JP4927020B2 - Quantitative determination method for sulfur in coal - Google Patents
Quantitative determination method for sulfur in coal Download PDFInfo
- Publication number
- JP4927020B2 JP4927020B2 JP2008107015A JP2008107015A JP4927020B2 JP 4927020 B2 JP4927020 B2 JP 4927020B2 JP 2008107015 A JP2008107015 A JP 2008107015A JP 2008107015 A JP2008107015 A JP 2008107015A JP 4927020 B2 JP4927020 B2 JP 4927020B2
- Authority
- JP
- Japan
- Prior art keywords
- coal
- sulfur
- generated
- gas
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
本発明は、石炭中に存在する硫黄化合物を形態別に定量する方法に関する。 The present invention relates to a method for quantifying sulfur compounds present in coal by form.
石炭は、火力発電等の燃料として、また、製鉄プロセスにおいて鉄鉱石を溶製するときの燃料や還元材として、汎用的に用いられている。しかし、近年、確保できる石炭の品質が劣化してきており、他の不純物と共に、石炭中に存在する硫黄成分の量は増加してきている。 Coal is generally used as a fuel for thermal power generation and the like, and as a fuel and a reducing material for melting iron ore in an iron making process. However, in recent years, the quality of coal that can be secured has deteriorated, and the amount of sulfur components present in the coal has increased along with other impurities.
このような背景から、石炭の有効な利用方法、例えば、石炭の液化・ガス化、又は、コークス用原料炭の範囲の拡大等のために、原料炭の性状をより精密に求めること、又は、石炭の液化において触媒として機能する黄鉄鉱（ＦｅＳ2）の含量を求めること等、全硫黄分の含量だけでなく、硫黄分を、存在形態別に求めることが要求されるようになってきている。 From such a background, for the effective utilization of coal, for example, liquefaction / gasification of coal, expansion of the range of coking coal, etc., more accurately determining the properties of the raw coal, or In addition to determining the content of pyrite (FeS 2 ), which functions as a catalyst in coal liquefaction, it is now required to determine not only the total sulfur content but also the sulfur content by form of existence.
石炭中の硫黄が原因で発生する問題について、製鉄プロセスの例を挙げて説明する。石炭が製鉄プロセスで使用されると、石炭の硫黄成分の殆どは、最終的には、ガス成分又はタールやミスト等の油状成分となる。石炭の使用形態として、最も割合が高いのは、乾留してコークスにし、高炉で使用する場合であるが、このコークス化工程において、タールやガスを産出する。 A problem caused by sulfur in coal will be described with an example of an iron making process. When coal is used in an iron making process, most of the sulfur component of the coal eventually becomes a gas component or an oily component such as tar or mist. As the use form of coal, the ratio is the highest when it is dry-distilled into coke and used in a blast furnace. In this coking process, tar and gas are produced.
タールは、化学製品の原料に、ガスは、エネルギー源として主に製鉄所で使用される。このガスは、ＣＯＧ（Coke Oven Gas）と呼ばれ、熱源の燃料として使用されるが、硫黄分が含まれていると、硫黄分が、燃焼の際に、ＳＯxとなる問題があり、また、バーナーの腐食の原因にもなる場合がある。 Tar is used as a raw material for chemical products, and gas is used mainly as an energy source in steelworks. This gas is called COG (Coke Oven Gas) and is used as a fuel for the heat source, but if it contains a sulfur component, there is a problem that the sulfur component becomes SO x during combustion. It may also cause corrosion of the burner.
そこで、一般には、精製をして、硫黄分を除いて使用するが、石炭中の硫黄分が増大すれば、この精製能力やコストを圧迫する問題が起きる。コークスに残った硫黄は、高炉内での反応において、殆どが、スラグ中に回収されるが、銑鉄にも溶解量として約１％程度あるとされ、後工程である製鋼での脱硫を考えれば、なるべく低硫黄の石炭を用いることが望ましい。 Therefore, in general, refining is performed to remove the sulfur content. However, if the sulfur content in the coal is increased, there arises a problem of pressing the refining capacity and cost. Most of the sulfur remaining in the coke is recovered in the slag in the reaction in the blast furnace, but the amount of dissolved iron is also about 1%. It is desirable to use low sulfur coal as much as possible.
この点でも、乾留による、硫黄のコークス、ガス、タール等への分配を把握することは、後工程での脱硫を考慮するうえで重要なことである。この硫黄の分配を把握することを可能にするのは、石炭中の硫黄を、存在形態別に定量することである。 In this respect as well, it is important to grasp the distribution of sulfur to coke, gas, tar, etc., in consideration of desulfurization in the subsequent process. It is possible to determine the sulfur distribution by quantifying sulfur in coal according to the form of existence.
石炭中の硫黄は、無機物又は有機物として存在する。無機物は、金属の硫化物（特に、硫化鉄）や硫酸塩として存在し、有機物は、石炭の化学構造骨格内に存在する。 Sulfur in coal exists as an inorganic substance or an organic substance. Inorganic substances exist as metal sulfides (especially iron sulfide) and sulfates, and organic substances exist within the chemical structure skeleton of coal.
石炭中の硫黄を分析する方法は、その全量分析法として、エシュカ法や、燃焼法（例えば、非特許文献１、参照）がある。エシュカ法は、石炭試料を、エシュカ合剤と呼ばれる薬剤と共に、空気中で加熱し、石炭試料中の硫黄を、硫酸塩（硫酸バリウム）として回収し、これを測定する。 As a method for analyzing sulfur in coal, there are an Eshka method and a combustion method (for example, see Non-Patent Document 1) as a total amount analysis method. In the Eshka method, a coal sample is heated in air together with an agent called an Eshka mixture, and sulfur in the coal sample is recovered as sulfate (barium sulfate) and measured.
また、試料を、酸素気流中で高温（１３５０℃）に加熱して、燃焼させ、石炭試料中の硫黄を、酸化して、硫黄酸化物としてガス化し、これを、過酸化水素水で回収して、回収液中の硫黄を滴定法で求める方法もある。 Also, the sample is heated to a high temperature (1350 ° C.) in an oxygen stream and burned, and sulfur in the coal sample is oxidized and gasified as sulfur oxide, which is recovered with hydrogen peroxide water. There is also a method for obtaining sulfur in the recovered liquid by a titration method.
これらの方法は、石炭中の全硫黄分を、精度良く定量する方法であるが、石炭中に存在する全ての硫黄を、形態に係わらず、完全に、抽出、分離して分析する方法であり、硫黄を、存在形態別に定量することはできない。 These methods are methods for accurately quantifying the total sulfur content in coal. However, all sulfur present in coal is completely extracted, separated and analyzed regardless of the form. Sulfur cannot be quantified according to the form of existence.
石炭中の硫黄の形態別の分析方法としては、硫酸塩硫黄や黄鉄鉱を測定する方法がある（例えば、非特許文献２、参照）。この方法は、石炭中の硫酸塩硫黄を塩酸で抽出し、これを、塩化バリウムにより、硫酸バリウムとして沈殿させて、重量法により、硫黄を測定する方法である。また、黄鉄鉱中の硫黄と結合している鉄を、塩化第一すずで還元し、鉄の量を、重クロム酸カリウム滴定法で求める方法がある。 As an analysis method according to the form of sulfur in coal, there is a method of measuring sulfate sulfur and pyrite (for example, see Non-Patent Document 2). In this method, sulfate sulfur in coal is extracted with hydrochloric acid, precipitated as barium sulfate with barium chloride, and sulfur is measured by a gravimetric method. In addition, there is a method in which iron combined with sulfur in pyrite is reduced with stannous chloride and the amount of iron is obtained by a potassium dichromate titration method.
これらの方法は、石炭に存在する硫黄化合物の特性を利用して、化学的に分解し、硫黄又はそれと化合する成分を定量することによって、本来、石炭に含まれる硫黄化合物を形態別に定量するものである。しかしながら、これらの方法は、煩雑で、分析技術の熟練を必要とし、また、専用の器具を利用しなければならず、日常的に、簡便に分析操作することが難かしいという問題がある。 In these methods, the sulfur compounds contained in coal are quantified according to their form by chemically decomposing using the characteristics of sulfur compounds present in coal and quantifying sulfur or components combined therewith. It is. However, these methods are complicated, require skill in analysis techniques, and have to use dedicated instruments, which makes it difficult to perform analysis operations on a daily basis.
本発明は、上記従来技術の現状に鑑みて、石炭中の硫黄成分を、簡便に、その存在状態に従って定量する方法を提供することを目的とする。 An object of the present invention is to provide a method for easily quantifying a sulfur component in coal according to its existing state in view of the current state of the prior art.
本発明は、上記課題を解決するためになされたものであり、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 to solve the above problems, and the gist of the present invention is as follows.
（１） 石炭を、不活性ガス中で、室温から１０００℃まで昇温加熱し、硫黄化合物が熱分解して発生する硫黄含有ガスを、連続モニタリング測定して、石炭中の硫黄を存在形態別に定量することを特徴とする石炭中硫黄の形態別定量方法。 (1) Coal is heated and heated from room temperature to 1000 ° C in an inert gas, and sulfur-containing gas generated by the thermal decomposition of sulfur compounds is continuously monitored and measured. A method for quantitative determination of sulfur in coal, characterized by quantitative determination.
（２） 前記硫黄含有ガスが、二酸化硫黄、及び／又は、硫化水素であることを特徴とする前記（１）に記載の石炭中硫黄の形態別定量方法。 (2) The method according to (1) above, wherein the sulfur-containing gas is sulfur dioxide and / or hydrogen sulfide.
（３） 前記不活性ガス中に、酸素が１体積％以下存在することを特徴とする前記（１）又は（２）に記載の石炭中硫黄の形態別定量方法。 (3) The method according to (1) or (2) above, wherein oxygen is present in an amount of 1% by volume or less in the inert gas.
本発明によれば、石炭中に存在する硫黄化合物を、簡便に、形態別に分析することが可能になる。本発明を、製鉄又は火力発電等で使用する石炭の評価法に適用することにより、使用できる石炭品種の拡大を図ることができ、硫黄濃度の高い劣質な石炭を有効に利用することが可能となる。 According to the present invention, sulfur compounds present in coal can be easily analyzed by form. By applying the present invention to an evaluation method for coal used in iron making, thermal power generation, etc., it is possible to expand the variety of coal that can be used, and it is possible to effectively use inferior coal with a high sulfur concentration. Become.
以下に、本発明の詳細を説明する。 Details of the present invention will be described below.
一般に、石炭を、不活性ガス中で乾留すると、石炭の様々な化学構造、又は、含まれる不純物の形態に起因するガス種が発生する。 Generally, when coal is carbonized in an inert gas, gas species are generated due to various chemical structures of coal or the form of impurities contained therein.
例えば、製鉄で使用する瀝青炭を中心とするコークス原料炭の場合、コークス炉にて乾留すると、ＣＨ4、Ｃ2Ｈ4、Ｃ2Ｈ6等の炭化水素、及び、Ｈ2やＣＯ、ＣＯ2等が主たるガス成分として生成するが、これらの発生挙動は、石炭種によって大きく異なる。また、硫黄を含むガスも発生するが、この場合、Ｈ2Ｓが殆どであり、一部、硫黄を含む有機化合物が発生する。 For example, in the case of coke coking coal, mainly bituminous coal used in iron making, when carbonized in a coke oven, hydrocarbons such as CH 4 , C 2 H 4 , C 2 H 6 , and H 2 , CO, CO 2 Etc. are produced as main gas components, but their generation behavior varies greatly depending on the coal type. Moreover, although the gas containing sulfur is also generated, in this case, most of H 2 S is generated, and an organic compound containing sulfur is partially generated.
本発明者らは、上記の課題を解決するため、石炭中の硫黄を形態別に、簡便に定量するための方法を鋭意検討した。即ち、石炭試料を昇温加熱した際に発生するガスを、連続的に測定し、その発生挙動を、詳細に観察した。 In order to solve the above-mentioned problems, the present inventors diligently studied a method for simply quantifying sulfur in coal according to its form. That is, the gas generated when the coal sample was heated and heated was continuously measured, and the generation behavior was observed in detail.
その結果、不活性ガス中、又は、１体積％以下の酸素が混入する不活性ガス雰囲気において、石炭を昇温加熱すると、石炭中に含まれる硫黄化合物のガス分解が起こり、特定の温度域において、硫黄化合物に応じた硫黄含有ガスが生成することを見出した。即ち、次の（Ｉ）及び（II）のことを見出した。 As a result, when the coal is heated and heated in an inert gas or in an inert gas atmosphere mixed with 1% by volume or less of oxygen, gas decomposition of sulfur compounds contained in the coal occurs, and in a specific temperature range. The present inventors have found that a sulfur-containing gas corresponding to a sulfur compound is generated. That is, the following (I) and (II) were found.
（Ｉ） 石炭中の硫酸鉄（ＦｅＳＯ4）は、３００〜４００℃に、ＳＯ2発生のピークを持ち、硫化第二鉄（ＦｅＳ2）は、５００〜６００℃に、ＳＯ2発生のピークを持つ。 (I) Iron sulfate (FeSO 4 ) in coal has an SO 2 generation peak at 300 to 400 ° C., and ferric sulfide (FeS 2 ) has an SO 2 generation peak at 500 to 600 ° C. Have.
（II） Ｈ2Ｓの発生は、４００℃以上で見られ、これは、石炭の化学構造の緩和、分解の温度に一致する。４００℃程度では、主に、チオール類の分解が起きている。また、石炭の中には、６００℃近傍において、急峻なピークを持つものがある。この温度において発生する硫化水素は、比較的安定なチオフェン類の分解により発生したものである。したがって、同じ温度域で発生する硫黄化合物ガスであっても、（Ｉ）の硫化鉄由来の硫黄と明確に区別することができる。 (II) The generation of H 2 S is observed at 400 ° C. or higher, which coincides with the relaxation and decomposition temperature of the chemical structure of coal. At about 400 ° C., thiols are mainly decomposed. Some coal has a steep peak around 600 ° C. The hydrogen sulfide generated at this temperature is generated by the decomposition of relatively stable thiophenes. Therefore, even sulfur compound gas generated in the same temperature range can be clearly distinguished from sulfur derived from iron sulfide (I).
有機物由来のＳがＳＯ2とならないのは、雰囲気の酸素ポテンシャルが、有機硫黄化合物を酸化するには低い上、熱分解だけで、ガス体のＨ2Ｓに変換される（外から供給される酸素との反応とは異なる）ためである。 The reason why S derived from organic matter does not become SO 2 is that the oxygen potential of the atmosphere is low to oxidize organic sulfur compounds, and is converted into gaseous H 2 S only by thermal decomposition (supplied from the outside). This is different from the reaction with oxygen).
このことにより、３００〜４００℃の温度域で発生するＳＯ2量から、石炭中のＦｅＳＯ4量を、また、５００〜６００℃の急峻なピークから、ＦｅＳ2量を求めることができる。また、発生するＨ2Ｓは、石炭中の有機硫黄分を発生の由来とするものであり、無機硫黄分と明確に分別することができる。 Thus, the amount of FeSO 4 in coal can be determined from the amount of SO 2 generated in the temperature range of 300 to 400 ° C., and the amount of FeS 2 can be determined from the steep peak at 500 to 600 ° C. The generated H 2 S is derived from the organic sulfur content in the coal and can be clearly separated from the inorganic sulfur content.
従来の石炭中の全硫黄分を測定する場合に用いる燃焼ガス化（酸素の強制的な供給）とは異なり、石炭中の硫黄を熱分解させ、生成するガスを測定することにより、初めて、石炭中の硫黄を形態別に測定することが可能となる。 Unlike conventional combustion gasification (forced supply of oxygen) used to measure the total sulfur content in coal, the first time coal is measured by pyrolyzing sulfur in coal and measuring the gas produced. It becomes possible to measure the sulfur in each form.
なお、不活性ガス中、又は、１体積％以下の酸素が混入する不活性ガス雰囲気において、石炭を昇温加熱することにより発生する硫黄含有ガス種としては、他に、硫化カルボニル（ＣＯＳ）があるが、発生量は、発生ガスの１体積％未満で、極めて少ないので、硫化カルボニル（ＣＯＳ）は、測定するガス種から除いても問題ない。 In addition, carbonyl sulfide (COS) is another example of a sulfur-containing gas generated by heating and heating coal in an inert gas or an inert gas atmosphere in which 1% by volume or less of oxygen is mixed. However, since the generated amount is very small, less than 1% by volume of the generated gas, carbonyl sulfide (COS) can be removed from the gas species to be measured.
本発明は、これらの知見を基になされたものである。以下に、本発明の実施形態の一例を説明する。 The present invention has been made based on these findings. Hereinafter, an example of an embodiment of the present invention will be described.
石炭試料を粉砕して粉状にし（１００〜２５０μｍが好ましい）、これを、炉心管内に、適切な量、充填し、管状の電気炉で、６℃／ｍｉｎで加熱する。発生するガスを、赤外線吸収法（ＳＯ2）、定電位電解法（Ｈ2Ｓ）、質量分析法（ＳＯ2、Ｈ2Ｓの双方）等を用いて、ガスの発生が連続する間、モニタリングする。 A coal sample is pulverized into a powder form (preferably 100 to 250 μm), and this is filled into a furnace core tube in an appropriate amount, and heated in a tubular electric furnace at 6 ° C./min. The generated gas is monitored during continuous gas generation using infrared absorption method (SO 2 ), constant potential electrolysis method (H 2 S), mass spectrometry (both SO 2 and H 2 S), etc. To do.
このとき、試料量や昇温速度は、各検出器でのＳＯ2又はＨ2Ｓの定量可能の範囲を超えないように、含まれる酸化物の量により調整することが必要である。通常は、０．５〜１ｇの試料を、昇温速度１〜１０℃／ｍｉｎで加熱することが望ましい。 At this time, it is necessary to adjust the amount of sample and the rate of temperature increase according to the amount of oxide contained so as not to exceed the quantifiable range of SO 2 or H 2 S in each detector. Usually, it is desirable to heat a 0.5 to 1 g sample at a heating rate of 1 to 10 ° C./min.
以下に、石炭を加熱したときに発生するＳＯ2を、質量分析計を用いてモニタリングした結果の一例を挙げて、本発明の詳細を説明する。 The details of the present invention will be described below by giving an example of the results of monitoring SO 2 generated when coal is heated using a mass spectrometer.
図１に、試料を加熱し、発生するＳＯ2とＨ2Ｓを測定するシステムの例を示す。 FIG. 1 shows an example of a system for heating a sample and measuring generated SO 2 and H 2 S.
ｂは、試料を加熱する加熱炉であり、炉中には、搬送及び雰囲気形成用不活性ガスが導入される。この不活性ガスで、加熱炉ｂ内で発生するＳＯ2とＨ2Ｓを、結露防止配管温度保持用ヒータｃを経て、Ｈ2Ｓ及びＳＯ2モニタリング用検出器ｄへ搬送する。 b is a heating furnace for heating the sample, and an inert gas for transport and atmosphere formation is introduced into the furnace. With this inert gas, SO 2 and H 2 S generated in the heating furnace b are conveyed to the detector 2 for monitoring H 2 S and SO 2 through the heater c for maintaining the temperature of the dew condensation prevention pipe.
このシステムを用い、原料炭Ａを、６℃／ｍｉｎの昇温速度で加熱したときの、ＳＯ2とＨ2Ｓの発生挙動を、図２に示す。 FIG. 2 shows the generation behavior of SO 2 and H 2 S when coking coal A is heated at a rate of temperature increase of 6 ° C./min using this system.
ＳＯ2は、３００〜４００℃、及び、４００〜６００℃にピークを持つ挙動を示した。これは、式（１）又は式（２）に示すように、石炭中の無機硫黄分が分解して、ＳＯ2が発生したことによる。
ＦｅＳＯ4 → １／２Ｆｅ2Ｏ3 ＋ ＳＯ2 ・・・（１）
ＦｅＳ2 （＋２Ｏ） → ＦｅＳ ＋ ＳＯ2 ・・・（２）
SO 2 showed a behavior having peaks at 300 to 400 ° C. and 400 to 600 ° C. This is because, as shown in the formula (1) or (2), the inorganic sulfur content in the coal is decomposed and SO 2 is generated.
FeSO 4 → 1 / 2Fe 2 O 3 + SO 2 (1)
FeS 2 (+ 2O) → FeS + SO 2 (2)
即ち、このピークを測定してＳＯ2を定量することにより、ＦｅＳＯ4及びＦｅＳ2の量を求めることができる。例として、図５に、ＦｅＳ2試薬を加熱したときのＳＯ2の発生パターンを示すが、石炭から発生したＳＯ2のパターンと比較すると、ほぼ同様の発生挙動を示している。 That is, the amount of FeSO 4 and FeS 2 can be determined by measuring this peak and quantifying SO 2 . As an example, FIG. 5 shows the generation pattern of SO 2 when the FeS 2 reagent is heated. Compared with the pattern of SO 2 generated from coal, almost the same generation behavior is shown.
なお、このとき、石炭中の酸素量が硫黄量に比べて十分に多い場合は、式（２）における酸素分を分解時に供給することができるが、酸素濃度が低い場合は、雰囲気ガスに酸素を混入するとよい。 At this time, when the amount of oxygen in the coal is sufficiently larger than the amount of sulfur, the oxygen content in the formula (2) can be supplied at the time of decomposition, but when the oxygen concentration is low, oxygen is added to the atmosphere gas. It is good to mix.
このとき、本発明者らの検討によれば、１体積％超の酸素を混入した場合は、酸素ポテンシャルが高くなり、試料自体も燃焼し、温度の制御が難しくなるとともに、不活性な雰囲気ならばＨ2Ｓとして発生するＳも酸化されるため、酸素濃度を制御する必要がある。通常の石炭で、試料量が１ｇ以下の場合は、特に、酸素の供給をしなくても、雰囲気中の酸素量で十分である。 At this time, according to the study by the present inventors, when more than 1% by volume of oxygen is mixed, the oxygen potential increases, the sample itself burns, the temperature becomes difficult to control, and an inert atmosphere is used. For example, since S generated as H 2 S is also oxidized, it is necessary to control the oxygen concentration. When the amount of sample is 1 g or less with ordinary coal, the amount of oxygen in the atmosphere is sufficient even if oxygen is not supplied.
Ａ、Ｂ、及び、Ｃの３種類の石炭試料を用いて、図１に示す発生ガスモニタリングのシステムにより、乾留操作により発生する硫黄化合物ガスのモニタリングを行った。石炭試料を反応炉心管内（不活性ガス；Ｈｅ気流中）で、電気炉（管状炉）により６℃／ｍｉｎで昇温し、１０００℃まで加熱した。 Using the three types of coal samples A, B, and C, the generated gas monitoring system shown in FIG. 1 was used to monitor the sulfur compound gas generated by the dry distillation operation. The coal sample was heated at 6 ° C./min by an electric furnace (tubular furnace) in a reactor core tube (inert gas; He flow) and heated to 1000 ° C.
ガスの測定は、質量分析計を用い、試料量は０．５ｇとした。このとき着目する質量数は、３４、及び、６４で、それぞれ、Ｈ2Ｓ、及び、ＳＯ2に対応する。石炭Ａ〜Ｃを測定した結果を、図２〜４に示す。 The gas was measured using a mass spectrometer, and the sample amount was 0.5 g. The mass numbers of interest at this time are 34 and 64, which correspond to H 2 S and SO 2 , respectively. The results of measuring coals A to C are shown in FIGS.
Ａ炭は、２００℃近傍からＳＯ2が発生し、３００℃、５３０℃付近にピークを持つ。Ｈ2Ｓの発生は、５２０℃、及び、６１０℃に、それぞれピークを示した。そこで、これらの発生ガス（ピーク）の根拠を調べた。 A charcoal generates SO 2 from around 200 ° C. and has peaks at around 300 ° C. and 530 ° C. The generation of H 2 S showed peaks at 520 ° C. and 610 ° C., respectively. Then, the basis of these generated gas (peak) was investigated.
例えば、図５に、ＦｅＳ2の試薬を加熱したときの発生ガスのパターンを示す。ＦｅＳ2の分解により発生するＳＯ2も、ピークは５３０℃付近にあり、これから明らかなように、５００℃近傍からのＳＯ2ピークはＦｅＳ2によるものである。 For example, FIG. 5 shows a generated gas pattern when a FeS 2 reagent is heated. The SO 2 generated by the decomposition of FeS 2 also has a peak at around 530 ° C., and as is clear from this, the SO 2 peak from around 500 ° C. is due to FeS 2 .
同様に、３００℃付近のピークは、ＦｅＳ2が酸化して生成するといわれるＦｅ2ＳＯ4の分解による発生ピークと確認される。また、Ｈ2Ｓのピークは、４５０℃及び６００℃を中心とする温度域でピークが見られ、石炭の軟化溶融時に起きる有機物の分解により発生したＨ2Ｓであると思われる。 Similarly, the peak around 300 ° C. is confirmed to be a peak generated by the decomposition of Fe 2 SO 4 , which is said to be generated by oxidation of FeS 2 . Further, the peak of H 2 S is observed peak in the temperature range around the 450 ° C. and 600 ° C., it appears to be H 2 S generated by the decomposition of organic matter occurs during thermal plastic coal.
石炭Ｂは、石炭Ａと、ほぼ、硫黄含有率が同じであるが、発生硫黄ガスのパターンが、大きく異なっている。即ち、発生は、Ｈ2Ｓが殆どであり、しかも、６２０℃に、特徴的なピークが見られる。化学構造解析の結果から、石炭Ｂは、チオフェン類の化合物が多いことが確認された。 Coal B has almost the same sulfur content as coal A, but the pattern of generated sulfur gas is greatly different. That is, the generation is mostly H 2 S, and a characteristic peak is observed at 620 ° C. From the results of chemical structure analysis, it was confirmed that coal B has a large amount of thiophene compounds.
石炭Ｃは、石炭Ａ及び石炭Ｂと比較すると、硫黄含有率が半分程度であるので、それぞれの発生ガス成分の量も少ない。 Coal C has a sulfur content of about half that of Coal A and Coal B, so the amount of each generated gas component is also small.
このように、それぞれの発生成分とピーク位置から、発生起因を推定することができるが、その発生量は、大きく異なっている。表１に、これらのガスの組成をまとめて示す。発生ガス及びその発生温度から、各々、発生起因の化学種を求め、その量比を示す。 In this way, the cause of occurrence can be estimated from each generated component and the peak position, but the amount of occurrence is greatly different. Table 1 summarizes the composition of these gases. From the generated gas and the generated temperature, chemical species resulting from the generation are obtained, and the ratios thereof are shown.
それぞれの石炭について、従来のＪＩＳ法により求めた値を、比較値として示す。両者は、ほぼ一致している。このように、本発明によれば、熟練性や専用の器具等が必要な化学分析を基本としたＪＩＳ法等に比べ、簡便な方法でありながら、十分な定量精度で、石炭中の硫黄分を形態別に求めることができる。 The values determined by the conventional JIS method for each coal are shown as comparative values. Both are almost in agreement. Thus, according to the present invention, the sulfur content in coal can be obtained with sufficient quantitative accuracy while being a simple method as compared with JIS method based on chemical analysis that requires skill and specialized equipment. Can be obtained by form.
ａ 搬送及び雰囲気形成用不活性ガス
ｂ 加熱炉
ｃ 結露防止配管温度保持用ヒータ
ｄ Ｈ2Ｓ及びＳＯ2モニタリング用検出器
a Inert gas for conveying and atmosphere formation b Heating furnace c Heater for preventing dew condensation piping temperature d Detector for monitoring H 2 S and SO 2
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008107015A JP4927020B2 (en) | 2008-04-16 | 2008-04-16 | Quantitative determination method for sulfur in coal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008107015A JP4927020B2 (en) | 2008-04-16 | 2008-04-16 | Quantitative determination method for sulfur in coal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009257920A JP2009257920A (en) | 2009-11-05 |
| JP4927020B2 true JP4927020B2 (en) | 2012-05-09 |
Family
ID=41385528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008107015A Active JP4927020B2 (en) | 2008-04-16 | 2008-04-16 | Quantitative determination method for sulfur in coal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4927020B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5877542B2 (en) * | 2012-04-16 | 2016-03-08 | 一般財団法人電力中央研究所 | Generation method, estimation method and estimation system of sulfur release amount |
| JP6048087B2 (en) * | 2012-11-20 | 2016-12-21 | Ｊｆｅスチール株式会社 | Method for estimating ratio of organic sulfur in coke, method for estimating ratio of total sulfur in coke, method for blending coal for coke production, and method for producing coke |
| JP2023114530A (en) * | 2022-02-07 | 2023-08-18 | Ｊｆｅスチール株式会社 | Method for quantifying gas generated from coal, method for estimating amount of gas generated during carbonization of coal, and method for producing coke |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2210637B2 (en) * | 1972-03-06 | 1975-12-04 | Davy Powergas Gmbh, 5000 Koeln | Process for the production of a gas containing sulfur dioxide from a dilute acid obtained during the production of titanium |
| JPH0350296A (en) * | 1989-07-18 | 1991-03-04 | Ishikawajima Harima Heavy Ind Co Ltd | Technique for recovery of sulfur in coal gasification |
| JP3299063B2 (en) * | 1995-01-20 | 2002-07-08 | 義章 井口 | Iron carbide manufacturing method |
| JPH10273681A (en) * | 1997-03-31 | 1998-10-13 | Toshiba Corp | Dry desulfurization system |
| JPH119954A (en) * | 1997-06-25 | 1999-01-19 | Asahi Glass Co Ltd | Highly efficient desulfurization method |
| JP2003206488A (en) * | 2002-01-11 | 2003-07-22 | Mitsubishi Materials Corp | Method for reforming hydrocarbon heavy raw material and apparatus for reforming |
| CN1768126A (en) * | 2003-03-31 | 2006-05-03 | 科学与工业研究委员会 | A process for removal of organic sulphur from high sulphur coal and a device thereof |
| AU2004299837B2 (en) * | 2003-12-12 | 2010-09-23 | Jy Capital Investment Llc | A pre-burning, dry process methodology and systems for enhancing solid fuel properties |
-
2008
- 2008-04-16 JP JP2008107015A patent/JP4927020B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009257920A (en) | 2009-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bläsing et al. | Release of alkali metal, sulphur, and chlorine species from high temperature gasification of high-and low-rank coals | |
| Wang et al. | Transformation of sulfur during pyrolysis of inertinite-rich coals and correlation with their characteristics | |
| Li et al. | Oxidation mechanisms of H2S by oxygen and oxygen-containing functional groups on activated carbon | |
| Nowicki et al. | Comprehensive characterization of thermal decomposition of sewage sludge by TG–MS | |
| Bläsing et al. | Mass spectrometric investigations on the release of inorganic species during gasification and combustion of German hard coals | |
| Zhang et al. | Emission reduction effect on PM2. 5, SO2 and NOx by using red mud as additive in clean coal briquetting | |
| El-Melih et al. | Hydrogen sulfide reformation in the presence of methane | |
| Bläsing et al. | Mass spectrometric investigations on the release of inorganic species during gasification and combustion of Rhenish lignite | |
| Janković et al. | Model-free and model-based kinetics of the combustion process of low rank coals with high ash contents using TGA-DTG-DTA-MS and FTIR techniques | |
| Bläsing et al. | Release of alkali metal, sulphur and chlorine species during high-temperature gasification and co-gasification of hard coal, refinery residue, and petroleum coke | |
| Bläsing et al. | Influence of temperature on the release of inorganic species during high temperature gasification of Rhenish lignite | |
| Duan et al. | Sulfur evolution from coal combustion in O2/CO2 mixture | |
| Guo et al. | Sulfur release and its transformation behavior of sulfur-containing model compounds during pyrolysis under CO2 atmosphere | |
| JP4927020B2 (en) | Quantitative determination method for sulfur in coal | |
| Jia et al. | Sulfur transformation during the pyrolysis of coal with the addition of CaSO4 in a fixed-bed reactor | |
| Gu et al. | Characterisation of volatile organic sulphur compounds release during coal pyrolysis in inert, hydrogen and CO2 atmosphere | |
| Ibrahim et al. | Toluene destruction in thermal stage of Claus reactor with oxygen enriched air | |
| Ibrahim et al. | Role of toluene to acid gas (H2S and CO2) combustion in H2/O2–N2 flame under Claus condition | |
| CN104024439A (en) | Process for the carbothermic or electrothermic production of crude iron or base products | |
| Luo et al. | Migration of sulfur in in-situ gasification chemical looping combustion of Beisu coal with iron-and copper-based oxygen carriers | |
| Ibrahim et al. | Aromatics oxidation in the furnace of sulfur recovery units: Model development and optimization | |
| Tanner et al. | The temperature-dependent release of volatile inorganic species from Victorian brown coals and German lignites under CO2 and H2O gasification conditions | |
| Ströhle et al. | Validation of a detailed reaction mechanism for sulfur species in coal combustion | |
| JPH0436386A (en) | Improvement of slag | |
| Zheng et al. | Pyrolysis Behavior of Pyrite under a CO–H2 Atmosphere |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100810 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111227 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120117 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120208 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150217 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4927020 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150217 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150217 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150217 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |