WO2016024512A1 - 冶金用コークスおよびその製造方法 - Google Patents

冶金用コークスおよびその製造方法 Download PDF

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WO2016024512A1
WO2016024512A1 PCT/JP2015/072307 JP2015072307W WO2016024512A1 WO 2016024512 A1 WO2016024512 A1 WO 2016024512A1 JP 2015072307 W JP2015072307 W JP 2015072307W WO 2016024512 A1 WO2016024512 A1 WO 2016024512A1
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Prior art keywords
coal
coke
less
mass
inert
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PCT/JP2015/072307
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English (en)
French (fr)
Japanese (ja)
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幹也 永山
深田　喜代志
松井　貴
勇介 土肥
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Ｊｆｅスチール株式会社
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Priority to CN201580042617.2A priority Critical patent/CN106661458B/zh
Priority to JP2016542547A priority patent/JP6694161B2/ja
Priority to KR1020177003117A priority patent/KR101879554B1/ko
Publication of WO2016024512A1 publication Critical patent/WO2016024512A1/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
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition

Definitions

  • the present invention relates to a metallurgical coke from which high strength metallurgical coke can be obtained by adjusting the type and amount of coal contained in the coal blend, and a method for producing the same.
  • the metallurgical coke is usually strength-managed by measuring the strength by a rotational strength test or the like specified in JIS K 2151.
  • coal is softened and melted by dry distillation and caking into coke. Therefore, since the strength of coke is greatly influenced by the softening and melting characteristics of coal, it is necessary to correctly evaluate the softening and melting characteristics of coal in order to improve the strength of coke.
  • the softening and melting properties are properties of softening and melting when coal is heated, and can usually be evaluated by the fluidity, viscosity, adhesiveness, expandability, etc. of the softened melt.
  • coal has a mixture of an active component that softens and melts when heated and an inert component that does not soften and melt, and the inert component adheres via the active component. Therefore, the coke strength is strongly influenced by the balance between the amount of active component and the amount of inert component, and it is considered that the amount of inert component is particularly important.
  • the amount of inert component there is a method for measuring the fine structure component of coal as defined in JIS M 8816.
  • coal pulverized to 850 ⁇ m or less is mixed with a thermoplastic or thermosetting binder to briquette, the surface to be tested is polished, and then optical and morphological properties are identified using a microscope. is there.
  • the content rate of each fine structure component in the sample is a method in which the percentage of the number measured for each component is taken as a volume percentage.
  • the total inert amount (TI) can be obtained by the following equation (1).
  • Total inert amount (%) Fuji knit (%) + miclinit (%) + (2/3) x semi-fuji knit (%) + mineral (%) (1) Here, all contents are vol. %.
  • the mineral content can be calculated from the anhydrous base ash content and the anhydrous base total sulfur content using the Parr formula described in JIS M 8816.
  • Non-Patent Document 1 A general method is to develop this way of thinking about coal blending and perform blending design based on two properties of a coalification degree parameter and a caking property parameter.
  • JIS M 8816 Vitrinite average maximum reflectance (Ro), coal volatile matter, and the like are mentioned.
  • the caking property parameter include maximum fluidity (MF) and CBI (Composition Balance Index) (for example, Non-Patent Document 2).
  • This CBI is an index based on the idea that there is an optimum amount of caking component according to the amount of inert component contained in the blended coal, and the coke strength increases as the ratio of the two components approaches the optimum value. It is.
  • the average maximum reflectance (Ro), the maximum fluidity (MF), and the maximum fluidity (MF) are calculated in consideration of the interrelationship between the average maximum reflectance (Ro), the maximum fluidity (MF), and the total inertness (TI).
  • the coke strength obtained when the value is set to a predetermined value shows a parabolic relationship that is convex upward according to the value of the total inert amount (TI), and the amount of the inert component that maximizes the strength is the maximum fluidity (MF). It has been reported that it varies with size.
  • Patent Document 2 reports a method for estimating coke strength from various raw coal properties including maximum fluidity (MF) and total inert amount (TI).
  • MF maximum fluidity
  • TI total inert amount
  • Coke has a desired coke strength by adjusting the properties of the blended coal.
  • the pore structure of the coke is substantially similar.
  • Coke is a porous body having a porosity of about 50%, and the structure of the pores was expected to affect the coke strength, but a method for controlling the pore structure was not known.
  • the properties of the blended coal are generally managed with the average quality of the blended coal because of the addition of the simple coal properties that make up this blended coal and the ease of quality control.
  • the effects of the coal that makes up the blended coal on coke quality and what kind of coal can effectively improve the coke strength. There are cases where it cannot be obtained.
  • An object of the present invention is to propose a metallurgical coke excellent in quality such as strength and a method for producing the same.
  • the present invention relates to a high-strength coke having a pore structure that has not been conventionally known by utilizing coal with a low content of inert components (low inert coal) that has been rarely used as a raw material for producing coke. It is to propose a manufacturing method.
  • the present invention can solve the above-mentioned problems.
  • the maximum fluidity is 80 ddpm or more and 3000 ddpm or less and the total inert amount is 3.5 vol. % Or more 11.7 vol. % Coke obtained by dry distillation of blended coal containing 10 mass% or more and 75 mass% or less of low inert coal, and the degree of circularity is 0.8 in the coarse air holes having a diameter of 100 ⁇ m or more and 3 mm or less in the coke.
  • the metallurgical coke is characterized in that the ratio of the total cross-sectional area of the pores to the total cross-sectional area of the rough air holes is 10% or more.
  • a metallurgical coke is proposed in which the average circularity of coarse air holes having a diameter of 100 ⁇ m to 3 mm in the coke is 0.35 or more.
  • the present invention is a blended coal composed of a plurality of brands of coal, having a maximum fluidity of 80 ddpm or more and 3000 ddpm or less and a total inert amount of 3.5 vol. % Or more 11.7 vol. % Coke obtained by dry distillation of coal blended with 10 mass% or more and 75 mass% or less of low inert charcoal, and the degree of circularity is 0.8 in the coarse air holes having a diameter of 50 ⁇ m or more and 200 ⁇ m or less in the coke.
  • the metallurgical coke is characterized in that the ratio of the total cross-sectional area of the pores to the total cross-sectional area of the rough air holes is 10% or more.
  • a metallurgical coke is proposed in which the average circularity of coarse air holes having a diameter of 50 ⁇ m or more and 200 ⁇ m or less in the coke is 0.55 or more.
  • the low inert charcoal has a maximum fluidity of 80 ddpm or more and less than 1000 ddpm and a total inert amount of 3.5 vol. % Or more 11.7 vol.
  • the low inert coal contained in the blended coal has an ash content of 4.8 mass% to 8.6 mass%, (4)
  • the maximum fluidity is a value measured in accordance with a coal fluidity test method by the Gisela plastometer method defined in JIS M8801; (5)
  • all contents are vol. % However, it is considered as a more preferable means for solving the above-mentioned problem.
  • the maximum fluidity is 80 ddpm or more and 3000 ddpm or less and the total inert amount is 3.5 vol. % Or more 11.7 vol. % Of low inert charcoal that is 10 mass% or less and 75 mass% or less is dry-distilled, and among the rough atmospheric pores having a diameter of 100 ⁇ m or more and 3 mm or less in coke, the breakage of pores having a circularity of 0.8 or more
  • the present invention proposes a method for producing metallurgical coke, characterized in that coke having a ratio of the total area value to the total cross-sectional area of the rough atmospheric pores of 10% or more is manufactured.
  • a method for producing metallurgical coke characterized in that coke is produced in which the average circularity of coarse air holes having a diameter of 100 ⁇ m or more and 3 mm or less in the coke is 0.35 or more.
  • the present invention is a blended coal composed of a plurality of brands of coal, having a maximum fluidity of 80 ddpm or more and 3000 ddpm or less and a total inert amount of 3.5 vol. % Or more 11.7 vol. % Of low inert charcoal that is 10 mass% or more and 75 mass% or less is dry-distilled, and among the rough atmospheric pores having a diameter of 50 ⁇ m or more and 200 ⁇ m or less in coke, the breakage of pores having a circularity of 0.8 or more
  • the present invention proposes a method for producing metallurgical coke, characterized in that coke having a ratio of the total area value to the total cross-sectional area of the rough atmospheric pores of 10% or more is manufactured.
  • the present invention proposes a method for producing metallurgical coke, characterized in that coke is produced in which the average circularity of coarse air holes having a diameter of 50 ⁇ m or more and 200 ⁇ m or less in the coke is 0.55 or more.
  • the method for producing metallurgical coke according to the present invention (1) As said combination charcoal, using what blended 20 mass% or more and 75 mass% or less of low inert charcoal, (2) The low inert charcoal has a maximum fluidity of 80 ddpm or more and less than 1000 ddpm and a total inert amount of 3.5 vol. % Or more 11.7 vol.
  • the low inert coal contained in the blended coal has an ash content of 4.8 mass% to 8.6 mass%, (4)
  • the maximum fluidity is a value measured in accordance with a coal fluidity test method by the Gisela plastometer method defined in JIS M8801; (5)
  • all contents are vol. % However, it is considered as a more preferable means for solving the above-mentioned problem.
  • high-quality (high strength) coke having a structure different from that of conventional metallurgical coke can be produced.
  • high-quality coke When such high-quality coke is used in a blast furnace, it contributes to improvement of air permeability in a vertical furnace such as a blast furnace, and is effective for stable operation.
  • the inventors conducted extensive research on the relationship between the blending conditions of various coals and coke strength. As a result, from the relationship between the maximum fluidity (MF) of ordinary coal and the total amount of inert gas (TI), an appropriate amount of coal with a small total amount of inert gas (TI), that is, a low inert coal with a low content of inert components When blended, it was surprisingly found that coke having a structure different from that of conventional metallurgical coke is produced. Further, the present inventors have found that the strength of the coke is significantly higher than expected from the conventional way of thinking, leading to the development of the present invention.
  • coal having an average maximum reflectance (Ro) indicating the degree of coalification of about 0.9 to 1.2 contains all inert components.
  • Amount hereinafter simply referred to as “total inert amount” of 20 to 30 vol.
  • total inert amount 20 to 30 vol.
  • the total inert amount is 20-30 vol. It is reported that the drum strength of coke reaches a maximum at%.
  • the inventors have not only reduced the coke strength but also the normal coke strength even if the coal has a low total inert amount, that is, low inert coal, as long as the maximum fluidity (MF) and blending amount are appropriate. It has been found that coke strength may improve rather than blend.
  • FIG. 1 shows the relationship between the Gieseler maximum fluidity (log MF) and the total inert amount (TI) of various simple coals (individual brand coals).
  • TI total inert amount
  • MF maximum fluidity
  • TI total inertness
  • the lower the total amount of inert coal the greater the viscosity of the liquid component in the softened melt. It is considered that the lower the viscosity of the liquid component is, the more easily the growth and coalescence of pores during dry distillation is facilitated to form connected pores and the formation of coke containing coarse defects.
  • the inventors set the coke obtained from the conventional blended coal (mixed coal a) and the total inert content to 3.5 vol. % Or more 11.7 vol.
  • MF maximum flow rate
  • FIG. 2 shows a photomicrograph of coke obtained by dry distillation of the blended coals of both comparisons under the same conditions.
  • pores near the circular shape exist independently in the blended coal b compared to the blended coal a, and the growth and coalescence of the pores are suppressed in the blended coal b compared to coke by the conventional blending. It can be seen that the connected pores are also difficult to form.
  • the inventors of the present invention have a conventional blended coal (for example, the blended coal a described above) and a total inert content of 3.5 vol. % Or more 11.7 vol. %
  • a conventional blended coal for example, the blended coal a described above
  • a total inert content of 3.5 vol. % Or more 11.7 vol. %
  • MF maximum fluidity
  • Examples of methods for observing the cross section of the pore include X-ray CT tomography and a method in which a coke sample is embedded in a resin, and then the cross section is polished and observed with a microscope. If an image of a coke cross section is obtained by such a method, the pore area and perimeter data observed using image analysis software can be obtained. In cross-sectional observation with an optical microscope, it is difficult to take a wide field of view for one image capture. Therefore, it is preferable to evaluate the circularity using observation images of three or more fields.
  • the maximum ferret diameter is used in the present invention.
  • the ferret diameter is the vertical and horizontal lengths of a rectangle circumscribing a certain figure, and the maximum ferret diameter is the length of the longest side of the rectangle circumscribing a certain pore.
  • the inventors made all the pores with a maximum ferret diameter of 100 ⁇ m or more and 3 mm or less as rough atmospheric pores for investigation on cross-sectional images obtained by X-ray CT tomography.
  • the observation magnification of the microscope was 200 times, and pores having a maximum ferret diameter of 50 ⁇ m or more and 200 ⁇ m or less were examined as rough atmospheric pores.
  • those in which the entire pores did not fit in the cross-sectional image were excluded from the evaluation targets because the maximum ferret diameter could not be obtained correctly.
  • the average circularity of the coarse atmospheric pores and the pores having a circularity of 0.8 or more in the coarse atmospheric pores are defined as circular pores, and the circular shape occupies the total pore area of the coarse atmospheric pores The percentage of pores was evaluated.
  • Fig. 3 shows the result of examining the blending ratio of low inert charcoal and the ratio of circular pores by changing the blending composition to produce coke, obtaining the ratio of circular pores from the X-ray CT image.
  • the ratio of circular pores was increased when the blending ratio of low inert coal was in the range of 10 mass% to 75 mass%. From the above, it was found that by adding an appropriate amount of low inert charcoal, the growth and coalescence of the pores were suppressed and the circular pores were more easily formed than the coke obtained by the conventional blending.
  • Table 1 shows the average circularity, the ratio of the circular pores in the coarse air holes determined from the optical microscope observation by the above-described method, the average, along with the ratio of the circular holes in the rough air holes obtained by the X-ray CT shown in FIG. The measurement results of the circularity, the average quality of the blended coal, and the coke strength are also shown.
  • the coke strength is 84.5 or more when the blending ratio of the low inert coal is 10 mass% or more and 75 mass% or less.
  • the maximum ferret diameter obtained by X-ray CT is coarser than 100 ⁇ m and 3 mm or less. It can be seen that the ratio of circular pores in the pores is 10% or more.
  • the ratio of circular pores in rough atmospheric pores having a maximum ferret diameter of 50 ⁇ m or more and 200 ⁇ m or less determined by observation with an optical microscope is 10% or more. Recognize.
  • the blend ratio of low inert charcoal is in the range of 10 mass% to 75 mass%, and the ratio of circular pores in the coarse air holes in the coke becomes 10% or more. It can be seen that it is preferable to do so.
  • the average circularity of the coarse air holes having a maximum ferret diameter of 100 ⁇ m or more and 3 mm or less determined by X-ray CT is 0.35 or more
  • the average circularity of the coarse air holes having a maximum ferret diameter of 50 ⁇ m or more and 200 ⁇ m or less determined from observation with an optical microscope is 0.55 or more. Therefore, in order to produce high-strength coke, the blend ratio of low inert coal is 10 to 75 mass%, and the average circularity of pores having a maximum ferret diameter of 100 ⁇ m or more and 3 mm or less in the coke. It can be seen that the average circularity of pores having a maximum ferret diameter of 50 ⁇ m or more and 200 ⁇ m or less is preferably 0.55 or more, or 0.35 or more.
  • FIG. 1 An example of the X-ray CT observation result is shown in FIG.
  • Non-Patent Document 4 shows that when the pore diameter is uniform, the strength of the coke having a low degree of circularity of the pores is reduced, but this is because the stress concentrates on the sharp part of the pores having a low degree of circularity. ing. Thus, it is known that stress is concentrated in pores with low circularity and lowers strength, and in coke produced by the method of the present invention, stress concentration is unlikely to occur due to increase in circular pores, and strength Will be higher.
  • the ratio of pores having a high degree of circularity occupying pores having a specific size or larger was used as a measure of increasing the number of pores having a high degree of circularity.
  • the size and the expression method of the circularity may be changed as appropriate.
  • the circularity of pores of 50 ⁇ m or more may be investigated, and the median, mode, range, etc. of the examined circularity of the pores may be used as an index.
  • the circularity threshold for defining the circular pores can be changed as appropriate.
  • the maximum fluidity (MF) that allows good fusion of coal particles and does not form connected pores.
  • a low total inert amount (TI) is desirable, and the ranges thereof include a maximum fluidity (MF) of 80 ddpm to 3000 ddpm and a total inert amount (TI) of 3.5 vol. % Or more 11.7 vol. % Or less is desirable.
  • MF low-inert coal Gieseller maximum fluidity
  • the total inert amount (TI) of low inert coal is 3.5 vol. If it is less than%, the amount of inert that contributes to strength improvement as an aggregate will be insufficient. On the other hand, this amount is 11.7 vol. If it exceeds 50%, the effect of using low inert charcoal is lost. A more desirable TI is 4 to 10 vol. %.
  • the desirable blending ratio of low inert charcoal is 10 mass% or more and 75 mass% or less. Desirably, it is about 20 to 75 mass%, and more desirably about 20 to 65 mass%.
  • the ash content in the inert charcoal is a component that exists in a solid state in the softened and melted state, like the entire inert structure.
  • the ash content is high and the volume ratio is low and tends to be more finely dispersed. Therefore, although the degree of influence is smaller than the total inert amount (TI), the ash content is preferably low, and the ash content is most preferably 4.8 mass% or more and 8.6 mass% or less as a dry base value. More desirably, it is 5.0 to 8.0 mass%.
  • the blending amount of low inert coal in the blended coal is recommended to be 10 to 75 mass%.
  • the total inert amount is 3.5 vol. % Or more 11.7 vol. % Or less, or suitable coals such as strong or weakly caking coal, semi-strongly caking coal, low volatile coal or non-caking coal, modified coal, etc. whose maximum fluidity is not 80 ddpm or more and 3000 ddpm or less.
  • the blending amount is about 25 to 90 mass%.
  • the blended coal may include additives such as caking additive, oils, powdered coke, petroleum coke, resins, and waste.
  • the present invention it is effective to blend a predetermined amount of low inert coal having the above-described conditions, that is, a predetermined maximum fluidity (MF) and a predetermined total inert amount (TI). . Furthermore, in order to always ensure a stable substrate strength as a blended coal, the average maximum reflectance (Ro) indicating the degree of coalification of the blended coal can be adjusted to about 0.95 to 1.20%. preferable.
  • Example 1 This example shows the test results when coke is produced by dry distillation of blended coal.
  • the blended coal prepared with the average maximum reflectance (Ro) of the blended coal which is a general strength controlling factor, and the weighted average value of the logarithmic logarithm (log MF) of the highest Gieseller fluidity (MF) were prepared to be almost constant. It was used.
  • the blended coal was prepared using coals AP shown in Table 2.
  • the average maximum reflectance (Ro) is measured in accordance with JIS M 8816, and the Gieseler maximum fluidity (MF) is measured in accordance with JIS M 8801.
  • the common logarithm (log MF) is also shown in Table 2. It was shown together.
  • Volatile content (VM) and ash content (Ash) are measured in accordance with JIS M 8812, and are each expressed in% dry base.
  • the total inert amount (TI) was determined using equation (1) based on JIS M 8816.
  • the total inert amount (TI) is 13.2 vol.
  • Formulation 1-2 in which 20% by mass of Coal I, which is larger than the preferred range, is blended, and Formula 1-3 in which 20% by mass of Coal J having a high maximum fluidity (MF) of 10964 ddpm is blended
  • MF maximum fluidity
  • MF The coke co-distilled using Formulation 1-1 containing 20 mass% of coal K, which has a low total inert amount (TI: 6.7 vol.%) And 447 ddpm, showed high strength.
  • High-strength coke could be produced in the same manner when coal N and coal O, which have relatively high maximum fluidity (MF) and total inertness (TI), were blended with coal K and coal M, which were confirmed to have improved coke strength. (Formulation 3-1 and Formulation 4-1).
  • the maximum fluidity (MF) is 80 ddpm or more and 3000 ddpm or less, and the total inert amount (TI) is 3.5 vol. % Or more 11.7 vol. It was found that high strength metallurgical coke can be produced by blending 20 mass% of low inert charcoal in a range of not more than%.
  • Example 2 In Example 1, the experiment was performed by unifying the average maximum reflectance (Ro) of the blended coal to 1.05.
  • the average maximum reflectance (Ro) of blended coal is said to affect the strength of the coke substrate part, and is not related to the formation of connected pores clarified in the present invention. Therefore, the technique of the present invention can also be applied to blended coals having different average maximum reflectivities (Ro).
  • the technique according to the present invention is not only effective as the exemplified metallurgical coke and its manufacturing technique, but also effective as other types of vertical metallurgical furnace coke or combustion furnace coke and their manufacturing method.

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  • Engineering & Computer Science (AREA)
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  • Coke Industry (AREA)
PCT/JP2015/072307 2014-08-15 2015-08-06 冶金用コークスおよびその製造方法 WO2016024512A1 (ja)

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CN201580042617.2A CN106661458B (zh) 2014-08-15 2015-08-06 冶金用焦炭及其制造方法
JP2016542547A JP6694161B2 (ja) 2014-08-15 2015-08-06 冶金用コークスの製造方法
KR1020177003117A KR101879554B1 (ko) 2014-08-15 2015-08-06 야금용 코크스 및 그 제조 방법

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US20220163501A1 (en) * 2019-03-04 2022-05-26 Jfe Steel Corporation Method of evaluating coal, methods of preparing coal blend, and method of producing coke

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CA3190626A1 (en) * 2020-08-13 2022-02-17 Chevron U.S.A. Inc. Coke morphology by image segmentation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220163501A1 (en) * 2019-03-04 2022-05-26 Jfe Steel Corporation Method of evaluating coal, methods of preparing coal blend, and method of producing coke
CN114410328A (zh) * 2022-02-10 2022-04-29 山西沁新能源集团股份有限公司 具有褶皱碳层的高碳焦及其制备方法
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CN106661458B (zh) 2019-12-24
KR20170027827A (ko) 2017-03-10
TWI570231B (zh) 2017-02-11
KR101879554B1 (ko) 2018-07-17
TW201615814A (zh) 2016-05-01
JP6694161B2 (ja) 2020-05-13

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