JP4181059B2 - Method for evaluating the transportability of pulverized coal - Google Patents
Method for evaluating the transportability of pulverized coal Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims description 186
- 238000000034 method Methods 0.000 title claims description 51
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 126
- 238000001228 spectrum Methods 0.000 claims description 49
- 239000000126 substance Substances 0.000 claims description 40
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 claims description 27
- 239000002734 clay mineral Substances 0.000 claims description 25
- 238000000523 multiple-quantum excitation in combination with magic angle spinning Methods 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010445 mica Substances 0.000 claims description 21
- 229910052618 mica group Inorganic materials 0.000 claims description 21
- 239000011707 mineral Substances 0.000 claims description 21
- 229910021647 smectite Inorganic materials 0.000 claims description 21
- 239000005995 Aluminium silicate Substances 0.000 claims description 19
- 235000012211 aluminium silicate Nutrition 0.000 claims description 19
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 19
- 238000007664 blowing Methods 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 8
- 230000000903 blocking effect Effects 0.000 claims description 7
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- 238000011156 evaluation Methods 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
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- 238000005481 NMR spectroscopy Methods 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000011002 quantification Methods 0.000 description 6
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- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 238000002347 injection Methods 0.000 description 4
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- 238000005004 MAS NMR spectroscopy Methods 0.000 description 2
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- 238000007796 conventional method Methods 0.000 description 2
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- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
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- 238000012935 Averaging Methods 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
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- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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Description
本発明は、微粉炭の搬送性を評価する方法に関する。詳しくは、核磁気共鳴（以下「ＮＭＲ」ということがある。）スペクトル測定法を利用して、高炉などの冶金炉やボイラーなどの燃焼炉に吹き込む微粉炭として使用する石炭の搬送性を評価する方法に関する。 The present invention relates to a method for evaluating the transportability of pulverized coal. Specifically, the transportability of coal used as pulverized coal to be blown into a metallurgical furnace such as a blast furnace or a combustion furnace such as a boiler is evaluated using a nuclear magnetic resonance (hereinafter sometimes referred to as “NMR”) spectrum measurement method. Regarding the method.
製鉄プロセスにおける冶金炉、例えば高炉の操業においては、一般に、鉄鉱石などの鉄含有原料とコークスなどの還元剤を炉頂から交互に装入するが、近年、炉頂から装入するコークスの一部を安価な微粉炭に代替し、微粉炭を熱風とともに高炉の羽口から吹き込むことが盛んに行われている。 In the operation of a metallurgical furnace such as a blast furnace in an iron making process, an iron-containing raw material such as iron ore and a reducing agent such as coke are generally charged alternately from the top of the furnace. Part of the pulverized coal is replaced with cheap pulverized coal, and the pulverized coal is blown together with hot air from the tuyere's tuyere.
このような高炉の微粉炭吹き込み操業は、安価な微粉炭を多量に吹き込むことによりコークス装入量を低減し、高炉燃料比を小さくすることを狙ったものである。 Such blast furnace pulverized coal injection operation aims to reduce the coke charging amount and reduce the blast furnace fuel ratio by injecting a large amount of inexpensive pulverized coal.
また、発電プロセスにおけるボイラー等の燃焼炉の運転においても、重油の代替燃料として石炭が見直されている。その石炭の使用形態としては、ＣＷＭ（石炭−水スラリー）、ＣＯＭ（石炭重油混合燃料）、微粉炭等の吹き込みが挙げられるが、中でも、水や油等を必要としない微粉炭の吹き込みが、特に注目されている。 Also, in the operation of a combustion furnace such as a boiler in a power generation process, coal is reviewed as an alternative fuel for heavy oil. Examples of the use form of the coal include CWM (coal-water slurry), COM (coal fuel oil blended fuel), pulverized coal, and the like. Among them, pulverized coal that does not require water, oil, etc. Particular attention has been paid.
このような吹き込み用の微粉炭は、一般に、原炭を粉砕、乾燥・分級し、一旦、ホッパーに貯蔵される。その後、微粉炭は、ホッパーから所定量切出され、高炉またはボイラーの吹き込み口まで配管を用いて気体輸送され、該吹き込み口から炉内に吹き込まれる。 Such pulverized coal for blowing is generally pulverized, dried and classified, and once stored in a hopper. Thereafter, a predetermined amount of the pulverized coal is cut out from the hopper, gas transported to the blast furnace or the boiler inlet using a pipe, and blown into the furnace from the inlet.
この際、微粉炭の石炭銘柄、粒度、水分量などの違いによって、気体輸送する微粉炭の搬送性が大きく変化する。その結果、気体輸送中に微粉炭が配管に付着する、さらに、配管が閉塞するなどの問題を引き起こす。 At this time, the transportability of the pulverized coal that is transported by gas varies greatly depending on the coal brand, particle size, moisture content and the like of the pulverized coal. As a result, problems such as pulverized coal adhering to the pipe during gas transportation and further blocking the pipe are caused.
配管が閉塞または閉塞に近い状態になれば、配管内における圧力損失が増大し、微粉炭を高炉またはボイラー内へ安定して連続的に吹き込むことが困難となるので、このような微粉炭搬送性の問題点を解決するため、従来から種々の方法が開示されている。 If the pipe is closed or close to the blockage, the pressure loss in the pipe increases and it becomes difficult to stably and continuously blow pulverized coal into the blast furnace or boiler. In order to solve this problem, various methods have been disclosed.
例えば、特許文献１には、微粉炭中に搬送性が良好なチャー（石炭熱分解物）を所定量添加、混合する方法、特許文献２には、微粉炭に界面活性剤等を添着する方法、特許文献３には、粘結炭の粒度調整や２種以上の微粉炭を混合することにより微粉炭と輸送配管との摩擦係数を所定範囲に調整する方法、特許文献４には、微粉炭の流動性指数（安息角、圧縮度、スパチュラ角、凝集度の測定指数の総和）を基準値以上とするように調整する方法が開示されている。
For example, Patent Document 1 discloses a method of adding and mixing a predetermined amount of char (coal pyrolysis product) having good transportability in pulverized coal, and Patent Document 2 discloses a method of attaching a surfactant or the like to pulverized coal. Patent Document 3 discloses a method for adjusting the coefficient of friction between a pulverized coal and a transportation pipe by adjusting the particle size of caking coal or mixing two or more kinds of pulverized coal, and
しかし、特許文献１及び２の開示技術は、微粉炭に搬送性を高める作用をもつ添加剤を添加または添着する新たな工程が必要であり、特に、界面活性剤を使用する場合は、コスト増加の原因となる。また、特許文献３及び４の開示技術は、粘結炭の粒度調整のための粉砕や、粘結炭の性状の管理をする必要がある。
However, the disclosed techniques of Patent Documents 1 and 2 require a new process for adding or attaching an additive having an effect of improving transportability to pulverized coal, and particularly when using a surfactant, the cost increases. Cause. Moreover, it is necessary for the disclosed technique of
また、特許文献５には、微粉炭として粘結炭を使用する際に、粘結炭中のイナート量（ＪＩＳ Ｍ８８１６−１９７９で規定される、ミクリニット、セミフジニットの２／３、フジニット、鉱物質およびビトリニット反射率２．４以上の熱可塑性を有しない成分）を所定量以上にして微粉砕する方法が開示されている。 Patent Document 5 discloses that when caking coal is used as pulverized coal, the amount of inert in the caking coal (as defined in JIS M8816-1979, 2/3 of miclinite, semi-fujinit, fuzinite, mineral substances and A method of finely pulverizing a component having a vitrinite reflectance of 2.4 or more and having no thermoplasticity to a predetermined amount or more is disclosed.
しかし、この方法は、粘結炭を多量に使用することを前提とするもので、粘結炭中に含有する搬送性が良好なイナート量を所定量以上に管理することが必要となる。 However, this method is based on the premise that a large amount of caking coal is used, and it is necessary to manage the amount of inert contained in the caking coal with good transportability to a predetermined amount or more.
上記特許文献１〜５で開示された従来技術は、事前処理や添加剤を必要とするので生産性、経済性の点で不利であり、また、搬送性を阻害する石炭中の原因物質の解明または特定がなされていない。それ故、上記従来技術においては、微粉炭中に配合する石炭銘柄およびその配合比を変更した場合に、搬送性が大きく低下することがあった。 The conventional techniques disclosed in Patent Documents 1 to 5 are disadvantageous in terms of productivity and economy because they require pretreatment and additives, and elucidation of causative substances in coal that impede transportability. Or not specified. Therefore, in the above prior art, when the coal brand to be blended in the pulverized coal and the blending ratio thereof are changed, the transportability may be greatly lowered.
また、１５０ｋｇ／ｔ（銑鉄）以上の微粉炭を吹き込む高炉操業において、微粉炭が気送配管内に付着し、さらに、該配管が閉塞すると、該配管内における圧力損失が増大し、微粉炭吹き込み量が大きく低減する。この吹き込み量の低減は、高炉の燃料比の増加、または、生産性の低下の原因となる。 In addition, in blast furnace operation in which pulverized coal of 150 kg / t (pig iron) or more is blown, if pulverized coal adheres to the inside of the pneumatic piping and further closes, the pressure loss in the piping increases, and pulverized coal is blown. The amount is greatly reduced. This reduction in the amount of blowing causes an increase in the fuel ratio of the blast furnace or a decrease in productivity.
本発明は、このような従来技術の現状に鑑み、従来のような特殊な事前処理や添加剤を用いずとも、微粉炭の搬送性を安定して向上させることを課題とし、その解決方法として、ＮＭＲ法を利用し、高炉などの冶金炉やボイラーなどの燃焼炉に吹き込む微粉炭の搬送性を適正に評価する方法を提供するものである。 In view of the current state of the prior art, the present invention aims to stably improve the transportability of pulverized coal without using special pretreatment and additives as in the past, and as a solution to that problem The present invention provides a method for appropriately evaluating the transportability of pulverized coal to be blown into a metallurgical furnace such as a blast furnace or a combustion furnace such as a boiler, using an NMR method.
本発明者は、鋭意研究の結果、高炉などの冶金炉やボイラーなどの燃焼炉に吹き込む微粉炭中に存在し、配管付着や配管閉塞を引き起こす原因となる無機鉱物の化学形態を、ＮＭＲ法を利用して特定するとともに、該無機鉱物の存在比を定量し、この特定・定量に基づいて、各種石炭の搬送性を評価できることを知見した。 As a result of diligent research, the present inventor found that the chemical form of inorganic minerals present in pulverized coal blown into metallurgical furnaces such as blast furnaces and combustion furnaces such as boilers, causing the adhesion of pipes and clogging of pipes, NMR method. It was found that the abundance ratio of the inorganic mineral was quantified and the transportability of various coals could be evaluated based on the identification and quantification.
本発明は、上記知見に基づいてなされたもので、その要旨とするところは、以下の通りである。 The present invention has been made on the basis of the above findings, and the gist thereof is as follows.
（１）冶金炉や燃焼炉の吹き込み口まで配管を用いて気体輸送され、該吹き込み口から炉内に吹き込まれる微粉炭として使用する石炭の搬送性を評価する方法であって、
上記石炭中に存在する27Ａｌの核磁気共鳴スペクトルを測定し、該測定スペクトルのピーク位置と、カオリン鉱物、スメクタイト、雲母粘土鉱物またはＡｌ 2 Ｏ 3 に相当するピーク位置とを照合し、上記石炭中に存在するＡｌとＳｉを主成分とする無機鉱物の化学形態を特定し、さらに、全ピーク積分値に対する該無機鉱物のピーク積分値の比率から該無機鉱物の存在比を定量し、
続いて、上記配管に付着または配管を閉塞する配管固着物から採取した試料中の 27 Ａｌの核磁気共鳴スペクトルを測定し、該測定スペクトルのピーク位置と、カオリン鉱物、スメクタイト、雲母粘土鉱物またはＡｌ 2 Ｏ 3 に相当するピーク位置とを照合し、上記配管固着物中に存在するＡｌとＳｉを主成分とする無機鉱物の化学形態を特定し、さらに、全ピーク積分値に対する該無機鉱物のピーク積分値の比率から該無機鉱物の存在比を定量し、
上記石炭中に存在するＡｌとＳｉを主成分とする無機鉱物の存在比と、上記配管固着物中に存在するＡｌとＳｉを主成分とする無機鉱物の存在比を対比して、両存在比の類似関係から、上記石炭の搬送性を評価することを特徴とする微粉炭の搬送性評価方法。
（２）冶金炉や燃焼炉の吹き込み口まで配管を用いて気体輸送され、該吹き込み口から炉内に吹き込まれる微粉炭として使用する石炭の搬送性を評価する方法であって、
上記石炭中に存在する 29 Ｓｉの核磁気共鳴スペクトルを測定し、該測定スペクトルのピーク位置と、カオリン鉱物、スメクタイト、雲母粘土鉱物またはＳｉＯ 2 に相当するピーク位置とを照合し、上記石炭中に存在するＡｌとＳｉを主成分とする無機鉱物の化学形態を特定し、さらに、全ピーク積分値に対する該無機鉱物のピーク積分値の比率から該無機鉱物の存在比を定量し、
続いて、上記配管に付着または配管を閉塞する配管固着物から採取した試料中の 29 Ｓｉの核磁気共鳴スペクトルを測定し、該測定スペクトルのピーク位置と、カオリン鉱物、スメクタイト、雲母粘土鉱物またはＳｉＯ 2 に相当するピーク位置とを照合し、上記配管固着物中に存在するＡｌとＳｉを主成分とする無機鉱物の化学形態を特定し、さらに、全ピーク積分値に対する該無機鉱物のピーク積分値の比率から該無機鉱物の存在比を定量し、
上記石炭中に存在するＡｌとＳｉを主成分とする無機鉱物の存在比と、上記配管固着物中に存在するＡｌとＳｉを主成分とする無機鉱物の存在比を対比して、両存在比の類似関係から、上記石炭の搬送性を評価することを特徴とする微粉炭の搬送性評価方法。
(1) A method for evaluating the transportability of coal used as pulverized coal that is gas transported to a metallurgical furnace or combustion furnace through a pipe and is blown into the furnace from the blow opening,
The nuclear magnetic resonance spectrum 27 Al present in the coal is measured, compares the peak position of the measured spectrum, kaolin minerals, smectites, and a peak position corresponding to mica clay minerals or Al 2 O 3, the coal Identifying the chemical form of the inorganic mineral mainly composed of Al and Si present therein, and further quantifying the abundance ratio of the inorganic mineral from the ratio of the peak integral value of the inorganic mineral to the total peak integral value;
Subsequently, the nuclear magnetic resonance spectrum of 27 Al in the sample collected from the pipe adhering material adhering to or blocking the pipe is measured, and the peak position of the measurement spectrum and the kaolin mineral, smectite, mica clay mineral or Al The peak position corresponding to 2 O 3 is collated, the chemical form of the inorganic mineral mainly composed of Al and Si present in the above-mentioned pipe fixed matter is specified , and the peak of the inorganic mineral relative to the total peak integral value is further determined. Quantifying the abundance ratio of the inorganic mineral from the ratio of the integral value,
By comparing the abundance ratio of the inorganic minerals mainly composed of Al and Si present in the coal with the abundance ratio of the inorganic minerals mainly composed of Al and Si present in the fixed pipe, both abundance ratios A method for evaluating the transportability of pulverized coal, wherein the transportability of the coal is evaluated from the similar relationship .
(2) It is a method for evaluating the transportability of coal used as pulverized coal that is gas-transported using piping to a metallurgical furnace or a combustion furnace, and is blown into the furnace from the inlet,
The nuclear magnetic resonance spectrum of 29 Si present in the coal is measured, and the peak position of the measured spectrum is compared with the peak position corresponding to kaolin mineral, smectite, mica clay mineral or SiO 2 , Identifying the chemical form of the inorganic mineral mainly composed of Al and Si present, further quantifying the abundance ratio of the inorganic mineral from the ratio of the peak integral value of the inorganic mineral to the total peak integral value,
Subsequently, 29 Si nuclear magnetic resonance spectrum in the sample collected from the pipe adhering material adhering to or blocking the pipe is measured, and the peak position of the measurement spectrum and kaolin mineral, smectite, mica clay mineral or SiO The peak position corresponding to 2 is collated, the chemical form of the inorganic mineral mainly composed of Al and Si present in the above-mentioned pipe fixed matter is specified, and the peak integral value of the inorganic mineral with respect to the total peak integral value Quantifying the abundance ratio of the inorganic mineral from the ratio of
By comparing the abundance ratio of the inorganic minerals mainly composed of Al and Si present in the coal with the abundance ratio of the inorganic minerals mainly composed of Al and Si present in the fixed pipe, both abundance ratios A method for evaluating the transportability of pulverized coal, wherein the transportability of the coal is evaluated from the similar relationship.
（３）前記無機鉱物が粘土鉱物および酸化物であることを特徴とする上記（１）または（２）に記載の微粉炭の搬送性評価方法。 ( 3 ) The method for evaluating the transportability of pulverized coal according to (1) or (2) above, wherein the inorganic mineral is a clay mineral and an oxide.
（４）前記石炭中に存在する27Ａｌの核磁気共鳴スペクトルを、27Ａｌ−マジック角回転（ＭＡＳ）法、または、27Ａｌ−多量子マジック角回転（ＭＱＭＡＳ）法を用いて測定することを特徴とする上記（１）に記載の微粉炭の搬送性評価方法。 (4) Measuring the nuclear magnetic resonance spectrum of 27 Al present in the coal using the 27 Al-magic angle rotation (MAS) method or the 27 Al-multi-quantum magic angle rotation (MQMAS) method. The method for evaluating the transportability of pulverized coal as described in ( 1) above.
（５）前記石炭の29Ｓｉの核磁気共鳴スペクトルを、29Ｓｉ−マジック角回転（ＭＡＳ）法を用いて測定することを特徴とする上記（２）に記載の微粉炭の搬送性評価方法。 ( 5 ) The method for evaluating the transportability of pulverized coal according to (2 ) above, wherein the 29 Si nuclear magnetic resonance spectrum of the coal is measured using a 29 Si-magic angle rotation (MAS) method.
本発明によれば、高炉などの冶金炉やボイラーなどの燃焼炉に吹き込む微粉炭中に存在し、配管付着や配管閉塞を引き起こす原因となる無機鉱物の化学形態を特定するとともに、該無機鉱物の存在比を定量し、この特定・定量に基づいて、各種石炭の搬送性を適正に評価することができるので、従来のような特殊な事前処理や添加剤を用いずとも、吹き込み用の微粉炭として使用する石炭の銘柄および配合比を適宜調節して、微粉炭の搬送性を安定して向上せしめ維持することができる。 According to the present invention, it is present in pulverized coal that is blown into a metallurgical furnace such as a blast furnace and a combustion furnace such as a boiler, and specifies the chemical form of the inorganic mineral that causes pipe adhesion and pipe clogging. Since the abundance ratio can be quantified and the transportability of various types of coal can be properly evaluated based on this identification and quantification, pulverized coal for blowing can be used without using special pretreatment and additives as in the past. It is possible to stably improve and maintain the transportability of the pulverized coal by appropriately adjusting the brand and blending ratio of the coal used as the coal.
本発明の実施形態について、以下に説明する。 Embodiments of the present invention will be described below.
本発明は、高炉などの冶金炉やボイラーなどの燃焼炉に吹き込む微粉炭中に存在し、配管付着や配管閉塞を引き起こす原因となる無機鉱物の化学形態を特定するとともに、この特定・定量に基づいて、各種石炭の搬送性を適正に評価することを基本的な技術思想とする。 The present invention specifies a chemical form of an inorganic mineral that is present in pulverized coal blown into a metallurgical furnace such as a blast furnace or a combustion furnace such as a boiler, and causes pipe adhesion or pipe clogging. The basic technical idea is to properly evaluate the transportability of various types of coal.
そして、本発明においては、従来の成分化学分析法では不可能であった無機鉱物の化学形態を特定するための手段、および、該無機鉱物の存在比を定量する手段として、ＮＭＲ法を利用する。この点が本発明の特徴である。 In the present invention, the NMR method is used as a means for specifying the chemical form of an inorganic mineral that has been impossible with the conventional component chemical analysis method and a means for quantifying the abundance ratio of the inorganic mineral. . This is a feature of the present invention.
表１に、高炉の微粉炭吹き込み操業で使用した微粉炭（Ａ〜Ｄの４種類の混合微粉炭）と、微粉炭吹き込み配管の内から採取した配管固着物に含まれるＡｌ量、Ｓｉ量および全金属量を成分化学分析により測定した結果を質量％で示す。 Table 1 shows the amount of Al and Si contained in pulverized coal (four types of mixed pulverized coals A to D) used in the operation of blowing pulverized coal in the blast furnace and the fixed pipes collected from the pulverized coal-injected piping. The result of measuring the total metal amount by component chemical analysis is shown in mass%.
表１に示すように、配管固着物中のＡｌ量およびＳｉ量は、Ａ〜Ｄの何れの微粉炭中のＡｌ量およびＳｉ量よりも多い、つまり、微粉炭中のＡｌおよびＳｉが配管固着物の中に濃化している。 As shown in Table 1, the amount of Al and the amount of Si in the fixed pipe are larger than the amounts of Al and Si in any pulverized coal of A to D, that is, the Al and Si in the pulverized coal are solid. It is concentrated in the kimono.
本発明者は、このことから、微粉炭の気体輸送の際において、配管付着または配管閉塞を引き起こす原因物質は、石炭中に存在する“ＡｌとＳｉを主成分とする無機鉱物”（以下「Ａｌ・Ｓｉ無機鉱物」ということがある。）であると予測し、その化学形態を解明ないし特定することについて鋭意検討した。 From this, the present inventor has determined that the causative substance that causes pipe adhesion or pipe blockage during gas transportation of pulverized coal is “an inorganic mineral mainly composed of Al and Si” (hereinafter “Al”).・ Since it is sometimes called “Si inorganic minerals”), we sought to clarify or identify its chemical form.
図１に、本発明において測定対象とする石炭中のＡｌ・Ｓｉ無機鉱物の代表例である、カオリン鉱物（図中（ａ））、スメクタイト（図中（ｂ））、および、雲母粘土鉱物（図中（ｃ））の化学形態を示す。 FIG. 1 shows kaolin mineral ((a) in the figure), smectite ((b) in the figure), and mica clay mineral (which is a representative example of the Al / Si inorganic mineral in the coal to be measured in the present invention. The chemical form of (c)) is shown in the figure.
石炭中には、それぞれ化学構造の異なるＡｌ・Ｓｉ無機鉱物として、図１に示すような、カオリン鉱物（Ａｌ2Ｓｉ2Ｏ5（ＯＨ）4）、スメクタイト（Ｘ（＝Ｎａ，１／２Ｃａ）0.33（Ａｌ1.67Ｍｇ0.33）Ｓｉ4Ｏ10（ＯＨ）2・ｎＨ2Ｏ）、雲母粘土鉱物（Ｋ0.75（Ａｌ1.75Ｒ（＝２価金属）0.25.）（Ｓｉ3.50Ａｌ0.50）Ｏ10（ＯＨ）2・nＨ2Ｏ）等のアルミノケイ酸塩の粘土鉱物、さらに、酸化物として、アルミナ（Ａｌ2Ｏ3）、シリカ（ＳｉＯ2）等が含有されている。 In coal, kaolin minerals (Al 2 Si 2 O 5 (OH) 4 ) and smectites (X (= Na, 1 / 2Ca) as shown in FIG. 1 are used as Al / Si inorganic minerals having different chemical structures. 0.33 (Al 1.67 Mg 0.33 ) Si 4 O 10 (OH) 2 .nH 2 O), mica clay mineral (K 0.75 (Al 1.75 R (= divalent metal) 0.25. ) (Si 3.50 Al 0.50 ) O 10 (OH 2 ) n · H 2 O) and other aluminosilicate clay minerals, and alumina (Al 2 O 3 ), silica (SiO 2 ) and the like as oxides.
カオリン鉱物の化学構造は、Ａｌ3+イオンを中心とした８面体（６配位型Ａｌ）構造とＳｉ4+イオンを中心とした４面体（６配位型Ｓｉ）構造とが１：１で層を形成した構造である（図１中（ａ）参照）。 The chemical structure of kaolin minerals is 1: 1 with an octahedral (6-coordinated Al) structure centered on Al 3+ ions and a tetrahedral (6-coordinated Si) structure centered on Si 4+ ions. This is a structure in which a layer is formed (see FIG. 1A).
スメクタイトの化学構造は、Ｓｉ4+イオンを中心とした４面体（４配位型Ｓｉ）構造がＡｌ3+イオンを中心とした８面体（６配位型Ａｌ）構造を上下から挟み込んだような、２：１の層構造である。上記化学構造は、４配位型Ｓｉ4+イオンの一部をＡｌ3+イオンで置換した構造をとっているから、該構造中には４配位型Ａｌも存在する（図１中（ｂ）参照）。 The smectite chemical structure is such that a tetrahedral (tetracoordinated Si) structure centered on Si 4+ ions sandwiches an octahedral (6-coordinated Al) structure centered on Al 3+ ions from above and below. 2: 1 layer structure. Since the above chemical structure has a structure in which a part of the tetracoordinated Si 4+ ion is substituted with Al 3+ ion, tetracoordinated Al is also present in the structure ((b in FIG. 1) )reference).
雲母粘土鉱物の化学構造も、スメクタイトと同様に、ＳｉＯ4の４面体構造とＡｌＯ6の８面体構造構造が２：１で層を形成した構造で、ＳｉＯ4のＳｉ4+イオンの一部がＡｌ3+イオンで置き換わっている（図１中（ｃ）参照）。上記化学構造は、該構造中の４配位型Ａｌの量がスメクタイトにおける４配位型Ａｌの量よりも多いのが特徴である。 The chemical structure of the mica clay mineral is the same as that of smectite, but the SiO 4 tetrahedral structure and AlO 6 octahedral structure are 2: 1 layered, and some of the Si 4+ ions in SiO 4 are part of the structure. Al 3+ ions are replaced (see (c) in FIG. 1). The chemical structure is characterized in that the amount of tetracoordinated Al in the structure is larger than the amount of tetracoordinated Al in smectite.
アルミナ中のＡｌは６配位型構造をとり、シリカは４配位型Ｓｉで、Ｑ4（ＳｉＯ4ユニット中の酸素が全て隣接するＳｉＯ4ユニットと共有されている）の構造をとっている。 Al in alumina takes 6 coordinated structure, the silica has a structure of four coordinated Si, Q 4 (oxygen in SiO 4 units are shared with all neighboring SiO 4 units) .
本発明は、石炭中に存在する27Ａｌまたは29Ｓｉの核磁気共鳴スペクトルを測定し、該測定スペクトルに基づいて、上記石炭中に存在するＡｌ・Ｓｉ無機鉱物の化学形態を分類し、該分類に基づいて、上記石炭の搬送性を評価することを特徴とする。 The present invention measures the nuclear magnetic resonance spectrum of 27 Al or 29 Si present in coal, classifies the chemical form of the Al / Si inorganic mineral present in the coal based on the measured spectrum, Based on the above, the transportability of the coal is evaluated.
そして、上記測定、分類および評価は、具体的には、以下のように行うことができる。 The measurement, classification, and evaluation can be specifically performed as follows.
まず、上述した石炭中に存在するＡｌ・Ｓｉ無機鉱物の標準試料を用いて、各々のＡｌ・Ｓｉ無機鉱物中の27Ａｌまたは29ＳｉのＮＭＲスペクトルを測定し、各々のＡｌ・Ｓｉ無機鉱物について、ピークの位置を特定する。 First, using the Al / Si inorganic mineral standard sample present in the coal, the 27 Al or 29 Si NMR spectrum in each Al / Si inorganic mineral was measured. Identify the peak position.
続いて、高炉の微粉炭吹き込み操業において配管に付着した固着物または配管を閉塞した固着物（以下、併せて「配管固着物」ということがある。）から採取した試料について、該試料中の27Ａｌまたは29ＳｉのＮＭＲスペクトルを測定し、観測されるピーク位置と、上記の既に測定した各々のＡｌ・Ｓｉ無機鉱物の27Ａｌまたは29ＳｉのＮＭＲスペクトルピーク位置とを照合し、その結果から、配管固着物中に存在するＡｌ・Ｓｉ無機鉱物の化学形態を特定する。 Subsequently, a sample collected from a fixed matter adhering to the pipe or a fixed matter clogging the pipe in the operation of blowing pulverized coal in the blast furnace (hereinafter, also referred to as “pipe-fixed matter”) is 27 % of the sample. The NMR spectrum of Al or 29 Si is measured, and the observed peak position is collated with the 27 Al or 29 Si NMR spectrum peak position of each Al · Si inorganic mineral that has already been measured. The chemical form of the Al / Si inorganic mineral present in the fixed pipe is specified.
さらに、配管固着物中に存在する27Ａｌまたは29ＳｉのＮＭＲスペクトルに基づいて、27Ａｌまたは29Ｓｉの全ピークに係る積分値（全ピーク積分値）と、上記照合で特定されたＡｌ・Ｓｉ無機鉱物別に、該無機鉱物に該当する全てのピークに係る積分値（特定無機鉱物ピーク積分値）を求め、全ピーク積分値に対する特定無機化合物ピーク積分値の比率から、配管固着物中に含まれるＡｌ・Ｓｉ無機鉱物の存在比を定量する。 Furthermore, based on the NMR spectrum of 27 Al or 29 Si present in the pipe adhering material, the integrated value (total peak integrated value) for all 27 Al or 29 Si peaks and the Al · Si specified in the above collation For each inorganic mineral, the integral value (specific inorganic mineral peak integral value) relating to all the peaks corresponding to the inorganic mineral is obtained, and is included in the fixed pipe from the ratio of the specific inorganic compound peak integral value to the total peak integral value. Quantify the abundance ratio of Al / Si inorganic minerals.
次に、混合微粉炭を構成する各種銘柄の石炭のそれぞれについて、27Ａｌまたは29ＳｉのＮＭＲスペクトルを測定し、観測されるピーク位置を、上記の既に測定した各々のＡｌ・Ｓｉ無機鉱物の27Ａｌまたは29ＳｉのＮＭＲスペクトルピーク位置と照合し、その結果から、混合微粉炭を構成する各種銘柄の石炭中に存在するＡｌ・Ｓｉ無機鉱物の化学形態を特定する。 Next, for each of the coal various issues comprising mixing pulverized coal, by measuring the NMR spectra of 27 Al or 29 Si, the the observed peak position, the Al · Si inorganic minerals each already measured in the 27 It collates with the NMR spectrum peak position of Al or 29 Si, and the chemical form of the Al / Si inorganic mineral present in various brands of coal composing the mixed pulverized coal is specified from the result.
さらに、混合微粉炭を構成する各種銘柄の石炭中に存在する27Ａｌまたは29ＳｉのＮＭＲスペクトルに基づいて、27Ａｌまたは29Ｓｉの全ピークに係る積分値（全ピーク積分値）と、上記照合で特定されたＡｌ・Ｓｉ無機鉱物別に、該無機鉱物に該当する全てのピークに係る積分値（特定無機鉱物ピーク積分値）を求め、全ピーク積分値に対する特定無機化合物ピーク積分値の比率から、混合微粉炭を構成する各種銘柄の石炭中に含まれるＡｌ・Ｓｉ無機鉱物の存在比を銘柄毎に定量する。 Furthermore, based on the NMR spectra of 27 Al or 29 Si present in various brands of coal that constitute mixed pulverized coal, the integrated value (total peak integrated value) for all 27 Al or 29 Si peaks and the above verification For each of the Al and Si inorganic minerals identified in (1), the integral value (specific inorganic mineral peak integral value) relating to all the peaks corresponding to the inorganic mineral is obtained, and from the ratio of the specific inorganic compound peak integral value to the total peak integral value, The abundance ratio of Al / Si inorganic minerals contained in various brands of coal composing mixed pulverized coal is quantified for each brand.
最後に、以上の特定・定量結果に基づいて、混合微粉炭を構成する各種銘柄の石炭中に存在するＡｌ・Ｓｉ無機鉱物の存在比と、配管固着物中に存在するＡｌ・Ｓｉ無機鉱物の存在比を対比して、両存在比の類似関係から、混合微粉炭を構成する各種銘柄の石炭の搬送性を評価する。 Finally, based on the above identification / quantitative results, the abundance ratio of Al / Si inorganic minerals present in various brands of coal composing the mixed pulverized coal and the Al / Si inorganic minerals present in the fixed pipes By comparing the abundance ratios, the transportability of various brands of coal composing mixed pulverized coal is evaluated from the similar relationship between the abundance ratios.
さらに、この石炭の搬送性評価結果に基づいて、配管付着または配管閉塞の原因物質となっている微粉炭中の石炭銘柄、つまり、搬送性の低い石炭銘柄を特定し、その使用量を制限するか、または、搬送性の良好な石炭銘柄に変更して、微粉炭の搬送性を安定して高めることができる。 Furthermore, based on the coal transportability evaluation results, identify the coal brand in the pulverized coal that is the causative agent of pipe adhesion or pipe clogging, that is, the coal brand with low transportability, and limit the amount used. Alternatively, it is possible to stably improve the transportability of pulverized coal by changing to a coal brand having good transportability.
本発明によれば、配管内から採取した配管固着物中に存在するＡｌ・Ｓｉ無機鉱物の化学形態の特定とその存在比の定量に基づいて、微粉炭として使用する各種石炭の搬送性を評価できるので、原料炭の需給事情や操業変更により微粉炭を構成する各石炭銘柄を変更する時にも、その配合比を、適宜、適正に調整して、微粉炭の搬送性を安定して良好に維持することができる。 According to the present invention, the transportability of various coals used as pulverized coal is evaluated based on the identification of the chemical form of Al / Si inorganic minerals present in the fixed pipes collected from the pipes and the determination of their abundance ratios. Therefore, when changing the coal brands that make up pulverized coal due to the supply and demand situation of coking coal and operation changes, the mixing ratio is adjusted appropriately and appropriately, and the transportability of pulverized coal is stable and good Can be maintained.
本発明において、石炭中に存在するＡｌ・Ｓｉ無機鉱物の化学構造の特定は、その骨格の中心を担う27Ａｌまたは29ＳｉのＮＭＲスペクトルを測定する（以下、それぞれを「27Ａｌ−ＮＭＲ測定」、「29Ｓｉ−ＮＭＲ測定」という。）ことより行うことができる。 In the present invention, the chemical structure of the Al / Si inorganic mineral present in the coal is determined by measuring the NMR spectrum of 27 Al or 29 Si that plays a central role in the skeleton (hereinafter referred to as “ 27 Al-NMR measurement”). , " 29 Si-NMR measurement").
27Ａｌ−ＮＭＲ測定では、アルミノケイ酸塩やアルミナ等、アルミニウムを含む化合物の化学形態を特定することができる。 In 27 Al-NMR measurement, the chemical form of a compound containing aluminum such as aluminosilicate and alumina can be specified.
27Ａｌ核は、核スピンが２／５で核四極子相互作用を有するので、27Ａｌ−ＮＭＲ測定では、27Ａｌ−マジック角回転（Magic Angle Spinning、以下「ＭＡＳ」と略称する。）法に比べてより核四極子相互作用を平均化できる27Ａｌ−多量子マジック角回転（Multiple Quantum Magic Angle Spinning、以下「ＭＱＭＡＳ」と略称する。）法が、測定精度の点で好ましい。 Since 27 Al nuclei have a nuclear spin of 2/5 and a nuclear quadrupole interaction, the 27 Al-NMR measurement uses the 27 Al-magic angle spinning (hereinafter abbreviated as “MAS”) method. In comparison, the 27 Al-Multiple Quantum Magic Angle Spinning (hereinafter abbreviated as “MQMAS”) method that can average the nuclear quadrupole interaction is more preferable in terms of measurement accuracy.
ＭＱＭＡＳ法により得られるスペクトル（ＭＱＭＡＳスペクトル）は、ＭＡＳ法により得られるスペクトル（ＭＡＳスペクトル）の線形を示すＦ２軸と核四極子相互作用が平均化された線形を示すＦ１軸の両軸から成る２次元スペクトルとして表されるので、Ｆ２軸上での見かけの化学シフト値（以下「ＭＡＳシフト値」と表記する。）が同じ化合物でも、四極子結合定数（核四極子相互作用の大きさを表すパラメータ）が異なれば、Ｆ１軸上で異なるシフト値（以下「Isotropicシフト値」と表記する。）を表示する。 A spectrum (MQMAS spectrum) obtained by the MQMAS method is composed of both F2 axis indicating the linearity of the spectrum (MAS spectrum) obtained by the MAS method and F1 axis indicating the linearity obtained by averaging the nuclear quadrupole interactions. Since it is expressed as a two-dimensional spectrum, even if the compound has the same apparent chemical shift value on the F2 axis (hereinafter referred to as “MAS shift value”), the quadrupole coupling constant (represents the magnitude of the nuclear quadrupole interaction). If the parameters are different, different shift values (hereinafter referred to as “Isotropic shift values”) on the F1 axis are displayed.
それ故、ＭＱＭＡＳスペクトルによれば、２次元スペクトル上で化合物をより明確に区別することが可能となる。 Therefore, according to the MQMAS spectrum, it becomes possible to distinguish the compounds more clearly on the two-dimensional spectrum.
一方、29Ｓｉ−ＮＭＲ測定においてＭＡＳ法を用いると、アルミノケイ酸塩やシリカ等のケイ素を含む化合物の化学形態を特定することができる。 On the other hand, when the MAS method is used in 29 Si-NMR measurement, the chemical form of a compound containing silicon such as aluminosilicate or silica can be specified.
29Ｓｉ−ＮＭＲ測定では、一般的に、化学シフトの異方性が強いので、スペクトルの線幅が広幅化し易く、石炭中に化学構造が類似する複数種のＡｌ・Ｓｉ無機鉱物が存在すると、それらを判別することが困難となる場合がある。 In 29 Si-NMR measurement, since the chemical shift anisotropy is generally strong, it is easy to broaden the line width of the spectrum, and when there are multiple types of Al · Si inorganic minerals with similar chemical structures in coal, It may be difficult to distinguish them.
また、29Ｓｉ−ＮＭＲ測定では、29Ｓｉ核のスピン−格子緩和時間（以下「Ｔ１」と略称する。）が一般に長く、そのため長時間の測定時間を要する。 In 29 Si-NMR measurement, the spin-lattice relaxation time of 29 Si nuclei (hereinafter abbreviated as “T1”) is generally long, and therefore a long measurement time is required.
本発明においては、27Ａｌ−ＮＭＲ測定および29Ｓｉ−ＮＭＲ測定のいずれを用いても、石炭の搬送性評価において、従来手法に比べ、前記の優れた効果を得ることができるが、測定精度および測定時間などの実用面で、27Ａｌ−ＮＭＲ測定法の方が好ましい。 In the present invention, any of the 27 Al-NMR measurement and the 29 Si-NMR measurement can be used to obtain the above-mentioned excellent effects in the coal transportability evaluation as compared with the conventional method. In terms of practical use such as measurement time, the 27 Al-NMR measurement method is preferred.
本発明の実施形態の一例として、27Ａｌ−ＭＱＭＡＳ法を用いて、石炭中に存在する27ＡｌのＮＭＲスペクトルを測定してＡｌ・Ｓｉ無機鉱物を特定し、かつ、該Ａｌ・Ｓｉ無機鉱物の存在比を定量する方法について、図２および図３を用いて説明する。 As an example of an embodiment of the present invention, 27 with Al-MQMAS method, by measuring the NMR spectra of 27 Al present in the coal identify Al · Si inorganic minerals, and, of the Al · Si inorganic minerals A method for quantifying the abundance ratio will be described with reference to FIGS.
図２に、27Ａｌ−ＭＱＭＡＳ法を用いて、Ａｌ・Ｓｉ無機鉱物（カオリン鉱物、スメクタイト、雲母粘土鉱物またはアルミナ）の標準試料のＮＭＲスペクトルを測定した結果を示す。なお、図２は、各々のＡｌ・Ｓｉ無機鉱物の２次元スペクトルを便宜上１つにまとめたものである。 FIG. 2 shows the results of measuring the NMR spectrum of a standard sample of Al.Si inorganic mineral (kaolin mineral, smectite, mica clay mineral or alumina) using the 27 Al-MQMAS method. Note that FIG. 2 summarizes the two-dimensional spectra of the respective Al · Si inorganic minerals into one for convenience.
図２に示す２次元スペクトルから、例えば、スメクタイトの６配位型Ａｌに相当するピークは、Ｆ２＝３．４ｐｐｍ、Ｆ１＝７．６ｐｐｍ、雲母粘土鉱物の６配位型Ａｌに相当するピークは、Ｆ２＝４．２ｐｐｍ、Ｆ１＝９．０ｐｐｍ、カオリン鉱物の６配位型Ａｌに相当するピークは、Ｆ２＝５．７ｐｐｍ、Ｆ１＝９．３ｐｐｍ、アルミナの６配位型Ａｌに相当するピークは、Ｆ２＝１２．５ｐｐｍ、Ｆ１＝１５．７ｐｐｍ、とそれぞれ特定される。 From the two-dimensional spectrum shown in FIG. 2, for example, peaks corresponding to smectite 6-coordinated Al are F2 = 3.4 ppm, F1 = 7.6 ppm, and peaks corresponding to 6-coordinated Al of mica clay mineral are F2 = 4.2 ppm, F1 = 9.0 ppm, peaks corresponding to kaolin mineral 6-coordinated Al, F2 = 5.7 ppm, F1 = 9.3 ppm, peaks corresponding to alumina 6-coordinated Al Are specified as F2 = 12.5 ppm and F1 = 15.7 ppm, respectively.
また、図２に示す２次元スペクトルには、Ａｌ・Ｓｉ無機鉱物の６配位型Ａｌに相当するピークの他に、スメクタイトおよび雲母粘土鉱物の４配位型Ａｌに相当するピークも存在する。 In addition, in the two-dimensional spectrum shown in FIG. 2, there are peaks corresponding to tetracoordinate Al of smectite and mica clay mineral, in addition to peaks corresponding to hexacoordinate Al of Si / Si inorganic mineral.
しかし、上記ピークは重なっていて判別し難いので、後述する石炭中に存在するＡｌ・Ｓｉ無機鉱物の特定・定量には、標準無機鉱物のピークとして、各々のＡｌ・Ｓｉ無機鉱物のピークが判別し易い６配位型Ａｌに相当するピークを用いるのが好ましい。 However, since the above peaks overlap, it is difficult to distinguish them. Therefore, when identifying and quantifying the Al / Si inorganic minerals present in coal, which will be described later, the peak of each Al / Si inorganic mineral is identified as the peak of the standard inorganic mineral. It is preferable to use a peak corresponding to 6-coordinated Al that is easily formed.
なお、ｐｐｍは“part per million”の略称であり、各ピークに対して、（ピークの観測周波数／共鳴周波数×１０6）×１０6で定義され、ＮＭＲスペクトル測定に用いる装置の静磁場強度の大きさに依存しない無次元の単位である。 In addition, ppm is an abbreviation for “part per million”, and is defined as (peak observation frequency / resonance frequency × 10 6 ) × 10 6 for each peak, and represents the static magnetic field strength of the apparatus used for NMR spectrum measurement. It is a dimensionless unit that does not depend on size.
また、図３に、27Ａｌ−ＭＱＭＡＳ法を用いて、表２に示す微粉炭Ａの石炭の27Ａｌ−ＮＭＲスペクトルを測定した結果（２次元スペクトル）を示す。 FIG. 3 shows the result (two-dimensional spectrum) of 27 Al-NMR spectrum of coal of pulverized coal A shown in Table 2 using 27 Al-MQMAS method.
図３に示す微粉炭Ａの石炭の２次元スペクトルにおけるピーク位置と、図２に示す各々のＡｌ・Ｓｉ無機鉱物のピーク位置を照合すると、微粉炭Ａの石炭において観測されるピークは、Ｆ１＝１５．７ｐｐｍ、Ｆ２＝１２．１ｐｐｍの位置、および、Ｆ１＝８．５ｐｐｍ、Ｆ２＝３．９ｐｐｍの位置にピークトップがある。 When the peak position in the two-dimensional spectrum of coal of pulverized coal A shown in FIG. 3 and the peak position of each of the Al · Si inorganic minerals shown in FIG. 2 are collated, the peak observed in the coal of pulverized coal A is F1 = There is a peak top at the position of 15.7 ppm, F2 = 12.1 ppm, and at the position of F1 = 8.5 ppm, F2 = 3.9 ppm.
前者の位置はアルミナのピーク位置に相当するから、この照合から、石炭中に存在するＡｌ・Ｓｉ無機鉱物の一つとしてアルミナを特定することができる。また、後者の位置は、スメクタイトのピークと雲母粘土鉱物のピークの間にあるから、石炭中に存在するＡｌ・Ｓｉ無機鉱物として、スメクタイトと雲母粘土鉱物の両方、または、両者の混合層鉱物を特定することができる。 Since the former position corresponds to the peak position of alumina, it is possible to identify alumina as one of Al · Si inorganic minerals present in coal from this comparison. In addition, since the latter position is between the smectite peak and the mica clay mineral peak, both the smectite and mica clay mineral, or a mixed layer mineral of both, is used as the Al / Si inorganic mineral present in coal. Can be identified.
また、微粉炭Ａの石炭中に存在するスメクタイト、雲母粘土鉱物、および、アルミナそれぞれの存在比は、各々の無機鉱物のスペクトルについて、Ｆ２軸方向への積分値を求め、その後、27Ａｌ−ＮＭＲスペクトルの全ピークの積分値に対するに上記積分値の比率を求めることによって定量できる。 The abundance ratios of smectite, mica clay mineral, and alumina present in the coal of pulverized coal A were determined as integral values in the F2 axis direction for each inorganic mineral spectrum, and then 27 Al-NMR. It can be quantified by determining the ratio of the integrated value to the integrated value of all the peaks of the spectrum.
図３に示す微粉炭Ａの石炭のスペクトルについて、Ｆ２軸方向への積分をとったスペクトルを図４に示す。 FIG. 4 shows a spectrum obtained by integrating the pulverized coal A shown in FIG. 3 in the F2-axis direction.
各々のＡｌ・Ｓｉ無機鉱物の存在比を求めるには、まず、図２に示す、各々のＡｌ・Ｓｉ無機鉱物の２次元スペクトルのピークについて、Ｆ２軸方向への積分をとったスペクトルを得る必要がある。これにより、各々のＡｌ・Ｓｉ無機鉱物が示すスペクトルピークに関して、ピークトップの位置および半値幅を定義できる。 In order to obtain the abundance ratio of each Al · Si inorganic mineral, it is first necessary to obtain a spectrum obtained by integrating the two-dimensional spectrum peak of each Al · Si inorganic mineral shown in FIG. There is. Thereby, the position of a peak top and a half value width can be defined about the spectrum peak which each Al * Si inorganic mineral shows.
このピークトップの位置および半値幅の値を、図４に示すスペクトルの波形分離に適用し、実測したピークに対して最小二乗近似を行うことにより、表２に示すように、各々のＡｌ・Ｓｉ無機鉱物の定量を行うことが可能となる。 By applying the peak top position and half width value to the waveform separation of the spectrum shown in FIG. 4 and performing a least square approximation on the measured peak, as shown in Table 2, each Al · Si Quantification of inorganic minerals can be performed.
続いて、実際に、配管に付着または配管を閉塞している配管固着物を採取し、上記方法で、配管固着物中のＡｌ・Ｓｉ無機鉱物の特定および定量を行い、複数の微粉炭の中から、Ａｌ・Ｓｉ無機鉱物の存在比が配管固着物中のＡｌ・Ｓｉ無機鉱物の存在比と最も近い微粉炭を選出することにより、配管付着または配管閉塞の原因となっている微粉炭を特定することができる。 Subsequently, the pipe adhering substance that actually adheres to or closes the pipe is collected, and the above method is used to identify and quantify the Al / Si inorganic minerals in the pipe adhering substance. From the above, by selecting the pulverized coal whose Al / Si inorganic mineral abundance ratio is the closest to the Al / Si inorganic mineral abundance ratio in the fixed pipe, identify the pulverized coal that causes piping adhesion or blockage can do.
そして、微粉炭の配合に際し、配管付着または配管閉塞の原因となっている微粉炭の使用量を低減するか、または、該微粉炭を他の微粉炭に変更することにより、微粉炭の搬送性を向上させ、微粉炭の配管付着または微粉炭による配管閉塞を防止することが可能となる。 And, when blending pulverized coal, by reducing the amount of pulverized coal used causing piping adhesion or piping blockage, or by changing the pulverized coal to another pulverized coal, the transportability of pulverized coal And it is possible to prevent the pulverized coal from adhering to the pipe or preventing the pulverized coal from blocking the pipe.
以下に、本発明の実施例について説明するが、実施例の条件は、本発明の実施可能性及び効果を確認するために採用した一条件例であり、本発明は、この一条件例に限定されるものではない。本発明は、本発明の要旨を逸脱せず、本発明の目的を達成する限りにおいて、種々の条件を採用し得るものである。 Examples of the present invention will be described below, but the conditions of the examples are one example of conditions adopted for confirming the feasibility and effects of the present invention, and the present invention is limited to these one example of conditions. Is not to be done. The present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
高炉吹き込み用の微粉炭として銘柄の異なる４種類（微粉炭Ａ、Ｂ、Ｃ、Ｄ）の微粉炭の各々を、直径４ｍｍのＮＭＲ固体用試料管に均一になるように充填し、７００ＭＨｚ固体専用ＮＭＲ装置（測定磁場強度１６．４Ｔ）にセットした後、外部磁場に対してマジック角（５４．７°）で、１８ｋＨｚの高速で回転させた。 Each of four types of pulverized coal (pulverized coal A, B, C, D) as pulverized coal for blast furnace injection is uniformly packed in an NMR solid sample tube with a diameter of 4 mm. After setting in the NMR apparatus (measured magnetic field strength 16.4T), it was rotated at a high speed of 18 kHz at a magic angle (54.7 °) with respect to the external magnetic field.
このときの27Ａｌ共鳴周波数は１８２．４ＭＨｚであった。27Ａｌ−ＮＭＲの化学シフト基準として、１ｍｏｌ／ｌＡｌＣｌ3水溶液を、−０．１ｐｐｍとした。 The 27 Al resonance frequency at this time was 182.4 MHz. As a reference for chemical shift of 27 Al-NMR, 1 mol / l AlCl 3 aqueous solution was set to -0.1 ppm.
上記条件下で、微粉炭Ａ、Ｂ、Ｃ、Ｄのそれぞれについて、27Ａｌ-ＭＱＭＡＳスペクトル（27Ａｌ−ＭＱＭＡＳ法によるＮＭＲスペクトル）を測定した（図３及び図５〜７、参照）。 Under the above conditions, 27 Al-MQMAS spectrum (NMR spectrum by 27 Al-MQMAS method) was measured for each of pulverized coals A, B, C, and D (see FIGS. 3 and 5 to 7).
本発明法を用いて測定した微粉炭Ａ、Ｂ、Ｃ、ＤのＭＱＭＡＳスペクトルのピーク位置と、予め標準試料を用いて測定したカオリン鉱物、スメクタイト、雲母粘土鉱物およびアルミナ（Ａｌ2Ｏ3）の27Ａｌ−ＭＱＭＡＳスペクトル（図２、参照）のピークト位置とを照合して、微粉炭Ａ、Ｂ、Ｃ、Ｄ中に存在するＡｌ・Ｓｉ無機鉱物を特定した。 The peak positions of the MQMAS spectra of pulverized coals A, B, C and D measured using the method of the present invention, and of kaolin mineral, smectite, mica clay mineral and alumina (Al 2 O 3 ) measured using a standard sample in advance. 27 Al-MQMAS spectra (see FIG. 2) were compared with the peak positions to identify Al / Si inorganic minerals present in pulverized coals A, B, C, and D.
また、微粉炭Ａ、Ｂ、Ｃ、Ｄの27Ａｌ−ＭＱＭＡＳスペクトルに基づいて、該ＭＱＭＡＳスペクトルの全ピークの積分値に対する各々のＡｌ・Ｓｉ無機鉱物に相当するピークの積分値の比率を求め、該比率から、各々のＡｌ・Ｓｉ無機鉱物の存在比を定量した。その結果を表２に示す。 Further, based on the 27 Al-MQMAS spectrum of pulverized coal A, B, C, D, the ratio of the integrated value of the peak corresponding to each Al · Si inorganic mineral to the integrated value of all the peaks of the MQMAS spectrum is obtained, From this ratio, the abundance ratio of each Al · Si inorganic mineral was quantified. The results are shown in Table 2.
なお、図７に示すとおり、微粉炭Ｄの27Ａｌ−ＭＱＭＡＳスペクトルにおいては、標準試料の無機鉱物（カオリン鉱物［６配位型Ａｌ］、スメクタイト［４配位型Ａｌ、６配位型Ａｌ］、雲母粘土鉱物［４配位型Ａｌ、６配位型Ａｌ］、アルミナ［６配位型Ａｌ］）に相当するピーク以外のピークとして、石炭中に存在する６配位型Ａｌおよび５配位型Ａｌに相当するピークが観測されている。 As shown in FIG. 7, in the 27 Al-MQMAS spectrum of pulverized coal D, inorganic minerals (kaolin mineral [6-coordinated Al], smectite [4-coordinated Al, 6-coordinated Al] of standard samples are used. As peaks other than those corresponding to mica clay minerals [tetracoordinated Al, hexacoordinated Al], alumina [sixcoordinated Al]), hexacoordinated Al and pentacoordinated in coal. A peak corresponding to type Al is observed.
表２に示すＡｌ・Ｓｉ無機鉱物の存在比（ｍｏｌ％）は、次のように算出した。まず、最小二乗近似により、各々の無機鉱物に相当するピークの積分値を求めた。 The abundance ratio (mol%) of Al · Si inorganic minerals shown in Table 2 was calculated as follows. First, the integral value of the peak corresponding to each inorganic mineral was determined by least square approximation.
この積分値の比（積分比）は、各々のＡｌ・Ｓｉ無機鉱物中のＡｌ原子のｍｏｌ比に相当するので、得られた積分比を、各々のＡｌ・Ｓｉ無機鉱物１ｍｏｌ中に含まれるＡｌ原子のｍｏｌ数（カオリン鉱物：２ｍｏｌ、スメクタイト：１．８１ｍｏｌ、雲母粘土鉱物：２．２５ｍｏｌ、アルミナ：２ｍｏｌ）で除することによって、各々のＡｌ・Ｓｉ無機鉱物のモル比として算出した。 The ratio of integration values (integration ratio) corresponds to the molar ratio of Al atoms in each Al · Si inorganic mineral, so that the obtained integration ratio is the Al contained in 1 mol of each Al · Si inorganic mineral. By dividing by the number of moles of atoms (kaolin mineral: 2 mol, smectite: 1.81 mol, mica clay mineral: 2.25 mol, alumina: 2 mol), the molar ratio of each Al · Si inorganic mineral was calculated.
なお、表２においては、カオリン鉱物、スメクタイトおよびアルミナ以外の６配位型Ａｌおよび５配位型Ａｌのピークに起因する無機鉱物１ｍｏｌ中には、カオリン鉱物同様、２ｍｏｌのＡｌイオンが存在していると仮定して、存在比（ｍｏ１％）を算出してある。 In Table 2, 2 mol of Al ions are present in 1 mol of inorganic mineral resulting from the peaks of 6-coordinated Al and 5-coordinated Al other than kaolin mineral, smectite and alumina, as in kaolin mineral. The abundance ratio (mo1%) is calculated on the assumption.
続いて、微粉炭Ａ、Ｂ、Ｃ、Ｄを表３に示す配合割合で混合した微粉炭（表中、対策前の微粉炭）を、吹込量４５Ｔ/Ｈで高炉に吹き込み、高炉操業を行った。 Subsequently, pulverized coal A, B, C, and D mixed at the blending ratio shown in Table 3 (in the table, pulverized coal before countermeasures) was blown into the blast furnace at a blowing rate of 45 T / H, and the blast furnace operation was performed. It was.
高炉の吹き込み口に至る配管内に固着していた配管固着物を採取し、図８に示すように、27Ａｌ−ＭＱＭＡＳスペクトルを測定し、該測定スペクトルに基づいて、配管固着物中に存在するＡｌ・Ｓｉ無機鉱物を特定するとともにそれらの存在比を定量した。その特定・定量結果を表３に示す。 Collecting the pipe adhering material that had been adhering to the pipe leading to the blast furnace inlet and measuring the 27 Al-MQMAS spectrum as shown in FIG. 8, and present in the pipe adhering material based on the measured spectrum. Al / Si inorganic minerals were identified and their abundance was quantified. The identification / quantification results are shown in Table 3.
表３に示す結果において、配管固着物中のＡｌ・Ｓｉ無機鉱物の存在比パターンと、微粉炭Ａ〜ＤのそれぞれにおけるＡｌ・Ｓｉ無機鉱物の存在比パターンとを照合・評価することにより、配管付着や配管閉塞の原因となる微粉炭が微粉炭Ｂであると解明できる。 In the results shown in Table 3, by comparing and evaluating the abundance ratio pattern of the Al / Si inorganic mineral in the fixed pipe and the abundance pattern of the Al / Si inorganic mineral in each of the pulverized coals A to D, It can be clarified that the pulverized coal causing the adhesion and the piping blockage is pulverized coal B.
この特定結果を踏まえ、表３に示すように、高炉の微粉炭吹き込み操業において、微粉炭Ｂの比率を５０％から２０％に低減した。その結果、微粉炭の配管内への付着または微粉炭による配管閉塞が抑制され、配管内の圧力損失が小さくなって、微粉炭の吹込量が、対策前の４５Ｔ/Ｈから５５Ｔ/Ｈに増加した。 Based on this specific result, as shown in Table 3, in the operation of blowing pulverized coal in the blast furnace, the ratio of pulverized coal B was reduced from 50% to 20%. As a result, adhesion of pulverized coal into the pipe or blockage of the pipe due to pulverized coal is suppressed, pressure loss in the pipe is reduced, and the amount of pulverized coal injection increases from 45 T / H before countermeasures to 55 T / H did.
以上の結果から、本発明が、石炭の搬送性の評価・向上の点で顕著な効果を奏することが解かる。 From the above results, it can be seen that the present invention has a remarkable effect in terms of evaluation and improvement of coal transportability.
実施例１で用いた吹き込み用の微粉炭と同じ微粉炭Ａ、Ｂ、Ｃ、Ｄのそれぞれを、直径７．５ｍｍのＮＭＲ固体用試料管に均一になるように充填し、３００ＭＨｚ固体専用ＮＭＲ装置（測定磁場強度７．０Ｔ）にセットした後、外部磁場に対してマジック角（５４．７°）で５ｋＨｚの速度で回転させた。 Each of the same pulverized coals A, B, C, and D as the pulverized coal used in Example 1 was uniformly packed in an NMR solid sample tube having a diameter of 7.5 mm, and a 300 MHz solid-dedicated NMR apparatus. After setting to (measured magnetic field intensity 7.0 T), it was rotated at a speed of 5 kHz with a magic angle (54.7 °) with respect to the external magnetic field.
このときの29Ｓｉ共鳴周波数は５９．７ＭＨｚであった。29Ｓｉ−ＮＭＲの化学シフト基準として、ポリジメチルシランの粉末を−３４ｐｐｍとした。 The 29 Si resonance frequency at this time was 59.7 MHz. As a chemical shift standard for 29 Si-NMR, the powder of polydimethylsilane was -34 ppm.
上記条件下で、微粉炭Ａ、Ｂ、Ｃ、Ｄのそれぞれにおける29Ｓｉ−ＭＡＳスペクトル（29Ｓｉ−マジック角回転（ＭＡＳ）法によるＮＭＲスペクトル）を測定した。 Under the above conditions, 29 Si-MAS spectra (NMR spectra obtained by 29 Si-magic angle rotation (MAS) method) in each of pulverized coals A, B, C, and D were measured.
本発明を用いて測定した微粉炭Ａ、Ｂ、Ｃ、Ｄそれぞれの29Ｓｉ−ＭＡＳスペクトルのピーク位置と、予め標準試料を用いて測定したカオリン鉱物、スメクタイト、雲母粘土鉱物およびシリカ（ＳｉＯ2）の29Ｓｉ−ＭＡＳスペクトルのピーク位置とを照合して、微粉炭Ａ、Ｂ、Ｃ、Ｄのそれぞれの中に存在するＡｌ・Ｓｉ無機鉱物を特定した。 29 Si-MAS spectrum peak positions of pulverized coals A, B, C and D measured using the present invention, and kaolin mineral, smectite, mica clay mineral and silica (SiO 2 ) measured in advance using a standard sample Were compared with the peak positions of the 29 Si-MAS spectra to identify Al · Si inorganic minerals present in each of the pulverized coals A, B, C, and D.
また、微粉炭Ａ、Ｂ、Ｃ、Ｄの29Ｓｉ−ＭＡＳスペクトルに基づいて、該ＭＡＳスペクトルの全ピークの積分値に対する各々のＡｌ・Ｓｉ無機鉱物に相当するピークの積分値の比率を求め、該比率から、各々のＡｌ・Ｓｉ無機鉱物の存在比を定量した。その結果を表４に示す。 Further, based on the 29 Si-MAS spectra of pulverized coal A, B, C, D, the ratio of the integrated value of the peak corresponding to each Al · Si inorganic mineral to the integrated value of all the peaks of the MAS spectrum is obtained, From this ratio, the abundance ratio of each Al · Si inorganic mineral was quantified. The results are shown in Table 4.
次に、実施例１で配管内から採取した配管固着物と同様のものを用いて、その29Ｓｉ−ＭＡＳスペクトルを測定し、該測定スペクトルに基づいて、配管固着物中に存在するＡｌ・Ｓｉ無機鉱物を特定するとともにそれらの存在比を定量した。その特定・定量結果を表４に示す。 Next, the 29 Si-MAS spectrum was measured using the same thing as the fixed pipe collected from the pipe in Example 1, and Al · Si present in the fixed pipe was measured based on the measured spectrum. Inorganic minerals were identified and their abundance was quantified. The identification / quantification results are shown in Table 4.
表４に示す特定・定量結果において、配管固着物中のＡｌ・Ｓｉ無機鉱物の存在比パターンと、微粉炭Ａ〜Ｄ中の存在比パターンとを照合・評価して、配管内に配管固着物を形成するかまたは配管を閉塞する原因炭が微粉炭Ｂであることを解明できた。 In the specific / quantitative results shown in Table 4, the presence ratio pattern of Al / Si inorganic mineral in the fixed pipe and the existing ratio pattern in pulverized coals A to D are collated and evaluated, and the fixed pipe in the pipe It has been clarified that the coal causing caustic or blocking the pipe is pulverized coal B.
以上のとおり、29Ｓｉ−ＭＡＳスペクトルを用いて微粉炭中に含まれるＳｉの化学構造を特定することにより、27Ａｌ−ＭＱＭＡＳスペクトルを用いて得た結果（実施例１）と同様に、配管付着や配管閉塞の原因となる微粉炭が微粉炭Ｂであることを解明できた。 As described above, by specifying the chemical structure of Si contained in the pulverized coal using the 29 Si-MAS spectrum, the result of using the 27 Al-MQMAS spectrum (Example 1), the pipe adhesion It was clarified that the pulverized coal causing the blockage of the pipes and the pulverized coal B was pulverized coal.
本発明によれば、前述したように、高炉などの冶金炉やボイラーなどの燃焼炉に吹き込む微粉炭に存在し、配管付着や配管閉塞を引き起こす原因となる無機鉱物の化学形態を特定するとともに、該無機鉱物の存在比を定量し、この特定・定量に基づいて、各種石炭の搬送性を適正に評価することができるので、従来のような特殊な事前処理や添加剤を用いずとも、吹き込み用の微粉炭として使用する石炭の銘柄及び配合比を適宜調節して、微粉炭の搬送性を安定して向上せしめ維持することができる。 According to the present invention, as described above, present in pulverized coal blown into a metallurgical furnace such as a blast furnace and a combustion furnace such as a boiler, specify the chemical form of inorganic minerals that cause pipe adhesion and pipe blockage, Since the abundance ratio of the inorganic minerals can be quantified and the transportability of various coals can be properly evaluated based on the identification and quantification, blowing can be done without using special pretreatment and additives as in the past. By appropriately adjusting the brand and blending ratio of the coal used as the pulverized coal, the transportability of the pulverized coal can be stably improved and maintained.
したがって、本発明は、発電産業および製鉄産業などを代表とする石炭をエネルギー源として使用する産業において、利用価値が極めて高いものである。 Therefore, the present invention has extremely high utility value in industries that use coal as an energy source, such as the power generation industry and the steel industry.
Claims (5)
上記石炭中に存在する27Ａｌの核磁気共鳴スペクトルを測定し、該測定スペクトルのピーク位置と、カオリン鉱物、スメクタイト、雲母粘土鉱物またはＡｌ 2 Ｏ 3 に相当するピーク位置とを照合し、上記石炭中に存在するＡｌとＳｉを主成分とする無機鉱物の化学形態を特定し、さらに、全ピーク積分値に対する該無機鉱物のピーク積分値の比率から該無機鉱物の存在比を定量し、
続いて、上記配管に付着または配管を閉塞する配管固着物から採取した試料中の 27 Ａｌの核磁気共鳴スペクトルを測定し、該測定スペクトルのピーク位置と、カオリン鉱物、スメクタイト、雲母粘土鉱物またはＡｌ 2 Ｏ 3 に相当するピーク位置とを照合し、上記配管固着物中に存在するＡｌとＳｉを主成分とする無機鉱物の化学形態を特定し、さらに、全ピーク積分値に対する該無機鉱物のピーク積分値の比率から該無機鉱物の存在比を定量し、
上記石炭中に存在するＡｌとＳｉを主成分とする無機鉱物の存在比と、上記配管固着物中に存在するＡｌとＳｉを主成分とする無機鉱物の存在比を対比して、両存在比の類似関係から、上記石炭の搬送性を評価することを特徴とする微粉炭の搬送性評価方法。 It is a method of evaluating the transportability of coal used as pulverized coal that is gas-transported using pipes to a metallurgical furnace or a combustion furnace blowing port, and is blown into the furnace from the blowing port,
The nuclear magnetic resonance spectrum 27 Al present in the coal is measured, compares the peak position of the measured spectrum, kaolin minerals, smectites, and a peak position corresponding to mica clay minerals or Al 2 O 3, the coal Identifying the chemical form of the inorganic mineral mainly composed of Al and Si present therein, and further quantifying the abundance ratio of the inorganic mineral from the ratio of the peak integral value of the inorganic mineral to the total peak integral value;
Subsequently, the nuclear magnetic resonance spectrum of 27 Al in the sample collected from the pipe adhering material adhering to or blocking the pipe is measured, and the peak position of the measurement spectrum and the kaolin mineral, smectite, mica clay mineral or Al The peak position corresponding to 2 O 3 is collated, the chemical form of the inorganic mineral mainly composed of Al and Si present in the above-mentioned pipe fixed matter is specified , and the peak of the inorganic mineral relative to the total peak integral value is further determined. Quantifying the abundance ratio of the inorganic mineral from the ratio of the integral value,
By comparing the abundance ratio of the inorganic minerals mainly composed of Al and Si present in the coal with the abundance ratio of the inorganic minerals mainly composed of Al and Si present in the fixed pipe, both abundance ratios A method for evaluating the transportability of pulverized coal, wherein the transportability of the coal is evaluated from the similar relationship .
上記石炭中に存在するPresent in the above coal 2929 Ｓｉの核磁気共鳴スペクトルを測定し、該測定スペクトルのピーク位置と、カオリン鉱物、スメクタイト、雲母粘土鉱物またはＳｉＯThe nuclear magnetic resonance spectrum of Si is measured, the peak position of the measured spectrum, kaolin mineral, smectite, mica clay mineral or SiO 22 に相当するピーク位置とを照合し、上記石炭中に存在するＡｌとＳｉを主成分とする無機鉱物の化学形態を特定し、さらに、全ピーク積分値に対する該無機鉱物のピーク積分値の比率から該無機鉱物の存在比を定量し、Is identified, and the chemical form of the inorganic mineral mainly composed of Al and Si present in the coal is specified. Further, from the ratio of the peak integral value of the inorganic mineral to the total peak integral value, Quantifying the abundance ratio of the inorganic mineral,
続いて、上記配管に付着または配管を閉塞する配管固着物から採取した試料中のSubsequently, in the sample collected from the fixed pipe adhering to or blocking the pipe 2929 Ｓｉの核磁気共鳴スペクトルを測定し、該測定スペクトルのピーク位置と、カオリン鉱物、スメクタイト、雲母粘土鉱物またはＳｉＯThe nuclear magnetic resonance spectrum of Si is measured, the peak position of the measured spectrum, kaolin mineral, smectite, mica clay mineral or SiO 22 に相当するピーク位置とを照合し、上記配管固着物中に存在するＡｌとＳｉを主成分とする無機鉱物の化学形態を特定し、さらに、全ピーク積分値に対する該無機鉱物のピーク積分値の比率から該無機鉱物の存在比を定量し、To identify the chemical form of the inorganic mineral mainly composed of Al and Si present in the above-mentioned pipe fixed matter, and further, the peak integral value of the inorganic mineral relative to the total peak integral value Quantifying the abundance ratio of the inorganic mineral from the ratio,
上記石炭中に存在するＡｌとＳｉを主成分とする無機鉱物の存在比と、上記配管固着物中に存在するＡｌとＳｉを主成分とする無機鉱物の存在比を対比して、両存在比の類似関係から、上記石炭の搬送性を評価することを特徴とする微粉炭の搬送性評価方法。By comparing the abundance ratio of the inorganic minerals mainly composed of Al and Si present in the coal with the abundance ratio of the inorganic minerals mainly composed of Al and Si present in the fixed pipe, both abundance ratios A method for evaluating the transportability of pulverized coal, wherein the transportability of the coal is evaluated from the similar relationship.
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