JP2805372B2 - Coal chemical desulfurization method - Google Patents
Coal chemical desulfurization methodInfo
- Publication number
- JP2805372B2 JP2805372B2 JP2077990A JP7799090A JP2805372B2 JP 2805372 B2 JP2805372 B2 JP 2805372B2 JP 2077990 A JP2077990 A JP 2077990A JP 7799090 A JP7799090 A JP 7799090A JP 2805372 B2 JP2805372 B2 JP 2805372B2
- Authority
- JP
- Japan
- Prior art keywords
- coal
- desulfurization
- sulfur content
- present
- mixture
- 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.)
- Expired - Fee Related
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は，石炭の燃焼に際し，硫黄酸化物として大
気中に放出され，環境破壊の元凶の一つに挙げられてい
る石炭中に含有されている硫黄分を，有効に，経済的に
且つ簡便に除去する石炭の化学脱硫方法に関する。[Detailed description of the invention] [Industrial application field] This invention is released into the atmosphere as sulfur oxides during the combustion of coal and contained in coal, which is one of the main causes of environmental destruction. The present invention relates to a method for the chemical desulfurization of coal which effectively, economically and easily removes the sulfur content.
石炭中に存在する硫黄分には，無機性硫黄分と有機性
硫黄分とがあり，それらを除去するため，種々の物理的
脱硫法及び化学反応を用いる化学的脱硫法が開発されて
いる。The sulfur content in coal includes inorganic sulfur content and organic sulfur content, and various physical desulfurization methods and chemical desulfurization methods using chemical reactions have been developed to remove them.
例えば，無機性硫黄分（主に，パイライト）と石炭と
の比重差を利用する物理的脱硫法，酸素又は空気の存在
下で，炭酸ソーダ，生石灰，第一硫酸鉄等と石炭を加熱
する酸化的化学脱硫法，苛性ソーダと苛性カリ混合物と
石炭とを400℃で加熱溶融，或いは，マイクロウェーブ
を照射する脱硫法等の約14種類の化学脱硫法が，現在既
に開発されている。For example, a physical desulfurization method using the specific gravity difference between inorganic sulfur (mainly pyrite) and coal, oxidation by heating coal with sodium carbonate, quicklime, ferrous sulfate, etc. in the presence of oxygen or air Approximately 14 types of chemical desulfurization methods have already been developed, such as a chemical desulfurization method, a method of heating and melting a mixture of caustic soda, caustic potash and coal at 400 ° C., or a microwave irradiation method.
ところで，これらの石炭の脱硫方法は，その脱硫効率
及び経済性において必ずしも満足できるものでない。特
に，石炭から有機性硫黄分を除去することが困難であ
り，物理的脱硫法では，殆ど，不可能であると考えられ
ていることから，脱硫効率が高く，経済性の高い化学的
脱硫法の開発が望まれている。By the way, these coal desulfurization methods are not always satisfactory in their desulfurization efficiency and economy. In particular, it is difficult to remove organic sulfur from coal, and it is considered that physical desulfurization is almost impossible. Therefore, the desulfurization efficiency is high and the economical chemical desulfurization is highly economical. The development of is desired.
本発明の目的は，上記の問題点を解決するものであ
り，石炭を，酸素ガス，或いは空気の存在下で，苛性ア
ルカリ水溶液と処理することにより，高収率で且つ経済
的に石炭から硫黄分を除去することができる石炭の化学
脱硫方法を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems. By treating coal with an aqueous caustic solution in the presence of oxygen gas or air, a high yield and economical production of sulfur from coal is achieved. It is an object of the present invention to provide a method for chemical desulfurization of coal capable of removing coal.
この発明は，上記の目的を達成するため，次のように
構成されている。即ち，この発明は，粉砕した石炭に苛
性ソーダ又は苛性カリをそれぞれ単独又はそれらの混合
物の水溶液を混合し，酸素ガス，空気又はそれらの混合
物雰囲気下で,250℃〜400℃の温度範囲の温度で石炭水
溶液を加熱反応させ，石炭中の硫黄分を石炭から除去す
ることを特徴とする石炭の化学脱硫方法に関する。The present invention is configured as follows to achieve the above object. That is, the present invention relates to a method of mixing a pulverized coal with an aqueous solution of caustic soda or caustic potash alone or a mixture thereof and subjecting the coal to a temperature of 250 to 400 ° C in an atmosphere of oxygen gas, air or a mixture thereof. The present invention relates to a method for chemically desulfurizing coal, which comprises reacting an aqueous solution with heat to remove sulfur content from coal.
即ち，この発明による石炭の化学脱硫方法は，酸素ガ
ス又は空気を酸化剤として用い石炭中に存在する硫黄分
を全て４個の硫黄酸化物に変えて化学反応性を向上させ
た後に,250〜400℃，好ましくは,370℃で苛性ソーダ又
は苛性カリ又は，それらの混合物の水溶液で処理し，硫
黄分を水に可溶な亜硫酸塩及び硫酸塩として分解し，除
去することを特徴とする。That is, the method for chemically desulfurizing coal according to the present invention uses oxygen gas or air as an oxidizing agent to change all the sulfur present in the coal into four sulfur oxides to improve the chemical reactivity. It is characterized by treating with an aqueous solution of caustic soda or caustic potassium or a mixture thereof at 400 ° C., preferably 370 ° C., and decomposing and removing sulfur content as water-soluble sulfites and sulfates.
この発明は，高収率で石炭中の硫黄分を除去できるこ
との他に，酸化剤として，安価で取り扱いの容易な酸素
ガス又は空気を用いていることであり，しかも，引き続
く苛性アルカリとの分解反応を水溶液下で行なうことが
でき，更には，これらの逐次の反応を同一反応容器中
で,1段階のプロセスとして簡略化できる点にある。The present invention, in addition to being able to remove the sulfur content in coal at a high yield, uses oxygen gas or air which is inexpensive and easy to handle as an oxidizing agent, and furthermore, has the following decomposition with caustic. The reaction can be performed in an aqueous solution, and further, these successive reactions can be simplified as a one-step process in the same reaction vessel.
また，この発明は，石炭中の有機硫黄分を，全て４価
の硫黄酸化物に酸化してから苛性アルカリとの分解反応
を行なうために，従来法に見られた炭種による脱硫効率
の変化，特に，芳香族化の進んだ石炭に対する著しい脱
硫効率の低下を抑えることができ，幅広い炭種の石炭に
対して適用できるものである。In addition, the present invention oxidizes the organic sulfur content of coal into tetravalent sulfur oxides and then carries out a decomposition reaction with caustic alkali. In particular, it is possible to suppress a remarkable decrease in the desulfurization efficiency of coal with advanced aromatization, and it can be applied to coal of a wide variety of coal types.
従って，この発明に使用する石炭は，亜炭から無煙炭
までの何れの炭種のものでも良く，好ましくは,20〜200
メシュ或いはそれ以下の粒度に粉砕した石炭が原料とし
て供される。Therefore, the coal used in the present invention may be of any coal type from lignite to anthracite, preferably from 20 to 200
Coal pulverized to a mesh or smaller size is provided as a raw material.
この発明に使用する酸素源は，市販の酸素ガス，空
気，或いはその混合物が用いられ，酸素ガスの場合に
は,1〜30気圧，好ましくは,15気圧であり，空気の場合
には,1〜100気圧，好ましくは,50気圧に加圧することに
よりその目的を達成し得るものである。As the oxygen source used in the present invention, commercially available oxygen gas, air, or a mixture thereof is used. In the case of oxygen gas, the pressure is 1 to 30 atm, preferably 15 atm, and in the case of air, 1 to 30 atm. The purpose can be achieved by increasing the pressure to 100 atm, preferably 50 atm.
この発明に使用する苛性アルカリ水溶液は，苛性ソー
ダ，苛性カリ，或いはそれらのものを用い,0.5〜10規
定，好ましくは,5規定の濃度に調製したものが用いられ
る。As the aqueous caustic solution used in the present invention, caustic soda, caustic potash, or a mixture thereof is used, which is adjusted to a concentration of 0.5 to 10N, preferably 5N.
この発明による石炭の化学脱硫方法において，アルカ
リ水溶液による分解反応は，反応混合物を250〜400℃，
好ましくは,370℃に直接加熱して行なわれるものであ
る。In the chemical desulfurization method for coal according to the present invention, the decomposition reaction with the aqueous alkali solution is performed by heating the reaction mixture at 250 to 400 ° C
Preferably, it is carried out by directly heating to 370 ° C.
この発明による石炭の化学脱硫方法は，褐炭，及びれ
き青炭の場合，含有されている全硫黄分の92〜96％を除
去することができる。この石炭の化学脱硫方法の作用機
構については，定かでないが，石炭に対するアルカリ水
溶液の高い親和力に加えて，酸素ガス分子の石炭固相中
への拡散，浸透が容易なため，石炭中に埋没している硫
黄原子に対する酸化反応の選択性が著しく向上したため
と考えられる。The method for chemically desulfurizing coal according to the present invention can remove 92 to 96% of the total sulfur content of brown coal and bituminous coal. The mechanism of action of this method of chemical desulfurization of coal is unknown, but in addition to the high affinity of the aqueous alkali solution for coal, the diffusion and penetration of oxygen gas molecules into the solid phase of coal is easy, so the coal is buried in coal. It is considered that the selectivity of the oxidation reaction to the sulfur atom is significantly improved.
以下，この発明による石炭の化学脱硫法の実施例につ
いて説明する。Hereinafter, examples of the chemical desulfurization method for coal according to the present invention will be described.
−実施例１− 攪拌機付き200mlオートクレーブに，乾燥して20メシ
ュ以下に粉砕した全硫黄分3.13重量％のイリノイ炭を2
0.0g,及び,5規定の苛性ソーダ水溶液を130mlを取り，酸
素ガスを15kg/cm2Gに加圧する。これらを攪拌しながら
加熱器により内容物を370℃まで昇温した後に，その温
度で30分間保持する。これを冷却した後，反応容器内の
圧力を常圧に戻し，次いで，内容物を水洗しながら取り
出し，その懸濁液に炭酸ガスを吹き込んで中和し，少量
の塩酸で弱酸性にする。生成してくる沈殿物を濾過し，
十分な量の蒸留水で洗浄した後に，これを110℃で３時
間減圧して乾燥する。得られた精製石炭17.3g中の全硫
黄分は,0.21重量％であった。即ち，イリノイ炭に対す
る脱硫率は,93.1％であった。Example 1 In a 200 ml autoclave equipped with a stirrer, dried and ground to 20 mesh or less, Illinois coal having a total sulfur content of 3.13% by weight was added.
Take 0.0 g and 130 ml of 5N caustic soda aqueous solution, and pressurize oxygen gas to 15 kg / cm 2 G. The contents are heated to 370 ° C. by a heater while stirring them, and then kept at that temperature for 30 minutes. After cooling, the pressure in the reaction vessel is returned to normal pressure, and then the contents are taken out while washing with water, and the suspension is neutralized by blowing carbon dioxide gas thereto, and made weakly acidic with a small amount of hydrochloric acid. The resulting precipitate is filtered,
After washing with a sufficient amount of distilled water, it is dried under reduced pressure at 110 ° C. for 3 hours. The total sulfur content in 17.3 g of the obtained refined coal was 0.21% by weight. That is, the desulfurization rate for Illinois coal was 93.1%.
−実施例２− 攪拌機付き200mlオートクレーブに，乾燥して20メシ
ュ以下に粉砕した全硫黄分4.55重量％のピッツバーグ炭
を20.0g,及び,2規定の苛性カリ水溶液を130mlを取り，
酸素ガスを15kg/cm2Gに加圧する。これらを攪拌しなが
ら加熱器により内容物を370℃まで昇温した後に，その
温度で60分間保持する。これを冷却した後，反応容器内
の圧力を常圧に戻し，次いで，内容物を水洗しながら取
り出し，その懸濁液に炭酸ガスを吹き込んで中和し，少
量の塩酸で弱酸性にする。生成してくる沈殿物を濾過
し，十分な量の蒸留水で洗浄した後に，これを110℃で
３時間減圧して乾燥する。得られた精製石炭16.4g中の
全硫黄分は,0.18重量％であった。即ち，ピッツバーグ
炭に対する脱硫率は,96.1％であった。Example 2 In a 200 ml autoclave equipped with a stirrer, 20.0 g of Pittsburgh charcoal having a total sulfur content of 4.55% by weight and dried and pulverized to 20 mesh or less, and 130 ml of a 2N aqueous solution of potassium hydroxide, were taken.
Oxygen gas is pressurized to 15 kg / cm 2 G. The contents are heated to 370 ° C. by a heater while stirring them, and then kept at that temperature for 60 minutes. After cooling, the pressure in the reaction vessel is returned to normal pressure, and then the contents are taken out while washing with water, and the suspension is neutralized by blowing carbon dioxide gas thereto, and made weakly acidic with a small amount of hydrochloric acid. The resulting precipitate is filtered, washed with a sufficient amount of distilled water, and dried under reduced pressure at 110 ° C. for 3 hours. The total sulfur content in the obtained 16.4 g of refined coal was 0.18% by weight. That is, the desulfurization rate for Pittsburgh coal was 96.1%.
−実施例３− 攪拌機付き200mlオートクレーブに，乾燥して20メシ
ュ以下に粉砕した全硫黄分3.47重量％のウエストケンタ
ッキー炭を20.0g,及び,5規定の苛性ソーダ水溶液を130m
lを取り，空気を80kg/cm2Gに加圧する。これらを攪拌し
ながら加熱器により内容物を370℃迄昇温した後に，そ
の温度で60分間保持する。これを冷却した後に，反応容
器内の圧力を常圧に戻し，次いで，内容物を水洗しなが
ら取り出し，その懸濁液に炭酸ガスを吹き込んで中和
し，少量の塩酸で弱酸性にする。生成してくる沈殿物を
濾過し，十分な量の蒸留水で洗浄した後に,110℃で３時
間減圧して乾燥する。得られた精製石炭15.7g中の全硫
黄分は,0.24重量％であった。即ち，ウエストケンタッ
キー炭に対する脱硫率は,94.1％であった。Example 3 In a 200 ml autoclave equipped with a stirrer, 20.0 g of West Kentucky charcoal having a total sulfur content of 3.47% by weight and dried and pulverized to 20 mesh or less, and 130 m of a 5 N caustic soda aqueous solution were added.
Take l and pressurize the air to 80 kg / cm 2 G. The contents are heated to 370 ° C. by a heater while stirring them, and then maintained at that temperature for 60 minutes. After cooling, the pressure in the reaction vessel is returned to normal pressure, and then the contents are taken out while washing with water, and the suspension is neutralized by blowing carbon dioxide gas thereto, and made weakly acidic with a small amount of hydrochloric acid. The resulting precipitate is filtered, washed with a sufficient amount of distilled water, and dried under reduced pressure at 110 ° C. for 3 hours. The total sulfur content in 15.7 g of the obtained refined coal was 0.24% by weight. That is, the desulfurization rate for West Kentucky coal was 94.1%.
−比較例− 比較例は，従来法のAmes法であり，石炭を炭酸ソーダ
水溶液中で，酸素の存在下で,150℃で過熱し，脱硫を行
なったものである。-Comparative Example-The comparative example is a conventional Ames method, in which coal is heated in an aqueous solution of sodium carbonate at 150 ° C in the presence of oxygen to perform desulfurization.
以下に，この発明による石炭から硫黄分を除去する化
学脱硫法と，従来法による比較例との比較を，第１表及
び第２表に示す。Tables 1 and 2 show a comparison between the chemical desulfurization method for removing sulfur from coal according to the present invention and a comparative example according to the conventional method.
〔発明の効果〕 この発明による石炭の化学脱硫方法は，上記のように
構成されているので，石炭中に含有されている硫黄分を
高収率で経済的に除去することが可能になり，それによ
って，石炭の燃焼によって排出される排気ガス中に含ま
れる硫黄酸化物による環境汚染の問題を解決することが
でき，環境汚染防止に著しく貢献できるものである。 [Effects of the Invention] Since the method for chemically desulfurizing coal according to the present invention is configured as described above, it becomes possible to economically remove sulfur contained in coal with high yield, As a result, the problem of environmental pollution due to sulfur oxides contained in the exhaust gas discharged by the combustion of coal can be solved, and can significantly contribute to the prevention of environmental pollution.
Claims (1)
それぞれ単独又はそれらの混合物の水溶液を混合し，酸
素ガス，空気又はそれらの混合物雰囲気下で,250℃〜40
0℃の温度範囲の温度で石炭水溶液を加熱反応させ，石
炭中の硫黄分を石炭から除去することを特徴とする石炭
の化学脱硫方法。An aqueous solution of caustic soda or caustic potash alone or a mixture thereof is mixed with pulverized coal, and the mixture is heated at 250 ° C. to 40 ° C. in an atmosphere of oxygen gas, air or a mixture thereof.
A method for chemical desulfurization of coal, characterized in that a coal aqueous solution is heated and reacted at a temperature in a temperature range of 0 ° C to remove sulfur content in the coal from the coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2077990A JP2805372B2 (en) | 1990-03-26 | 1990-03-26 | Coal chemical desulfurization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2077990A JP2805372B2 (en) | 1990-03-26 | 1990-03-26 | Coal chemical desulfurization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03275795A JPH03275795A (en) | 1991-12-06 |
| JP2805372B2 true JP2805372B2 (en) | 1998-09-30 |
Family
ID=13649271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2077990A Expired - Fee Related JP2805372B2 (en) | 1990-03-26 | 1990-03-26 | Coal chemical desulfurization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2805372B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05311183A (en) * | 1992-05-11 | 1993-11-22 | Idemitsu Kosan Co Ltd | Chemical desulfurization of coal |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2620664A1 (en) * | 1975-05-12 | 1976-12-02 | Battelle Memorial Institute | CARBONATE TREATMENT OF COAL |
| US4213765A (en) * | 1979-01-02 | 1980-07-22 | Union Carbide Corporation | Oxidative coal desulfurization using lime to regenerate alkali metal hydroxide from reaction product |
-
1990
- 1990-03-26 JP JP2077990A patent/JP2805372B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03275795A (en) | 1991-12-06 |
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