CN1768126A - 从高硫煤中除去有机硫的方法及其设备 - Google Patents
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Abstract
本发明涉及从高硫煤中减少有机硫的设备及其方法,该设备包括管状炉,该管状炉由硅线石构成并以石英毛保温,管状炉有三个加热区,即蒸汽加热区、反应区和促进区,其中促进区(含有促进剂)的温度在1100±50摄氏度的温度范围内,蒸汽区的温度在400至500摄氏度的温度范围内。
Description
技术领域
本发明涉及从高硫煤中除去有机硫的方法及其设备。
本发明的用途适合于热煤电厂的发电、制造煤砖(briquette making)、活性炭和减少污染。
背景技术
煤中含有硫,这使得煤不适合使用,除非以昂贵和高效的还原设备回收硫的燃烧产物。其中一种燃烧产物是二氧化硫,它被认为是高度不受欢迎的大气污染物。一般认为煤中的硫以不同形式存在。共有三种基本的形式,即:黄铁矿硫、硫酸盐硫和有机硫。黄铁矿硫是与铁结合的硫。硫酸盐硫的量一般很少,即在给定的煤样品中,它通常在所有的硫中占1%或2%。有机硫是与煤中的碳相结合形成有机化合物的硫。一般会发现有机硫很难从煤中除去。在美国专利No.4233034中称,大部分研究者所面对的问题是如何从煤中除去有机硫。该专利公开了一种从煤中除去硫的方法,但此方法没有把有机硫的除去和黄铁矿硫的除去区别开来,所给出的只是对除去的硫不加以区分的除硫工艺。从煤中高效除去黄铁矿硫的方法已为众人所知。问题仍围绕着高效除去有机硫。
可以参考美国专利No.4441886,其中描述了一种从煤中除去有机硫的改进方法。该方法包括多个步骤。含有有机硫的煤被粉碎成颗粒。煤颗粒可以(但并不必需)进行处理以充分除去包含于煤中的全部水,以使煤干燥。然后干煤与选定量的含有小于4%水分的乙醇进行混合。乙醇量要使得在每种情形下煤乙醇混合物中的固体含量都小于61.7重量%。煤与乙醇的混合物放置在反应容器中,把容器的温度和压力升高到乙醇的临界温度和临界压力以上。混合物在临界温度和临界压力之上保持一段时间。收集产生的全部气体,并从液体中分离出混合物的煤固体。以文献纵览和专利数据库为基础,找寻从煤中除去有机硫及其相关设备的现有技术,但是并没有获得任何相关的参考。
发明内容
本发明的主要目的是提供能避免上述缺陷的从高硫煤中除去有机硫的设备。
本发明的另一个目的是提供从高硫煤中除去有机硫的方法。
因此本发明涉及一种使高硫煤中减少有机硫的设备,该设备包括主要由三个加热区组成的反应器,这些加热区比如有能够保持温度在450~500℃范围的蒸汽加热区、能够大约保持温度在950~1100℃范围的促进区和能够保持温度在900~950℃温度范围的反应区,所述反应器放置在能为所述反应器提供上述温度区的平板状炉内,所述内置有反应器的炉子被封闭在一个可移动的柜子中,所述反应器和炉子安装有能量调节器和指示器。
具体实施方式
本发明的一个实施方案涉及其中平板状炉由硅线石(silliminite)构成并以石英毛保温的设备。
本发明的另一个实施方案涉及使用如权利要求1中所要求的设备从高硫煤中除去有机硫的方法,该方法如下步骤:在1100±50摄氏度的范围温度下加热促进区(含有促进剂);在450至500摄氏度范围的温度下加热蒸汽区;把进入的煤碾碎至-72目BS,并加入反应区;在烧瓶中产生蒸汽并通过反应器,该烧瓶优选由玻璃制成;在900摄氏度温度保持约1小时;在蒸汽达到900摄氏度温度后,使由反应器放出的气体通过一系列装有加氨的氯化镉溶液的起泡器,该起泡器优选由玻璃制成;冷却炉子至室温,卸出产物焦煤/焦炭。
本发明的另一实施方案涉及如权利要求2所述的方法,其中所用的促进剂是比例为1∶9的铜铁切屑的混合物。
本发明的另一实施方案涉及如权利要求2和3所述的方法,其中在促进区和反应区的升温速率为每分钟5摄氏度。
在本方法中,促进区先是以5摄氏度温度的速度在950~1000摄氏度范围的温度下加热,蒸汽区是以5摄氏度温度的速度在450~500摄氏度范围的温度下加热。进入的煤被碾碎至-72目BS并加入到反应区。蒸汽在圆底烧瓶中产生并通过反应器。当温度达到900摄氏度时,蒸汽在该温度保持0.5~2小时的一段时间。放出的气体通过一系列装有加氨的氯化镉溶液的玻璃起泡器,在起泡器内形成硫化镉的黄色沉淀。冷却炉子至室温,卸出产物焦煤/焦炭。
附在本说明书的附图中,设备的各种组件为:
1.二氧化硅反应器
2.蒸汽加热区
3.促进区
4.反应区
5.带石英毛的保温体
6.炉子,由硅线石制成
7.带石英毛的保温体
8.嵌入内有反应器的硅线石炉子的框架
本发明提供了一种用于从高硫煤中除去有机硫的设备的方法,该设备包括:管状炉(6),由硅线石制成并以石英毛保温(5&7),外径为250mm,内径为40mm,长度为650mm,管口(tube bore)为37.5mm;反应器(1),优选由二氧化硅制成,它有三个加热区,即i)蒸汽加热区(2),长17mm,用于把温度保持在450至500摄氏度的范围,ii)加热促进区(3),长250mm,用于把温度保持在950至1200摄氏度的范围,iii)反应区(4),长200mm,用于使温度保持在300至1100摄氏度的温度范围;所述炉子装配有两个铬-铝热电耦,带多点开关的数字温度显示器和三个用于控制所述三个区温度的能量调节器(9);所述炉子(6)装配有一些辊,以便在长方形控制柜中安置的轨道上自由移动,在所述炉子中还装有能量调节器和指示器;反应器(1),优选由二氧化硅构成,长度为940mm,内径为21mm,外径为23mm,它嵌入在所述炉子内;框架(8),优选由软不锈钢制成,长度为750mm,宽度为325mm,深度为325mm,以容纳所述内置有二氧化硅反应器(1)的所述炉子。
本发明提供了一种从高硫煤中除去有机硫的方法,该方法包括如下步骤:促进区在300至1100摄氏度范围的温度下加热,蒸汽区在450至500摄氏度范围的温度下加热;把进入的煤碾碎至-72目BS,并加入反应区;蒸汽在烧瓶中产生并通过反应器,该烧瓶优选由玻璃制成;在900摄氏度下保持0.5~2小时的时间段,当蒸汽达到900摄氏度之后,放出蒸汽;从反应器放出的气体通过一系列装有加氨的氯化镉溶液的起泡器,该起泡器最好由玻璃制成;冷却炉子至室温,排出产物焦煤/焦炭。
在本发明的一个实施方案中所用的促进剂是比例为1∶9的铜铁切屑的混合物。
在本发明的另一实施方案中,促进区和反应区的升温速率为每分钟5摄氏度。
本发明的创新之处在于从高硫煤中除去有机硫,在全世界范围内还未利用这种技术。有机硫是与煤中的碳相结合形成有机化合物的硫。一般会发现有机硫很难从煤中除去。二氧化硫被认为是高度不受欢迎的大气污染物。本发明除去煤中的79.77%的硫,这是一项突破。
下面给出的实施例只是用于解释本发明,它不应当认为是对本发明范围的限制。
实施例
实施例1
先以每分钟升高5摄氏度温度把促进区和蒸汽区分别加热到高达1100摄氏度和450摄氏度。把10克煤碾碎至-72目BS,并加入反应区。把9g铁和1g铜的切屑放在促进室中。蒸汽在烧瓶中产生并通过反应器。当炉子温度达到900摄氏度时,蒸汽在该温度下保持1小时。放出的气体通过一系列装有加氨的氯化镉溶液的起泡器,在起泡器内形成硫化镉的黄色沉淀。冷却炉子至室温,卸出产物焦煤/焦炭。初始煤中含有5.39%的有机硫,经过上述过程后,有机硫含量减少到1.17%,因此有机硫总体减少了78.29%。
实施例2
先以5摄氏度的温度升高把促进区和蒸汽区分别加热到高达1000摄氏度和400摄氏度。把10克煤碾碎至-72目BS,并加入反应区。把9g铁和1g铜的切屑放在促进室中。蒸汽在烧瓶中产生并通过反应器。当炉温达到900摄氏度时,蒸汽在该温度下保持1小时。放出的气体通过一系列装有加氨的氯化镉溶液的起泡器,在起泡器内形成硫化镉的黄色沉淀。冷却炉子至室温,排出产物焦煤/焦炭。初始煤中含有5.39%的有机硫,经过上述过程后,有机硫含量减少到0.88%,因此有机硫总体减少了79.77%。
实施例3
先以5摄氏度的温度增加把促进区和蒸汽区分别加热到高达900摄氏度和550摄氏度。把10克煤碾碎至-72目SB,并加入反应区。把9g铁和1g铜的切屑放在催化室中。蒸汽在圆底烧瓶中产生并通过反应器。当炉温达到900摄氏度时,蒸汽在该温度下保持1小时。放出的气体通过一系列装有加氨的氯化镉溶液的起泡器,在起泡器内形成硫化镉的黄色沉淀。冷却炉子至室温,排出产物焦煤/焦炭。初始煤中含有5.39%的有机硫,经过上述过程后,有机硫含量减少到1.51%,因此有机硫总体减少了71.98%。
实施例4
先以5摄氏度的温度增加把促进区和蒸汽区分别加热到高达600摄氏度和400摄氏度。把10克煤碾碎至-72目BS,并加入反应区。把9g铁和1g铜的切屑放在催化室中。蒸汽在圆底烧瓶中产生并通过反应器。当炉温达到900摄氏度时,蒸汽在该温度保持1小时。放出的气体通过一系列装有加氨的氯化镉溶液的起泡器,在起泡器内形成硫化镉的黄色沉淀。冷却炉子至室温,排出产物焦煤/焦炭。初始煤中含有3.24%的有机硫,经过上述过程后,有机硫含量减少到2.32%,因此有机硫总体减少了28.39%。
本发明的主要优点是:
1.本方法非常简单且环境友好。
2.本方法涉及到的材料是最常用的,因而成本低廉。
Claims (6)
1.一种用于减少高硫煤中有机硫的设备,所述设备包括主要由三个加热区组成的反应器,所述加热区比如有能够使温度保持在450~500℃范围的蒸汽加热区、能够使温度约保持在950~1100℃范围的促进区和能够使温度保持在900~950℃温度范围的反应区,所述反应器被放置在能为所述反应器提供上述温度区的管状炉内,所述内置有反应器的炉子被封闭在可移动的柜子中,所述反应器和炉子装备有能量调节器和指示器。
2.如权利要求1所述的设备,其中管状炉由硅线石构成并以石英毛保温。
3.一种用于从高硫煤中除去有机硫的方法,该方法使用如权利要求1-2中所述的设备,所述方法包括如下步骤:在1100±50摄氏度的温度范围加热促进区(含有促进剂),以及在450至500摄氏度范围的温度下加热蒸汽区;将进入的煤碾碎至-72目BS,并加入反应区;蒸汽在烧瓶中产生并通过反应器,所述烧瓶优选由玻璃制成;在蒸汽达到约900摄氏度温度之后,在900摄氏度温度下保持约1小时;从反应器放出的气体通过一系列装有加氨的氯化镉溶液的起泡器,所述起泡器优选由玻璃制成;冷却炉子至室温,放出产物焦煤/焦炭。
4.如权利要求3中所述的方法,其中所用的促进剂是比例为1∶9的铜铁切屑混合物。
5.如权利要求2-4中所述的方法,其中在促进区和反应区的升温速率为每分钟5摄氏度。
6.如权利要求2-5中所述的方法,其中通过所述方法从煤中除去约80%的硫。
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US (1) | US20040244282A1 (zh) |
EP (1) | EP1622995A1 (zh) |
JP (1) | JP2006522201A (zh) |
KR (1) | KR20060006902A (zh) |
CN (1) | CN1768126A (zh) |
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CN114517116A (zh) * | 2022-02-14 | 2022-05-20 | 三门峡市精捷自动化设备有限公司 | 一种低挥发分煤体热蒸冷淬工艺 |
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JP4927020B2 (ja) * | 2008-04-16 | 2012-05-09 | 新日本製鐵株式会社 | 石炭中硫黄の形態別定量方法 |
KR100947556B1 (ko) | 2008-05-16 | 2010-03-12 | 장익병 | 싸이클 헬스카의 증속장치 |
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DE1136979B (de) * | 1955-10-24 | 1962-09-27 | Braunschweigische Kohlen Bergw | Verfahren zum Entschwefeln von Koks |
GB838605A (en) * | 1957-04-04 | 1960-06-22 | Collier Carbon & Chemical Co | Apparatus and method for calcining petroleum coke, coal and similar substances containing volatile combustible material |
US3361538A (en) * | 1964-11-13 | 1968-01-02 | Selas Corp Of America | Tube heater |
US3350845A (en) * | 1965-11-18 | 1967-11-07 | Union Carbide Corp | Metal alloy for hydrogen separation and purification |
GB1492600A (en) * | 1974-01-02 | 1977-11-23 | Occidental Petroleum Corp | Process for treating coal to produce a carbon char of low sulphur content |
US4118201A (en) * | 1976-07-14 | 1978-10-03 | Mobil Oil Corporation | Production of low sulfur fuels from coal |
DE2659752C3 (de) * | 1976-12-31 | 1981-04-23 | L. & C. Steinmüller GmbH, 5270 Gummersbach | Verfahren zum Entschwefeln von auf unter 0,1 mm zerkleinerter Kohle |
US4270928A (en) * | 1978-09-05 | 1981-06-02 | Occidental Research Corporation | Desulfurization of carbonaceous materials |
US4359451A (en) * | 1978-09-05 | 1982-11-16 | Occidental Research Corporation | Desulfurization of carbonaceous materials |
US4233034A (en) * | 1979-05-03 | 1980-11-11 | Union Oil Company Of California | Desulfurization of coal |
US4409094A (en) * | 1980-08-08 | 1983-10-11 | Massachusetts Institute Of Technology | Process for detoxifying coal tars |
US4704134A (en) * | 1981-03-24 | 1987-11-03 | Carbon Fuels Corporation | Coal derived/aqueous fuel system and method of manufacture |
US4441886A (en) * | 1982-11-22 | 1984-04-10 | Southern Illinois University Foundation | Process for removing organic sulphur from coal and material resulting from the process |
US5296007A (en) * | 1986-11-17 | 1994-03-22 | Ensci Inc. | Process for removing sulfur from coal |
US5178785A (en) * | 1990-07-11 | 1993-01-12 | Norton Company | Heat sink formulation |
JPH11226447A (ja) * | 1998-02-12 | 1999-08-24 | Mitsubishi Heavy Ind Ltd | 石炭の脱硫方法および装置 |
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EP1622995A1 (en) | 2006-02-08 |
JP2006522201A (ja) | 2006-09-28 |
KR20060006902A (ko) | 2006-01-20 |
AU2004225664A1 (en) | 2004-10-14 |
WO2004087844A1 (en) | 2004-10-14 |
US20040244282A1 (en) | 2004-12-09 |
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