CN101203455A - 使用钢厂炉渣和废料由热化学分解水制造氢气的装置 - Google Patents
使用钢厂炉渣和废料由热化学分解水制造氢气的装置 Download PDFInfo
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Abstract
一种由水产生氢气的新方法,包括向炉渣和含碳熔料中加入水以通过水的热化学分解制造氢。
Description
发明领域
本发明涉及一种由水产生氢气的新方法。
发明背景
氢正日益成为矿物燃料的最佳替换物。目前,主要使用氢作为原料、中间化学品或规模小的多的作为特种化学品。如今制造出的氢只有一小部分主要是由航天工业用作能量载体。汽车工业正在开发以基于氢的内燃机(ICEs)或汽油-燃料电池汽车为驱动的新模型。然而,并不将绝大部分的商业制氢方法看作是可再生的,因为这些技术仅仅是将污染源从分散的源头(例如汽车、家庭)转移到更加集中的源头,如制氢厂或火电厂。现在,仅美国制氢工业每年就制造九百万吨氢,供化学品制造、石油加工、金属处理和电气应用使用。
当前,利用氢作为燃料的技术比由可再生资源如太阳能、风、潮汐能或地热能高效制造氢的技术处于更加先进的阶段。迫切需要开发更好、更高效并且更廉价的由可再生资源制造氢的技术渡过氢的制造与消耗之间的这种距离,并在二者间达到最佳协同。印度政府的国家氢能路线图也将发展先进的制氢技术和基于氢燃料的技术应用置于突出的位置。
在全世界范围内使用电解法制造氢气。现在,使用这种方法来制造高纯度的氢。用这种方法生产的氢的成本明显更高,因此,其仅用于特种用途如半导体制造。但是,这种方法便于利用可再生资源或核资源制造的电进行更分散的氢制造,并将有助于以最低的分配和存储条件满足本地需求[1]。这种方法的主要副产品是氧。水蒸气-甲烷重整法也广泛用于制氢。在此催化法中,使天然气或其他轻质烃类与蒸汽反应以产生氢和二氧化碳的混合物。然后,将高纯度的氢从产物混合物中分离出来。这种方法是目前可用的能效最高的商业化技术,并且,当应用于大规模、恒负载时,也具有最高的成本效率。在气化器中部分氧化矿物燃料是另一种热制氢的方法。它包括燃料与有限供给的氧反应以产生氢混合物,然后将其提纯。可以将部分氧化法应用于包括天然气、重油、固体生物燃料和煤在内的大范围的烃类原料。其主要的副产品是二氧化碳。新出现的方法有望制造氢而无二氧化碳排放,但这些方法均处于初级开发阶段。一些这样的技术包括利用核能和太阳热的热化学水***(water-splitting),利用固态技术的光解(太阳)法(光电化学、电解),对利用碳鳌合作用(carbonsequestration)的矿物燃料制氢和生物技术(藻类和细菌)。
发明目的
本发明的一个目的是提出一种由水制造氢气的新方法。
本发明的另一个目的是提出一种在有含碳废料和催化熔料(catalyticfluxes)的存在下由水制造氢气的新方法。
本发明的又一个的目的是提出一种由水制造氢气的新方法,其中将熔渣用于水的热化学分解。
本发明的再一个目的是提出一种简单且具有高成本效率的由水制造氢气的新方法。
发明综述
根据本发明,提供一种由水制造氢气的新方法,包括将水加入炉渣和含碳催化熔料中,从而通过水的热化学分解制造氢。
附图简述
通过附图更详细地说明本发明:
图1a说明了基于在1873K下水-炉渣相平衡的计算结果,加入水对炉渣中FeO和Fe2O3的浓度和氢气形成的影响。
图1b涉及基于在1873K(b)下水-炉渣相平衡的计算结果,水-炉渣***相对水加入的焓的曲线图。
图2说明了通过FACT-sage程序计算的水加入对炉渣中FeO和Fe2O3的浓度和H2、CO和CO2形成的影响。
图3说明了制氢的实验装置。
图4说明了在工业级别下,于渣坑中制氢的装置的线路图和示意图。
发明详述
开发了一种新的方法用于在有含碳废料和催化熔料的存在下,通过水和炉渣反应制造氢气。氢气形成的整个反应是:
其中,A为加入***中的水的量,x为熔料中可用的C的量,y为炉渣中的FeO量,z为通过CO与水的反应形成的CO2量。在这个新方法中,炉渣不仅为吸热的水分解反应提供显热,并且阻止氢与氧气之间的逆反应。炉渣中的Fe和Fe的较低氧化物与产物气体混合物中的氧气反应,并形成Fe2O3,从而降低氧的热力学活性。可作为脱氧剂的不同类型废料可用作熔料来提高氢气制造。
在炉渣存在下纯水的热分解:
熔融炉渣的显热可用于水的热化学分解。在该方法中,炉渣作为热源,炉渣中的一些脱氧组分(Fe,FeO)也通过反应(2)与初生态氧反应而参与分解反应(1):
-(1)
-(2)
放热氧化反应提供反应(1)所需的额外能量,并且也降低***的氧分压,从而提高氢气的生成速率。由1600C 100g下LD炉渣与水之间的反应计算相平衡数据。水的量由0变化至100ml以研究水与炉渣的比对产生氢气的影响。计算结果示于图1a和图1b中。图1a说明加入水对氢气形成和炉渣中FeO和Fe2O3浓度变化的影响。不同的水加入下***的焓示于图1b中,其说明100gm炉渣的焓可以支持与至多11.3ml水反应,进一步加入的水则需要额外的能量输入。因此,在1873K的温度下,理论上,1kg炉渣与113ml水的反应将生成0.8摩尔,即19.2升氢气而无须任何能量输入。
在炉渣和含碳熔料存在下纯水的热分解:
可以使用含碳的或其它的工厂废料如粉煤(coal fines)、焦屑等作为会提高由水热化学分解形成氢的脱氧剂。水与碳之间的反应为:
100gm炉渣、<A>ml水和10gm碳的相平衡数据是对1873K计算的,计算结果示于图2中。计算结果表明加入超过碳反应所需化学计量的水提高了氢气的产量。过量的水与***中的CO气体在高温下反应,并生成CO2气体。如果<A>=5.55摩尔(100ml),x=0.20摩尔,则在1873K下形成1.20摩尔H2、0.46摩尔CO和0.37摩尔CO2所需的能量是ΔH1873K=740kJ。1900K下1kg炉渣的焓ΔH1900K=-2120kJ。在1600C下,并使用350mg炉渣的显热,100ml水与10gm碳反应理论上将产生1.20摩尔,即26.9升氢气。(H2O∶C比=10∶1)。因此,1kg炉渣之间的反应g理论上可产生~70升气体。考虑到形成反应的较低效率和热交换过程以及其他动力学限制,实践中,该方法实际可以生成~10升氢气/kg炉渣。
设计和制造了创新的设备(实验室和工厂)用于以钢厂炉渣作为热源的氢气制造。该设计的设备可使用炉渣中的废热有效地收获>35%氢的产物气体。
设计用于研究熔渣和水反应的实验装置示于图3中。如图3所示,在伽该装置进行实验的过程中所遵循的标准程序描述如下:
在开始实验以前,首先使用真空泵(13)排空冷凝器(6)和集气罐(11)以除去剩余空气,并产生负压以使气体流入罐中。实验开始前,通过关闭阀门(6,12)而使***与环境隔绝。在感应炉中融化来自LD钢厂的粒化炉渣并将其过加热至~1650-1700C。将熔渣倾入预热的石墨坩埚(1)中。然后将反应罩(2)(reaction hood)置于坩锅上。将控制量的水从水管线(3)喷洒到熔渣表面上。如前述部分讨论的,通过水、炉渣中的脱氧剂和坩锅中的碳之间的反应形成产物气体。用罩(2)经与罐连接的钢管(4)收集反应生成的产物气体。在实验过程中,从样品口(5)收集产物气体样品用于化学分析。通过开启气体阀门(6)使产物气体流经冷凝罐(7)。通过贮存于外罐(8)中的水冷却冷凝罐(7)。然后,通过打开气流控制阀(9,10)而将去除/反萃取(stripping)蒸汽后的产物气体收集到气体收集罐(11)中。通过将气体取样器分别与阀门(9)和(12)接触来收集冷凝罐和气体收集罐中的气体样品。开启连接在冷凝罐(7)底部的阀门(14)而从冷凝罐(7)中除去冷凝水。
从样品口(5)、冷凝器(7)和收集罐(11)收集的气体样品的典型分析列出如下:
(浓度,体积%)
样品/组分 | H2 | CO | CO2 | O2 | CH4 | CmHn | N2 |
口[5] | 22.8 | 11.2 | 7.0 | 3.0 | 6.2 | 0.6 | 33.4 |
冷凝罐[7] | 23.0 | 1.6 | 1.2 | 1.2 | 2.0 | 1.0 | 70.0 |
收集罐[11] | 20.0 | 1.8 | Nil | 2.0 | 4.0 | 1.2 | 71.0 |
工业测试用装置:
为在LD#2钢厂的渣坑中进行试验而设计并开发的装置示于图4中。遵循的标准程序(逐步)描述如下:
在LD#2炼钢车间(unit)的渣坑中进行实验。简单描述一下LD#2钢罐的堆渣程序。在工厂中,将来自转炉容器(分批式)的炉渣收集到容量为~25吨的渣罐中。然后,通过运渣车(slag trolley)将渣罐运送到堆渣区域。在渣罐车到达堆渣区域后,通过高架起重机从车上取下罐,然后将炉渣倒入渣坑中。约用2天时间填充渣抗。一旦用炉渣填满坑,就冷却炉渣一段时间,然后通过从侧面和顶部喷洒水流而将其急冷。炉渣在坑中冷却约耗时一天。在冷却炉渣的过程中,大量蒸汽释放到空气中。冷却后,用倾卸车从坑中取出炉渣,并转移到炉渣处理区。该试验在几乎填满的坑中进行。
开始实验前,使用真空泵(13)抽空(evaluated)包括气体收集罐(11)和冷凝罐(7)的整个装置。使用固定在冷凝罐(7)上的真空压力计(15)监视罐中的压力。一旦真空压力计指示-500mm的读数,就通过关闭阀门(6,12,17和18)隔绝该装置,即罐。当通过起重机将炉渣倾入坑中后,如图2所示,用拖车移动安装在轨道车(trolley)(24)上的实验装置接近渣坑。当携带该装置的轨道车到达标志区域时,首先通过使用聚乙烯包装袋(container bags)将含有含碳材料的熔料喷洒在熔渣表面上,然后使用链滑轮组***(23)降低反应罩(2)并置于热炉渣表面上。为了与周围气氛完全隔绝,将高温陶瓷纤维线(25)固定在反应罩的边缘上。将罩(2)置于炉渣表面上后,打开进水阀门(20),并通过与进水管线连接的流体指示器(21)监视水流。随后通过水喷嘴(26)将水均匀喷洒于熔渣的表面上。通过前述的水-炉渣-熔料熔料之间的反应形成产物气体。开启进水管线阀门(20)后,立即将气体鼓风机(22)转至开,并打开阀门(19)以从气体管线中除去空气和水蒸汽,一旦当带有水蒸汽的产物气体开始从鼓风机(22)的排气管排出,就关闭阀门(19),并缓慢开启阀门(6)。通过开启阀门(5)并连接气体取样器收集产物气体样品。当罐中的气压力达到+800mm(真空压力计(15)),开启气体阀门(6)并关闭气体阀门(19)。在向上移动反应罩(2)后,使用与阀门(17和18)连接的样品口从冷凝器(7)和收集罐(11)中收集样品。收集样品后,如前所述抽空装置以进行下一次实验。由于产物气体含>30%的氢和<10%的CO气体,是易爆易燃的,因此收集罐和冷凝罐上均装有***膜片以使***避免任何***。
对从样品口(5)收集的气体样品的典型分析列出如下:
样品/组分 | H2 | CO | CO2 | O2 | CH4 | CmHn | N2 |
实验/炉渣5/04/01 | 40.6 | 4.8 | 1.0 | 9.6 | - | - | 余量 |
实验/炉渣6/30/01 | 36.6 | 7.4 | 3.0 | 3.4 | - | - | 余量 |
Claims (7)
1.一种由水制造氢气的新方法,包括向炉渣和含碳熔料中加入水以通过水的热化学分解制造氢。
2.根据权利要求1的方法,其中所述矿渣作为热源,并且矿渣中的脱氧组分(Fe,FeO)参与分解反应。
3.根据权利要求的方法,其中放热的氧化反应为水的分解提供额外的能量,并降低***氧的分压,从而提高氢气的形成速率。
4.一种在炉渣的存在下由水制造氢的设备,包括含熔渣的石墨坩锅(1);安放在所述坩锅之上的反应罩(2);用于将水喷洒在坩锅(1)中的熔渣上的水管线;用于将制得的氢气从所述罩(2)中收集并传送到冷凝罐(7)中的钢管(4);使收集的氢气经至少一个控制阀门(9,10)传递至气体收集罐。
5.一种由水制造氢的设备,包括安装在链滑轮组装置(23)上的可移动的反应罩(2),设置在渣坑上的可移动的反应罩,将水喷洒到炉渣上的进水管线,使制得的氢气通过气体阀门(6)进入气体冷凝罐(7)中,其随后将其导入收集罐(11)中。
6.根据权利要求6的设备,包括用于在开始于反应罩(2)中制造氢气之前,将空气从气体管线中排出的气体鼓风机(22)。
7.根据权利要求6的设备,其中通过喷嘴(26)将水被均匀喷洒在熔渣的表面上。
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CN108467012A (zh) * | 2018-05-07 | 2018-08-31 | 浙江高成绿能科技有限公司 | 一种可快速持续产氢的化学制氢*** |
CN111943136A (zh) * | 2020-07-29 | 2020-11-17 | 浙江工业大学 | 一种直接利用生活垃圾焚烧炉渣制氢的方法 |
CN113023672A (zh) * | 2021-04-28 | 2021-06-25 | 北京中电企发能源科技有限公司 | 一种炼钢转炉铸余渣余热制氢的***和方法 |
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CN105209374A (zh) * | 2013-03-29 | 2015-12-30 | 国家科学研究中心 | 用于生成高纯度氢气的方法 |
CN108467012A (zh) * | 2018-05-07 | 2018-08-31 | 浙江高成绿能科技有限公司 | 一种可快速持续产氢的化学制氢*** |
CN111943136A (zh) * | 2020-07-29 | 2020-11-17 | 浙江工业大学 | 一种直接利用生活垃圾焚烧炉渣制氢的方法 |
CN113023672A (zh) * | 2021-04-28 | 2021-06-25 | 北京中电企发能源科技有限公司 | 一种炼钢转炉铸余渣余热制氢的***和方法 |
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US20100111826A1 (en) | 2010-05-06 |
KR20080110979A (ko) | 2008-12-22 |
CA2622171C (en) | 2014-12-23 |
MX2007016201A (es) | 2008-03-11 |
US9346675B2 (en) | 2016-05-24 |
RU2008101532A (ru) | 2009-07-20 |
KR101298052B1 (ko) | 2013-08-20 |
RU2415071C2 (ru) | 2011-03-27 |
EP2013139A1 (en) | 2009-01-14 |
WO2007125537A1 (en) | 2007-11-08 |
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JP5017362B2 (ja) | 2012-09-05 |
US20110027133A1 (en) | 2011-02-03 |
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