CN1370732A - 由固体碳和水生产氢气的方法和系统 - Google Patents
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Abstract
公开了一种由固体碳物质和进料水产生氢气的方法和系统,包括电弧等离子体反应器(APR),该电弧等离子体反应器具有电弧放电电极和装在等离子反应器中的固体碳物质形成的许多细小的电弧通道(35)。在等离子反应器中将进料水转变成水蒸气,并将水蒸气通入细小的电弧通道,在这些电弧通道中在电弧等离子体存在下水蒸气与固体碳物质反应生成富氢气体。
Description
发明背景
1.发明领域
本发明涉及生产氢气的方法和系统,更确切地说,涉及生产用作化工原料和用于各种用途的燃料的富氢气体的方法和系统。
2.相关技术的描述
人们对从水或天然气经过水蒸气转化生产氢气的方法已经进行了广泛的研究和开发。
美国专利5,030,661公开了一种将天然气转化成氢气的水蒸气转化方法。在这个现有技术方法中,使用天然气作为原料大大地增加了氢气的生产成本。此外,由于水蒸气转化过程需要大尺寸的加热炉,这种加热炉消耗了大量的能源。因此,制氢装置的尺寸很大,结果在生产装置的操作中步骤复杂,操作费用明显提高。另外,加热炉会排出大量的CO2,CO2是全球变热的主要原因。
美国专利5,159,900公开了一种使用相对的碳电极之间在水下电弧放电的方法的制氢系统。在该系统中,电弧放电区域被限制在相对电极的明显边缘之间非常小的区域内,因此,仅有非常少量的水蒸气与碳反应以非常低的产品收率生成富氢气体。
美国专利5,513,600公开了一种用于生产氢气和氧气的、包括许多相对电极的电解质反应器。在这种反应器结构中,大量的氢气泡和氧气泡被粘在电极表面,结果降低了水与电极表面的有效接触,从而降低了电解质反应器的操作效率。
美国专利5,690,902公开了一种使用装有铁粉的管子的制氢设备。在该设备中,虽然高温水与铁粉表面接触引起金属表面氧化,从而产生氢气,但是在水与铁粉反应期间铁表面形成了氢氧化铁,导致反应效率降低。
因此,现有技术的制氢方法和系统的效率都非常低,从现场和需求的角度看它都极其难以非常低的成本生产氢气。
发明概述
因此,本发明的目的是提供一种以最高效和非常低的成本从低成本的固体碳物质和水大量生产氢气的方法和系统。
根据本发明的一个方面,提供了从固体碳物质和进料水生产氢气的方法,该方法包括步骤:准备一个具有等离子反应室和位于该反应室中的电弧电极的电弧等离子体反应器;将固体碳物质放入反应室,并在固体碳物质中形成许许多多细小的电弧通道;给电弧电极分别供电以在细小的电弧通道中生产电弧放电等离子体;将水蒸气通过细小的电弧通道,使水蒸气与固体碳物质在电弧放电等离子体存在下反应,生成富氢气体。
根据本发明的另一个方面,提供了一种制氢系统,该系统包括:具有固体碳供给口、进料水供给口,具有合成气出口的隔离套管,在隔离套管中形成的电弧等离子体室,位于电弧等离子体室一端的交流电弧电极,位于电弧等离子体室另一端的中性电极,和在电弧等离子体室中装有的固体碳物质形成的许多细小的电弧通道的电弧等离子体反应器;通过进料水供给口将进料水供给电弧等离子体室的进料水供给泵,使进料水转变成水蒸气;向电弧电极供给交流电电能的交流电电源,以在细小的电弧通道中分别产生电弧放电等离子体,从而使水暴露于电弧放电等离子体中形成水蒸气,该水蒸气在经过细小的电弧通道时与固体碳物质反应产生富氢气体。
附图简要说明
通过参考下面对优选实施方案和附图的描述,可以更好地理解本发明、及其目的和优点,其中:
图1是按照本发明方法进行的制氢系统的示意图;和
图2是图1所示的电弧等离子体反应器的放大的横断面视图。
优选实施方案的详述
关于附图,图1显示了进行本发明方法的本发明优选实施方案的制氢系统10。
在图1中,制氢系统10由下列设备组成:固体碳加料装置12,该装置提供固体碳物质如粒状、颗粒、粉末状或球形石墨物质,活性碳物质或煤炭,供给进料水的供水泵P1,在水蒸气存在下将固体碳颗粒转化成富氢气体的电弧等离子体反应器APR,位于电弧等离子体反应器APR下游侧的用于冷却富氢气体同时预热循环水的换热器H,与换热器H连接用于进一步冷却富氢气体的冷却装置C,用于分离富氢气体和冷凝水的液/气分离器S,循环管线19,循环泵P2,关闭阀V1-V5,和用于除去富氢气体中所含的杂质如CO和CO2的第一和第二反应器15和17。液/气分离器S用于从富氢气体分离出冷凝水,使冷凝水通过循环管线19和循环泵P2作为循环水循环到电弧等离子体反应器APR。
图2显示了图1中所示的电弧等离子体反应器APR的详细结构。在图2中,电弧等离子体反应器APR包括与固体碳加料装置12连接的电弧反应器装置14,和电弧电源16。固体碳加料装置12由储存固体碳物质的进料斗20、螺旋进料机22和以预定的进料量连续供给固体碳粒子的旋转阀24组成。热反应器装置14包括由耐热陶瓷制成的圆筒形的外隔离套管26,和具有圆筒形等离子体反应室34的内部隔离套管32。绝缘电极支持物28通过固定螺栓30与内部绝缘套管32的上端连接在一起。等离子体反应室34具有由水蒸气产生区34A形成的上游侧和由富氢气体产生区34B形成的下游侧。实际上,富氢气体产生区34B占据了等离子体反应室34的较大部分。当固体碳颗粒供给等离子体反应室34时,在固体碳物质之间以缝隙的形式形成了许多细小的电弧通道35,通过这些细小的电弧通道35在作为等离子气体的水蒸气存在下由于均匀的电火花产生了许多电弧等离子体。此时,进料水暴露于水蒸气产生区34A的高温下,并转变成水蒸气流。水蒸气流通过大量的细小电弧通道35流向下游侧。在水蒸气流流动期间,在电弧等离子体存在下根据下列反应式水蒸气与固体碳物质反应形成了含有氢气、一氧化碳和二氧化碳的富氢气体:
富氢气体中的氢含量是根据反应室34中的操作温度变化的。也就是说,当反应室34的反应温度提高时,富氢气体中的氢含量增加。
绝缘电极支持物28支持着许多棒状电弧电极36,38,40。环状圆盘形中性电极42位于绝缘套管32的下部。中性电极42有一个锥形面42a和一个中心孔42b。装入中性电极42并用在绝缘套管26底部形成的电极支持物78支撑和用固定螺栓80就地固定。另一方面,电极支持物28具有一个与固体碳加料装置12连接的碳进料口50。外面的绝缘套管26的上部有一个在电弧电极36,38,40的上面区域附近形成的进料水进料口52以便将进料水引入水蒸气产生区34A。这有利于进料水作为冷却剂来防止电极36,38,40的温度升得过高,并且有利于进料水有效地转变为作为等离子气体的水蒸气,以便促进在合成气产生区35中产生电弧等离子体。内套管32和中性电极42的外围形成有由环状冷却剂通道54组成的冷却和热回收区63,相邻的冷却剂通道通过中间通道54相互连接。外绝缘套管26有一个进口74和一个出口76,该进口和出口通过冷却剂通道54彼此连通。由螺栓80经密封板83连接到电极支持物78上的是绝缘端板82。中性电极42和端板82分别具有同心孔42b和82a,其中合成气从过滤器84中穿过。端板82具有一个合成气出口86。
进口74连接到进料水管线11,出口76连接到进料水进料口52。进料水在冷却区63预热并从出口76排出进入进料水进料口52。然后将进料水引入水蒸气产生区34A形成由水蒸气组成的等离子气体。从出口86排出的一部分富氢气体通过再循环管道(未画出)循环到等离子体反应室34中,在等离子体反应室34中水以上述化学反应式(2)所示的方式发生转移反应。代号88表示密封部件。
在图2中,电极支持物28固定地支撑交流电三相电极36,38,40,这些电极提供有来自电弧电源16的交流三相电力。中性电极42与三相电弧电源16的中点连接,电源16提供了输出频率为10-60赫兹、输出电压为30-240伏特的电能。
现在再回到图1,第一反应器15由一对反应器150,150’组成,它们通过关闭阀V2-V5交替操作。每一个反应器150,150’装有活性炭颗粒150a和由钴/钼催化剂组成的一氧化碳转化催化剂150b,该催化剂由Nikki化学有限公司以″N938″的名称销售的,该催化剂可将CO转化成CO2。第二反应器由CO2吸收塔组成,该CO2吸收塔包括高压吸收反应器和低压吸收反应器,比如已知的PSA(压力回转吸收),这两种反应器都装有活性炭颗粒以吸收剩余的CO和CO2,从而生产高纯度的氢气H2。CO2及收塔17可装有二氧化碳吸收剂,其公开在日本专利临时公开号11-244652中。
在运行中,将三相电弧放电电力提供给电弧等离子体反应器APR的三相电弧电极36,38,40,同时驱动螺旋进料机22和旋转阀24,将固体碳物质加到电弧等离子体反应器APR中。然后,驱动进料水供给泵P1,将进料水从进料水进料口52供给等离子体反应室34的水蒸气产生区34A,进料水经受高温产生作为等离子气体的水蒸气。水蒸气流过许多细小的等离子体通道35,水蒸气与固体碳物质在高于1000℃的温度下反应,转化成富氢气体。富氢气体在换热器H中冷却,然后在冷却器C中进一步冷却至60-90℃。将如此冷却的富氢气体提供给液/气分离器S,在分离器S中从富氢气体中分离出水份以产生冷凝水。当冷凝水达到给定高度时,驱动泵P2将冷凝水供给进料水供给管线11,与新鲜进料水混合。在电弧等离子体反应器APR的冷却区63预热混合水,然后提供给进料水供给口52。然后将干的富氢气体送入第一和第二反应器15和17以上述方式除去杂质如CO和CO2,产生纯化的氢气H2。
本发明的系统和方法与现有技术相比提供了许多优点,包括:
(1)可使用成本非常低的进料水和固体碳物质作为原料,从而使氢气的生产费用明显降低。
(2)所用的电弧等离子体反应器的结构小,但具有高的操作性能,能够从低成本的固体碳物质和进料水有效生产富氢气体。
(3)因为全部的固体碳物质仅消耗于生产富氢气体,而不象现有技术中所要求的那样碳物质作为燃料用于转化炉,因此,碳物质的利用率是非常高的,从而使富氢气体的生产成本明显降低。
(4)在现有技术中,将在富氢气体通过使用水蒸气转化方法生产期间得到的冷凝水排到外面,造成环境污染。相反,本发明的方法和系统可将冷凝水作为循环水循环到电弧等离子体反应器APR,结果使进料水的量明显减少,同时,消除了环境污染。
虽然已经详细描述了本发明的具体实施方案,但是本领域的技术人员都将理解,根据公开内容的全部教导可以对那些细节内容进行各种修改和替换。因此,公开的具体实施方案仅仅是说明性的,并且不限于附加的权利要求中所定义的发明范围。
Claims (5)
1.一种由固体碳物质和进料水生产氢的方法,包括步骤:
准备一个具有等离子反应室和位于该反应室中的电弧放电电极的电弧等离子体反应器;
将固体碳物质供入反应室,并在固体碳物质中形成大量细小的电弧通道;
给电弧放电电极分别供电以在所述细小的电弧通道中生产电弧放电等离子体;和
将水蒸气通过细小的电弧通道,使水蒸气与固体碳物质在电弧放电等离子体存在下反应,生成富氢气体。
2.根据权利要求1的方法,其中热等离子体反应器具有由水蒸气产生区形成的上游侧和由富氢气体产生区形成的下游侧,并还包括步骤:
将进料水供给电弧等离子体反应器的水蒸气产生区,在其上游侧形成水蒸气;
在氢气产生区中在电弧放电等离子体存在下水蒸气与固体碳物质反应,产生富氢气体;
冷却富氢气体以分离出冷凝水;和
循环冷凝水至水蒸气产生区以转变成水蒸气。
3.根据权利要求1或2的方法,还包括步骤:
从富氢气体分离出含CO和CO2的杂质。
4.一种制氢系统,包括:
具有固体碳供给口、进料水供给口,具有合成气出口的绝缘套管,在绝缘套管中形成的电弧等离子体室,位于电弧等离子体室一端的交流电弧放电电极,位于电弧等离子体室另一端的中性放电电极,和在电弧等离子体室中装有的固体碳物质形成的许多细小的电弧通道的电弧等离子体反应器;
通过进料水供给口将进料水供给电弧等离子体室的进料水供给泵,使进料水转变成水蒸气;和
向电弧电极供给交流电电能的交流电电源,以在细小的电弧通道中分别产生电弧放电等离子体,从而使水暴露于电弧放电等离子体中形成水蒸气,该水蒸气在经过细小的电弧通道时在电弧放电等离子体存在下与固体碳物质反应产生富氢气体。
5.根据权利要求4的制氢系统,还包括:
与电弧等离子体反应器连接的液/气分离器装置,用于分离富氢气体和冷凝水;和
用于将冷凝水循环到电弧等离子体反应器以形成富氢气体的循环管线。
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JP2001059208A JP2002226201A (ja) | 2001-01-29 | 2001-01-29 | 水素の製造法およびその装置 |
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Cited By (3)
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CN102009949A (zh) * | 2010-09-28 | 2011-04-13 | 周开根 | 一种用水产生气化剂的方法 |
CN102343245A (zh) * | 2010-07-01 | 2012-02-08 | 麦格尼磁分子技术(北京)有限公司 | 一种液下电弧发生装置及方法 |
CN108698818A (zh) * | 2016-02-25 | 2018-10-23 | 通用电气航空系统有限责任公司 | 固体氢反应系统和氢气放出方法 |
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CA2424805C (en) * | 2003-04-04 | 2009-05-26 | Pyrogenesis Inc. | Two-stage plasma process for converting waste into fuel gas and apparatus therefor |
FR2874023B1 (fr) * | 2004-08-04 | 2007-06-08 | Commissariat Energie Atomique | Procede de fabrication d'un gaz combustible par action d'un plasma immerge sur de la matiere organique en milieu aqueux |
DE102006007458B4 (de) * | 2006-02-17 | 2010-07-08 | Native Power Solutions Gmbh & Co. Kg | Verfahren und Vorrichtung zum Vergasen von kohlenstoffhaltigem Material sowie Vorrichtung zur Erzeugung von elektrischer Energie |
DE102006007457B4 (de) * | 2006-02-17 | 2007-12-27 | Native Power Solutions Gmbh & Co. Kg | Verfahren und Vorrichtung zum Erzeugen von Gas aus kohlenstoffhaltigem Material |
ES2317728B1 (es) * | 2006-04-19 | 2010-02-09 | Antonio Victor De La Vega Montero | Metodo de obtencion de hidrogeno por disociacion de agua. |
KR100861004B1 (ko) | 2006-12-18 | 2008-09-30 | 조선대학교산학협력단 | 합성 가스 생성용 글라이드 아크 플라즈마 개질장치 및 연료 개질방법 |
KR101594350B1 (ko) * | 2015-06-30 | 2016-02-16 | 주식회사 윈테크에너지 | 스팀 플라즈마를 이용한 수소 제조장치 및 수소 제조방법 |
CN109110730B (zh) * | 2018-09-11 | 2020-06-09 | 浙江工业职业技术学院 | 用于新能源汽车的动力制取装置 |
KR102252636B1 (ko) * | 2019-05-14 | 2021-05-18 | 주식회사 에이아이코리아 | 수소 정제 시스템 |
KR102262103B1 (ko) * | 2019-05-14 | 2021-06-09 | 주식회사 에이아이코리아 | 플라즈마 장치를 포함하는 개질 시스템 |
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US4181504A (en) * | 1975-12-30 | 1980-01-01 | Technology Application Services Corp. | Method for the gasification of carbonaceous matter by plasma arc pyrolysis |
BR7902079A (pt) * | 1979-04-04 | 1980-10-21 | E Oliveira | Processo para sintese do metanol |
CH646992A5 (de) * | 1980-02-26 | 1984-12-28 | Maurer A Ing Sa | Verfahren zur kontinuierlichen thermischen behandlung von verkohlbarem ausgangsmaterial. |
SE8201263L (sv) * | 1982-03-01 | 1983-09-02 | Skf Steel Eng Ab | Sett och anleggning for forgasning av kolhaltigt material |
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2001
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102343245A (zh) * | 2010-07-01 | 2012-02-08 | 麦格尼磁分子技术(北京)有限公司 | 一种液下电弧发生装置及方法 |
CN102009949A (zh) * | 2010-09-28 | 2011-04-13 | 周开根 | 一种用水产生气化剂的方法 |
CN102009949B (zh) * | 2010-09-28 | 2013-03-20 | 周开根 | 一种用水产生合成气的方法 |
CN108698818A (zh) * | 2016-02-25 | 2018-10-23 | 通用电气航空系统有限责任公司 | 固体氢反应系统和氢气放出方法 |
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JP2002226201A (ja) | 2002-08-14 |
EP1227142A3 (en) | 2002-08-07 |
US20020100215A1 (en) | 2002-08-01 |
EP1227142A2 (en) | 2002-07-31 |
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