WO2014020965A1 - 高炉吹込み炭及びその製造方法 - Google Patents

高炉吹込み炭及びその製造方法 Download PDF

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Publication number
WO2014020965A1
WO2014020965A1 PCT/JP2013/063506 JP2013063506W WO2014020965A1 WO 2014020965 A1 WO2014020965 A1 WO 2014020965A1 JP 2013063506 W JP2013063506 W JP 2013063506W WO 2014020965 A1 WO2014020965 A1 WO 2014020965A1
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WO
WIPO (PCT)
Prior art keywords
blast furnace
charcoal
coal
oxygen
blown
Prior art date
Application number
PCT/JP2013/063506
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English (en)
French (fr)
Japanese (ja)
Inventor
大本　節男
慶一 中川
務 濱田
雅一 坂口
Original Assignee
三菱重工業株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 三菱重工業株式会社 filed Critical 三菱重工業株式会社
Priority to US14/412,921 priority Critical patent/US20150191803A1/en
Priority to IN192DEN2015 priority patent/IN2015DN00192A/en
Priority to KR1020157001877A priority patent/KR101657427B1/ko
Priority to AU2013297837A priority patent/AU2013297837B2/en
Priority to DE112013003846.3T priority patent/DE112013003846T5/de
Priority to CN201380035147.8A priority patent/CN104411838B/zh
Priority to JP2014528025A priority patent/JP5843968B2/ja
Publication of WO2014020965A1 publication Critical patent/WO2014020965A1/ja

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    • 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
    • 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
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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-blown coal and a method for producing the same.
  • pig iron In the blast furnace facility, raw materials such as iron ore, limestone and coke are charged into the blast furnace body from the top, and hot air and pulverized coal (PCI charcoal) are blown from the tuyere at the lower side of the blast furnace as auxiliary fuel.
  • PCI charcoal hot air and pulverized coal
  • Patent Document 1 adds an oxidizer as described above to the pulverized coal, which increases the running cost.
  • an object of the present invention is to provide a blast furnace-blown coal that can improve the combustion efficiency and suppress the generation of unburned carbon (soot) at a low cost, and a method for producing the same.
  • the blast furnace injection coal according to the first invention for solving the above-mentioned problem is blast furnace injection coal injected from the tuyere into the blast furnace main body of the blast furnace equipment, and has an oxygen atom content ratio (dry base). Is 10 to 20% by weight, and the average pore diameter is 10 to 50 nm.
  • the blast furnace blown coal according to the second invention is characterized in that, in the first invention, the pore volume is 0.05 to 0.5 cm 3 / g.
  • the blast furnace blown coal according to the third invention is characterized in that, in the first or second invention, the specific surface area is 1 to 100 m 2 / g.
  • a method for producing blast furnace blown coal according to the fourth aspect of the invention for solving the above-described problem is a method for producing blast furnace blown coal according to any one of the first to third aspects of the invention.
  • a drying process for removing moisture by heating subbituminous coal or lignite and a carbonization process for carbonizing the charcoal dried in the drying process at 460 to 590 ° C. are performed.
  • a blast furnace-blown coal production method according to the fourth aspect of the present invention, wherein the charcoal dry-distilled in the dry distillation step is cooled to 50 to 150 ° C. and cooled in the cooling step.
  • the charcoal is exposed to an oxygen-containing atmosphere at 50 to 150 ° C. to perform a partial oxidation step in which oxygen is chemically adsorbed and partially oxidized.
  • the average pore diameter is 10 to 50 nm, that is, tar-generating groups such as oxygen-containing functional groups (carboxyl group, aldehyde group, ester group, hydroxyl group, etc.) are eliminated.
  • the oxygen atom content (dry base) is 10 to 20% by weight, that is, the decomposition (reduction) of the main skeleton (combustion components centering on C, H, O) is greatly suppressed. Therefore, when blowing with hot air from the tuyere into the inside of the blast furnace body, it contains not only oxygen atoms in the main skeleton, but also oxygen in the hot air is easily diffused into the interior by the large diameter pores. Because it is very difficult to generate a fraction, it can be burned completely with almost no unburned carbon (soot), so the combustion efficiency is improved at low cost and the generation of unburned carbon (soot) is suppressed. It can be.
  • the above-described blast furnace blow coal can be produced at low cost.
  • the blast furnace-blown coal according to the present embodiment has an oxygen atom content (dry base) of 10 to 18% by weight and an average pore diameter of 10 to 50 nm (nanometer) (preferably 20 to 50 nm (nanometer). ).
  • the blast furnace blown coal is a low-grade coal such as subbituminous coal or lignite (oxygen atom content ratio (dry base): more than 18% by weight, average pore diameter: 3
  • a low-grade coal such as subbituminous coal or lignite (oxygen atom content ratio (dry base): more than 18% by weight, average pore diameter: 3
  • dry distillation step S12 Water, carbon dioxide, tar content, etc.
  • the average pore diameter is 10 to 50 nm, that is, oxygen-containing functional groups (carboxyl group, aldehyde group, ester group, hydroxyl group, etc. ) And other tar-forming groups are greatly reduced, but the oxygen atom content (dry base) is 10 to 18% by weight, that is, a combustion component mainly composed of the main skeleton (C, H, O) ) Is greatly suppressed, and when hot air is blown into the blast furnace body together with hot air from the tuyere, the main skeleton contains a large amount of oxygen atoms, and the oxygen in the hot air is contained inside by the large-diameter pores. In addition to being easily diffused, the tar content is very difficult to generate, so that it is possible to complete combustion with almost no unburned carbon (soot).
  • the blast furnace blowing coal 12 according to the present embodiment, KMnO 4, H 2 O 2 , KClO 3, K 2 and be contained Cr oxidizing agent such as 2 O 4, so as to enrich the oxygen in a hot-air Even if nothing is done, the combustion efficiency can be improved and the generation of unburned carbon (soot) can be suppressed.
  • the average pore diameter needs to be 10 to 50 nm (preferably 20 to 50 nm). Because if it is less than 10 nm, the ease of diffusion of oxygen in the hot air will decrease, causing a decrease in combustibility, while if it exceeds 50 nm, it tends to crack and become fine due to heat shock or the like. This is because, when blown into the blast furnace body, if it breaks and becomes fine, it passes through the inside of the blast furnace body while riding on a gas stream and is discharged without burning.
  • the oxygen atom content (dry base) needs to be 10% by weight or more. This is because if it is less than 10% by weight, it becomes difficult to completely burn without containing an oxidant and enriching hot air with oxygen.
  • the pore volume is preferably 0.05 to 0.5 cm 3 / g, and particularly preferably 0.1 to 0.2 cm 3 / g. Because, if it is less than 0.05 cm 3 / g, the contact area with oxygen in the hot air (reaction area) is small, which may cause a decrease in combustibility, whereas if it exceeds 0.5 cm 3 / g, This is because the volatilization of many components results in excessively porous components due to being too porous.
  • the specific surface area is preferably 1 to 100 m 2 / g, and particularly preferably 5 to 20 m 2 / g. Because if it is less than 1 m 2 / g, the contact area (reaction area) with oxygen in the hot air is small, which may cause a decrease in combustibility, while if it exceeds 100 m 2 / g, many components This is because the volatilization of the fuel is too porous and the combustion components become too small.
  • the dry distillation temperature in the dry distillation step S12 needs to be 460 to 590 ° C. (preferably 500 to 550 ° C.). This is because if the temperature is lower than 460 ° C., tar-generating groups such as oxygen-containing functional groups cannot be sufficiently removed from the low-grade coal 11 and it is very difficult to make the average pore diameter 10 to 50 nm. On the other hand, when the temperature exceeds 590 ° C., decomposition of the main skeleton of the low-grade coal 11 (combustion components centering on C, H, O) starts to become remarkable, and the combustion components decrease due to volatilization of many components. This is because too much is done.
  • the blast furnace-blown coal according to this embodiment has an oxygen atom content (dry base) of 12 to 20% by weight and an average pore diameter of 10 to 50 nm (preferably 20 to 50 nm).
  • the blast furnace injection coal according to this embodiment is the same as the above-described embodiment in which the low-grade coal (oxygen atom content ratio (dry base): more than 18 wt%) 11 is used.
  • the charcoal carbonized in the carbonization step S12 is cooled to 50 to 150 ° C., and then oxygen is chemically adsorbed to the charcoal in the partial oxidation step S25 to partially oxidize the charcoal.
  • the blast furnace-blown coal 22 having an oxygen atom content (dry base) of 12 to 20% by weight was obtained.
  • the average pore diameter is 10 to 50 nm, that is, an oxygen-containing functional group (carboxyl) as in the above-described embodiment.
  • an oxygen-containing functional group carboxyl
  • the oxygen atom content dry base
  • the main skeleton C
  • the decomposition (decrease) of the combustion components, mainly H, O, and O) is greatly suppressed, and oxygen atoms are further chemically adsorbed.
  • the blast furnace blowing coal 22 according to the present embodiment KMnO 4, H 2 O 2 , KClO 3, K 2 and be contained Cr oxidizing agent such as 2 O 4, so as to enrich the oxygen in a hot-air Even if nothing is done, the combustion efficiency can be further improved and the generation of unburned carbon (soot) can be more reliably suppressed than in the above-described embodiment.
  • an oxygen atom content rate (dry base) needs to be 20 weight% or less. This is because if it exceeds 20% by weight, the oxygen content is too high and the calorific value becomes too low.
  • the treatment temperature in the partial oxidation step S25 is preferably 50 to 150 ° C. This is because, if the temperature is less than 50 ° C., even in an air (oxygen concentration: 21% by volume) atmosphere, the partial oxidation treatment is difficult to proceed. If the temperature exceeds 150 ° C., the oxygen concentration is about 5% by volume. Even so, there is a possibility that a large amount of carbon monoxide and carbon dioxide may be generated by the combustion reaction.
  • composition analysis Composition analysis (elemental analysis) of the blast furnace blown coal 12 (present coal) obtained by the manufacturing method according to the first embodiment described above was performed.
  • the coal of the present invention has a proportion of oxygen (O) smaller than that of dry coal and is much larger than that of conventional coal, while a proportion of carbon (C) is larger than that of dry coal. It is smaller than conventional charcoal. For this reason, this invention charcoal has a calorific value larger than that of dry charcoal and smaller than that of conventional charcoal.
  • ⁇ No. 2 Surface condition> The surface state (average pore diameter, pore volume, specific surface area) of the above-described coal of the present invention was measured. For comparison, the surface states of the above-described conventional charcoal and dry charcoal were also measured. The results are shown in Table 2 below.
  • the coal of the present invention has an average pore diameter much larger than that of conventional coal and dry coal.
  • ⁇ No. 3 Amount of oxygen-containing functional group>
  • oxygen-containing functional groups hydroxyl group (OH), carboxyl group (COOH), aldehyde
  • the content ratio of each group (COH) and ester group (COO) at each temperature was determined.
  • the horizontal axis represents temperature
  • the vertical axis represents the ratio of the peak area of each oxygen-containing functional group to the total peak area of the oxygen-containing functional group at 110 ° C.
  • the amount of unburned carbon gradually increases in the conventional coal and the dry coal as the excess oxygen concentration decreases.
  • the charcoal of the present invention can be burned substantially completely without increasing the amount of unburned carbon even when the excess oxygen concentration is lowered.
  • Os (Oa + Oc / 2) / (Cc + Hc / 4)
  • Oa is the molar flow rate of oxygen gas (molecules) in the supply air
  • Oc is the oxygen atomic molar flow rate in the supplied coal
  • Cc is the carbon atomic molar flow rate in the supplied coal
  • Hc is hydrogen in the supplied coal.
  • the heat generation amount of the present invention is less than that of the conventional coal, it was confirmed that the combustion temperature is higher than that of the conventional coal when the excess oxygen rate is the same as that of the conventional coal.
  • the present invention charcoal has a higher oxygen content than the conventional charcoal, and if the excess oxygen ratio is the same as that of the conventional charcoal, the supply air amount can be smaller than that of the conventional charcoal.
  • the blast furnace injection coal and the manufacturing method thereof according to the present invention can be used extremely beneficially in the coal industry, the steel industry, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Iron (AREA)
  • Coke Industry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
PCT/JP2013/063506 2012-08-03 2013-05-15 高炉吹込み炭及びその製造方法 WO2014020965A1 (ja)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US14/412,921 US20150191803A1 (en) 2012-08-03 2013-05-15 Blast-furnace-blow-in charcoal and method for producing same
IN192DEN2015 IN2015DN00192A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2012-08-03 2013-05-15
KR1020157001877A KR101657427B1 (ko) 2012-08-03 2013-05-15 고로 취입탄 및 그 제조 방법
AU2013297837A AU2013297837B2 (en) 2012-08-03 2013-05-15 Blast-furnace-blow-in charcoal and method for producing same
DE112013003846.3T DE112013003846T5 (de) 2012-08-03 2013-05-15 Hochofen-Einblaskohle, und Verfahren zu deren Herstellung
CN201380035147.8A CN104411838B (zh) 2012-08-03 2013-05-15 高炉喷吹煤及其制造方法
JP2014528025A JP5843968B2 (ja) 2012-08-03 2013-05-15 高炉吹込み炭及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-172756 2012-08-03
JP2012172756 2012-08-03

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WO2014020965A1 true WO2014020965A1 (ja) 2014-02-06

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CN (1) CN104411838B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU2013297837B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE112013003846T5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IN (1) IN2015DN00192A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO2014020965A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2018024942A (ja) * 2016-07-29 2018-02-15 Ｊｆｅスチール株式会社 高炉操業方法
JP2018024941A (ja) * 2016-07-29 2018-02-15 Ｊｆｅスチール株式会社 高炉操業方法

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Publication number Priority date Publication date Assignee Title
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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JP2011102439A (ja) * 2000-08-10 2011-05-26 Jfe Steel Corp 微粉炭の多量吹込みによる高炉操業方法
JP2007169750A (ja) * 2005-12-26 2007-07-05 Jfe Steel Kk 高炉操業方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018024942A (ja) * 2016-07-29 2018-02-15 Ｊｆｅスチール株式会社 高炉操業方法
JP2018024941A (ja) * 2016-07-29 2018-02-15 Ｊｆｅスチール株式会社 高炉操業方法

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CN104411838A (zh) 2015-03-11
US20150191803A1 (en) 2015-07-09
IN2015DN00192A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2015-06-12
JP5843968B2 (ja) 2016-01-13
AU2013297837B2 (en) 2016-03-10
AU2013297837A1 (en) 2015-01-29
CN104411838B (zh) 2017-03-29
KR101657427B1 (ko) 2016-09-13
KR20150024913A (ko) 2015-03-09
JPWO2014020965A1 (ja) 2016-07-21
DE112013003846T5 (de) 2015-04-23

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