultant coal (to 50 to 150° C.) in a low oxygen atmosphere (oxygen concentration: 2% by volume or lower) (cooling step S 23 ); partially oxidizing the resultant coal by exposing it to an oxygen-containing atmosphere (oxygen concentration: 5 to 21% by volume) (at 50 to 150° C. ⁇ 0.5 to 10 hours) to let the coal chemically adsorb oxygen (partially oxidizing step S 25 ); and pulverizing the resultant coal in a similar way to the foregoing embodiment (pulverizing step S 14 ).
  • the coal subjected to the pyrolysis in the pyrolysis step S 12 is cooled to 50 to 150° C., and the coal is then partially oxidized by letting the coal chemically adsorb oxygen in the partially oxidizing step S 25 , to thereby obtain blast furnace injection coal 22 having an oxygen atom content ratio (dry base) of 12 to 20% by weight.
  • the average pore size is 10 to 50 nm, that is, tar producing groups such as oxygen-containing functional groups (such as carboxyl groups, aldehyde groups, ester groups, and hydroxyl groups) desorb and greatly decrease, while the oxygen atom content ratio (dry base) is 12 to 20% by weight, that is, decomposition (decrease) of the main skeletons (combustion components mainly containing C, H, and O) is greatly suppressed, and more oxygen atoms have chemically adsorbed.
  • oxygen-containing functional groups such as carboxyl groups, aldehyde groups, ester groups, and hydroxyl groups
  • the blast furnace injection coal 22 when the blast furnace injection coal 22 is blown into the blast furnace main unit through the tuyere together with hot air, the blast furnace injection coal 22 can be completely combusted with less unburned carbon (soot) generated than in the foregoing embodiment because the main skeletons contains more oxygen atoms than in the foregoing embodiment and also because the large-sized pores allow the oxygen in the hot air to be easily spread to the inside and also significantly suppresses the production of tar like the foregoing embodiment.
  • the blast furnace injection coal 22 can improve the combustion efficiency to a greater extent and suppress generation of unburned carbon (soot) more reliably than in the foregoing embodiment without adding an oxidant such as KMn0 4 , H 2 O 2 , KClO 3 , or K 2 Cr 2 O 4 or enriching the oxygen in the hot air.
  • an oxidant such as KMn0 4 , H 2 O 2 , KClO 3 , or K 2 Cr 2 O 4 or enriching the oxygen in the hot air.
  • the oxygen atom content ratio (dry base) of the blast furnace injection coal 22 needs to be 20% by weight or lower. This is because the oxygen content will be excessively large and the amount of heat generation will be excessively reduced if the oxygen atom content ratio (dry base) is smaller than 20% by weight.
  • the temperature of the process in the partially oxidizing step S 25 is preferably 50 to 150° C. This is because it will be difficult to advance the partial oxidation process even in an air (oxygen concentration: 21% by volume) atmosphere if the temperature is lower than 50° C., whereas large amounts of carbon monoxide and carbon dioxide will possibly be generated by the combustion reaction even in an atmosphere where the oxygen concentration is about 5% by volume if the temperature is higher than 150° C.
  • a composition analysis was performed on the blast furnace injection coal 12 obtained by the manufacturing method according to the first embodiment described above (present invention coal). Moreover, for comparison, a composition analysis was performed also on conventional blast furnace injection coal (PCI coal: conventional coal), and on coal obtained by omitting the pyrolysis step S 12 in the first embodiment (dried coal). Table 1 given below shows the results. Note that the values are all on the dry base.
  • the oxygen (O) ratio of the present invention coal is smaller than that of the dried coal and significantly larger than that of the conventional coal, while the carbon (C) ratio is larger than that of the dried coal and smaller than that of the conventional coal.
  • the calorific value of the present invention coal is larger than that of the dried coal and smaller than that of the conventional coal.
  • the average pore size of the present invention coal is significantly larger than those of the conventional coal and the dried coal.
  • FIG. 3 shows the result. Note that the horizontal axis represents the temperature, and the vertical axis represents the ratio of the peak area of each oxygen-containing functional group to the whole peak area of the oxygen-containing functional groups at 110° C.
  • the above oxygen-containing functional groups i.e. the tar producing groups are confirmed to mostly disappear at 460° C. and completely disappear at 500° C.
  • FIG. 4 shows the results. Note that in FIG. 4 , the horizontal axis represents the concentration of residual oxygen in combustion exhaust gas after the combustion of the coal, i.e. excess oxygen concentration, and the vertical axis represents the ratio of unburned carbon collected after the combustion of the coal.
  • Oa is the molar flow rate of the oxygen gas (molecules) in the fed air
  • Oc is the molar flow rate of the oxygen atoms in the fed coal
  • Cc is the molar flow rate of the carbon atoms in the fed coal
  • Hc is the molar flow rate of the hydrogen atoms in the fed coal.
  • the calorific value of the present invention coal is smaller than that of the conventional coal, the combustion temperature is confirmed to be higher than that of the conventional coal in a case where the excess oxygen ratio is the same as that of the conventional coal.
  • the present invention coal has a larger oxygen content ratio than the conventional coal does, and therefore only requires a smaller amount of fed air than the conventional coal does on condition that the excess oxygen ratio is the same as that of the conventional coal.
  • blast furnace injection coals and the methods of manufacturing the same according to the present invention can be utilized significantly beneficially in the coal industry, steel industry, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Iron (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Coke Industry (AREA)
US14/412,921 2012-08-03 2013-05-15 Blast-furnace-blow-in charcoal and method for producing same Abandoned US20150191803A1 (en)

Applications Claiming Priority (3)

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JP2012-172756 2012-08-03
JP2012172756 2012-08-03
PCT/JP2013/063506 WO2014020965A1 (ja) 2012-08-03 2013-05-15 高炉吹込み炭及びその製造方法

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US (1) US20150191803A1 (ko)
JP (1) JP5843968B2 (ko)
KR (1) KR101657427B1 (ko)
CN (1) CN104411838B (ko)
AU (1) AU2013297837B2 (ko)
DE (1) DE112013003846T5 (ko)
IN (1) IN2015DN00192A (ko)
WO (1) WO2014020965A1 (ko)

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CN115353914A (zh) * 2022-09-13 2022-11-18 中国科学院广州能源研究所 一种焦油净化处理的方法及系统

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JP6551470B2 (ja) * 2016-07-29 2019-07-31 Ｊｆｅスチール株式会社 高炉操業方法
JP6551471B2 (ja) * 2016-07-29 2019-07-31 Ｊｆｅスチール株式会社 高炉操業方法

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DE112013003846T5 (de) 2015-04-23
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AU2013297837A1 (en) 2015-01-29
IN2015DN00192A (ko) 2015-06-12
AU2013297837B2 (en) 2016-03-10
JPWO2014020965A1 (ja) 2016-07-21
KR20150024913A (ko) 2015-03-09
WO2014020965A1 (ja) 2014-02-06
JP5843968B2 (ja) 2016-01-13
CN104411838B (zh) 2017-03-29

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