CN103501890B - 消耗臭氧层物质的蒸汽等离子体弧水解 - Google Patents

消耗臭氧层物质的蒸汽等离子体弧水解 Download PDF

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CN103501890B
CN103501890B CN201280020505.3A CN201280020505A CN103501890B CN 103501890 B CN103501890 B CN 103501890B CN 201280020505 A CN201280020505 A CN 201280020505A CN 103501890 B CN103501890 B CN 103501890B
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reactor
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CN103501890A (zh
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皮埃尔·卡拉宾
拉克希米纳拉亚南·米亚达拉·普拉拉达·拉奥
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Canada Pai Luojie Nice Co Ltd
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Abstract

一种用于在三区域反应器中使用蒸汽等离子体破坏前体材料的两步法，其中，作为第一步，将前体材料在反应器的高温区内水解，之后第二步，在反应器注入助燃氧气或空气的燃烧区内中温氧化反应物流，并且立即骤冷所得气流以避免形成不需要的副产物。相关设备包括：非转换直流蒸汽等离子体炬、外部冷却的三区域蒸汽等离子体反应器、用于将前体材料引入到等离子体炬的等离子体流中的装置、用于将助燃空气或氧气引入到反应器的燃烧区内的装置、用于使反应混合物离开反应器的装置和位于反应器出口端的用于骤冷反应混合物的装置。

Description

消耗臭氧层物质的蒸汽等离子体弧水解
相关申请的交叉引用
本申请要求于2011年3月18日提交、现在未决的美国临时申请No.61/454,368和于2011年9月23日提交、现在未决的加拿大申请No.2,753,043的优先权，其通过引用并入本文。
技术领域
本发明涉及大气中的臭氧的消耗，更具体地，涉及对消耗臭氧层物质的破坏。
背景技术
联合国环境规划署（theUnitedNationsEnvironmentalProgram，UNEP）的技术与经济评估小组（TheTechnologyandEconomic AssessmentPanel，TEAP）已经审核和批准了总计十二种用于破坏消耗臭氧层物质（ozonedepletingsubstances，ODS）的技术[1]。为了所述目的，这些经批准的技术可大致分类成焚烧技术、等离子体技术（包括电弧等离子体和射频等离子体）以及其他非焚烧技术[1]。从ODS处理速率和处理单元的数目二者来说，用于破坏ODS的最广泛使用的现行方法是通过焚烧或通过氩等离子体技术[1-2]。这两种技术使用热氧化作为主要破坏机理。将ODS供入被加热至约1200℃高温的耐火材料衬里反应器（refractorylinedreactor）中。焚烧炉使用燃烧化石燃料的燃烧器来达到必要的高温，而在氩等离子体技术的情况下使用氩等离子体弧[2-5]。
由于ODS是固有的燃烧抑制剂，因此需要极端的处理条件来用于其破坏。焚烧炉需要大量化石燃料以达到破坏ODS所需要的高温。消耗臭氧层物质以相对小的量与空气或氧气一起被供入至焚烧炉的高温区[2-5]。通常这些焚烧炉不具有第二燃烧室，所产生的废气被简单稀释后排放到大气中。因此，这些焚烧炉破坏少量的ODS需要大量化石燃料，产生大量烟道气，其包含大量难以从烟道气中除去的Cl2、F2、ΝΟX、SOX、VOC[2-5]。另外，焚烧过程极有可能排放不完全燃烧的有毒产物，例如二英和呋喃[6]。
等离子体破坏技术使用氩气、氮气或CO2作为等离子体形成介质来将能量由电弧转换成高的破坏温度[4,7-10]。这些技术依然使用热氧化作为其主要的破坏方法。使用直流等离子体炬（directcurrentplasmatorch）将耐火材料衬里反应器加热至高破坏温度。将ODS、空气和蒸汽引入到破坏区并且燃烧ODS。这些系统中的主要破坏机理仍然是热氧化，因此具有类似的问题，例如产生难以从烟道气中除去的Cl2、F2和CF4。在这些过程中，高温区过量氧和空气的存在还引起形成NOx的可能，然而在减少的氧气水平下操作导致形成难以除去的烟灰。氩等离子体技术需要高流量的高纯氩，这使其使用的成本昂贵。
因此，在本领域中需要改善的技术来破坏消耗臭氧层物质。
发明简述
因此，本发明的目的是提供用于破坏消耗臭氧层物质的新系统。
因此，根据本发明，提供了一种用于在反应器中使用蒸汽等离子体的前体材料破坏的两步法，其中，作为第一步，将所述前体材料在反应器的高温区内水解，随后第二步，在注入有助燃氧气或空气的反应器燃烧区中中温氧化反应物流，并且立即骤冷所得气体物流以避免形成不需要的副产物。
另外，根据本发明，提供了用于实施上述工艺的设备，其包括：非转换直流蒸汽等离子体炬、包含耐腐蚀耐火材料衬里的外部冷却的三区域蒸汽等离子体反应器、用于将等离子体炬附接到反应器的装置、用于将或以气体涡流或以细小的液体喷雾或以固体颗粒形式的前体材料引入到等离子体炬的等离子体流（plasmaplume）中的装置、用于将助燃空气或氧气引入到反应器的燃烧区内的装置、用于使反应混合物离开反应器的装置和用于骤冷位于反应器出口端的反应混合物的装置。
另外，根据本发明，提供了用于破坏前体材料的设备，其包括：包含高温区和燃烧区的反应器，高温区适合于水解前体材料，燃烧区适合于在注入助燃氧气或空气下对反应物流实施中温氧化，在反应器的出口端设置有骤冷装置，用于骤冷所得气体物流以避免形成不需要的副产物。
通过阅读以下仅参照附图以示例的方式给出的本发明实施方案的非限制性描述，本发明的优点和特征将变得更明显。
附图说明
现在参照附图，以举例说明的方式示出了本发明的说明性性实施方案，其中：
图1a是根据本发明一个实施方案的用于破坏消耗臭氧层物质的完整系统的示意图；
图1b是根据本发明另一实施方案的用于破坏消耗臭氧层物质的完整系统的示意图；
图2是用于破坏消耗臭氧层物质的本系统的破坏部分的纵向截面图。
本发明的说明性实施方案的描述
本发明使用蒸汽等离子体水解系统S来破坏ODS。本发明的主要破坏机理是等离子体蒸汽水解。在该系统中，定制设计的蒸汽等离子体炬作为唯一能源来将耐火材料衬里的主反应室加热至接近1500℃的温度。使用有少量惰性气体的由普通水形成的过热蒸汽作为主等离子体形成气体。使用蒸汽等离子体中存在的高反应性蒸汽等离子体（即，氢离子和氢氧根离子）在缺氧环境中将ODS转化成CO、HCl和HF。所产生的CO在工艺的下游燃烧掉，然后瞬时水骤冷。缺氧环境消除了有毒物质如Cl2、F2和CF4的形成，而快速骤冷消除了二英和呋喃的形成。工艺中形成的酸性气体可以：(i)用碱中和，或(ii)首先用水洗涤以回收弱酸混合物，然后中和酸性气体的不可回收部分。在这两种情况下，将主要包含CO2的经净化的废气流排放到大气中。
现在转向附图中的图，将详细描述本发明的蒸汽等离子体水解系统S。
将或以气体涡流或以细小液体喷雾或以固体流形式的前体材料1注入到如图2所示的系统S中。将待破坏的前体材料1通过特别设计的法兰12供应到等离子体炬4附近。该法兰12是水冷的，由耐酸材料制成并且被特别设计来有助于将供应的前体材料1与高温粘性蒸汽等离子体流均匀混合。
使用外部加热源（通常是蒸汽等离子体炬4）作为源将耐火材料衬里反应器加热至1500℃的温度。等离子体炬4被设计和构建成具有特征，以避免炬内的过热蒸汽在到达等离子体弧之前冷凝。等离子体炬的这些特征包括：(i)直接注射3主等离子体形成气体（过热蒸汽）至炬涡流（torch vortex）处，以使得其在到达弧流的过程中不冷凝并且使过热蒸汽在炬本体内的通路尽可能小；(ii)用热流体（丙二醇-水混合物）（在高压封闭回路中循环）冷却等离子体炬本体以避免过热蒸汽冷凝；以及(iii)使用耐高温聚合物如VespelTM或PEEK用于炬内部组件。
蒸汽等离子体炬4包括如图2所示布置的金属阴极2、金属点火阳极6和金属工作阳极8。等离子体弧在阴极2和点火阳极6之间由氦气或另外的单原子气体引发。一旦弧稳定10，在3处注入等离子体形成蒸汽并且弧从点火阳极6转移到工作阳极8。用氮气、氦气、氩气或其混合物作为保护气体（shroudgas）5。保护气体5保护金属阴极2不被过早氧化，从而增加阴极2的工作寿命。用过热蒸汽作为主等离子体形成气体3。
蒸汽等离子体炬4除了作为热源之外，还提供用于破坏前体材料1所需要的活性氧离子、氢氧根离子和氢离子，并且防止形成不需要的副产物，例如Cl2、F2、CFX。总反应可概括为：
CHxClyFz+aH2O→zHF+yHCl+aCO+bH2+cH2O
使用耐火材料衬里反应器14来破坏前体材料1。使用耐腐蚀高耐久性的耐火材料衬里16作为反应器14中的工作耐火材料。例如，用已知耐腐蚀性HF和HCl气体的高氧化铝耐火材料（氧化铝含量＞98%）如Kricon34TM或类似物作为工作耐火材料。
反应器14的内壁涂覆有耐酸高温金属涂层，例如，hastealloyTM或类似物。为了安全原因和限制对熔炉间的加热，通过空气或通过水从外部冷却反应器14的外壁。
如图2所示，耐火材料衬里反应器14包括三个区。这三个区是：
1)锥形收敛的高温蒸汽水解区11，其中所供应的前体材料1经历蒸汽水解；
2)狭窄的管状区13，其产生气体的高温湍流混合并且有助于水解反应的完成；和
3)锥形发散的中温燃烧区15，其中气体用助燃空气或氧气燃烧。
仍然如图2所示，将助燃空气或氧气9添加到反应器4中。量取助燃空气或氧气9到达反应器14以控制反应器14的低温区中的温度，同时达到完全燃烧并且消除不需要的副产物如Cl2的形成。
如图2所示，水骤冷单元20直接附接在反应器14的燃烧区15的出口。一组喷雾嘴18在骤冷单元20内产生水17的细小喷雾，水17的喷雾瞬间冷却气体。这种气体的瞬间骤冷可防止二英和呋喃的再形成（reformation）。骤冷单元20用耐酸材料构建成双壁水冷却管段。
如图2最佳示出的，洗气罐22附接在骤冷单元20的底部。洗气罐22在所有密封面上使用耐酸塑料密封材料。洗气罐22的内壁衬里有耐酸TeflonTM基涂层，例如或类似物质。洗气罐22作为收集骤冷水19的容器并且为洗涤器水再循环泵28提供必要的水头（见图1a）。
用标准烟道气净化技术（即，使用酸性气体中和洗涤器24（如图1a所示）的湿法废气净化技术或干法气体净化技术）除去烟道气中的酸性气体。
如图1所示，引风机26抽吸废气通过系统S并且在系统S中产生轻微负压。整个系统S保持在轻微负压下（几英寸H2O柱）以防止任何酸性气体从系统S逸出。在引风机的出口，废气被排放到堆叠体23。
在运行时，蒸汽等离子体炬4将反应器14加热至期望的运行条件，并且将前体材料1注入到等离子体流中。在高温水解区11中，蒸汽等离子体中存在的高活性氢离子和氢氧根离子水解前体材料1。向水解区11添加额外的蒸汽7。经反应流流过狭窄管状区13（其为反应提供必要的湍流和停留时间）到达反应器14的燃烧区15。向燃烧室14添加助燃空气或氧气9，并且离开反应器14的废气进入位于燃烧区15的出口的水骤冷20。废气被喷嘴18产生的水17的细小喷雾快速骤冷。液流进入洗气罐22，而废气离开洗气罐22并且通过标准废气净化技术。用湿法洗涤技术或干法洗涤技术从废气中净化酸性气体如HF和HCl并且将其转化成无害的盐。用引风机26驱动废气通过系统S并且在系统S内产生轻微负压。
用计量泵30将来自罐或桶25的烧碱或其它碱输送给洗涤器水再循环线31以不断地调节洗涤器溶液的pH，中和来自废气的任何酸组分（HCl、HF）。通过排污线32从洗气罐中除去经中和的水21。
现在转到图1b，其描述了变体蒸汽等离子体系统S'，其包括吸气净化选择(ii)，从而产生弱酸，随后中和酸性气体。
离开骤冷单元20的气体被输送到酸回收罐22b，在其中用烯酸洗涤离开骤冷单元20的酸性气体。如图2最佳显示的，酸回收罐22b直接附接在骤冷单元20的底部。酸回收罐22b在所有密封面上使用耐酸塑料密封材料。酸回收罐22b作为收集骤冷水19的储液器并且为再循环泵41提供必要的液头（图1b）。向酸回收罐22b中持续地或以开/关模式添加鲜水42以控制酸浓度。
在包封的酸洗涤器单元43中，气体与洗涤液体的流动逆向行进。在酸性气体经过酸洗涤单元43行进时，所述酸性气体被洗涤。定期从酸回收罐22b中移除在酸回收罐22b的底部收集的弱酸混合物（流44）。
离开酸洗涤单元43的经洗涤气体流（流45）进入气体净化洗涤器单元46。洗气罐单元47附接在气体净化洗涤器单元46的底部。洗气罐单元47在所有密封面使用耐酸塑料密封材料。洗气罐单元47作为收集洗涤水的储液器并且为洗涤器水再循环泵48提供必要的水头。
用计量泵51将来自罐或桶52的烧碱或其它碱输送给洗涤器水再循环线54以不断地调节洗涤器溶液的pH，中和来自废气的任何酸组分（HCl、HF）。通过排污线53从气体净化洗气罐中除去经中和的水49。
用标准烟道气净化技术（即，使用中和洗涤器46（如图1b所示）的湿法废气净化技术气体或干法气体净化技术）净化烟道气。
尽管在上文已经通过其实施方案的方式对本发明进行了描述，但是可对其进行修改而不脱离本文所述主题发明的性质和教导。
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Claims (32)

1.一种用于在反应器中使用蒸汽等离子体破坏前体材料的两步法，其中，作为第一步，将所述前体材料在所述反应器的高温区内水解，随后第二步，在注入助燃氧气或空气的所述反应器的燃烧区内中温氧化反应物流，并且立即骤冷所得气体流以避免不需要的副产物的形成。
2.根据权利要求1所述的方法，其中所述蒸汽等离子体由非转换直流蒸汽等离子体炬产生，由此在金属电极和过热蒸汽之间产生的电弧在所述等离子体炬的出口端形成富含活性氢离子和氢氧根离子的高温的等离子体流。
3.根据权利要求2所述的方法，其中所述等离子体炬使用少量惰性气体作为保护气体以保护背电极不被过度氧化。
4.根据权利要求3所述的方法，其中所述惰性气体为氮气、氩气或氦气或者它们的混合物。
5.根据权利要求2至4中任一项所述的方法，其中在所述反应器的所述高温区内，用所述等离子体流的活性氢氧根离子和氢离子在高温下水解所述前体材料。
6.根据权利要求1至4中任一项所述的方法，在其中注入必要的助燃氧气或空气的富氧环境下，在所述反应器的所述燃烧区内在中温下燃烧离开所述反应器的水解区的气体混合物。
7.根据权利要求1至4中任一项所述的方法，其中使用冷水的细小喷雾快速骤冷燃烧之后所得到的工艺流，以避免形成任何不需要的副产物。
8.根据权利要求7所述的方法，其中所述反应器包括三个区：即，锥形收敛的高温蒸汽水解区，其为所述前体材料的完全水解提供必要的停留时间；随后是狭窄的管状区，其为反应提供必要的湍流和另外的停留时间；和锥形发散的中温燃烧区，其为所述工艺流的完全燃烧提供停留时间。
9.根据权利要求2至4中任一项所述的方法，其中来自所述等离子体炬的所述等离子体流延伸至所述反应器的第一区中并且容纳在所述反应器内。
10.根据权利要求2至4中任一项所述的方法，其中使用气体涡流将所述前体材料注入到相邻于所述等离子体炬并且在所述等离子体炬和所述反应器的水解区之间的所述等离子体流的芯，所述气体涡流产生湍流并且使所述前体材料与所述芯的等离子体流充分混合。
11.根据权利要求10所述的方法，其中将所述前体材料或作为气体或作为细小液体喷雾或作为细小固体颗粒注入到所述芯中。
12.根据权利要求1至4中任一项所述的方法，其中活性氢和氢氧根蒸汽等离子体存在于所述反应器的水解区内。
13.根据权利要求1至4中任一项所述的方法，其中缺氧环境存在于所述反应器的水解区内，富氧环境存在于所述反应器的所述燃烧区内。
14.根据权利要求1至4中任一项所述的方法，其中使用相邻于所述燃烧区出口的冷水的细小喷雾快速骤冷离开所述反应器的所述燃烧区的所述反应物流，以避免形成不需要的副产物。
15.根据权利要求1至4中任一项所述的方法，其中所述反应器的所述高温区中的温度为接近1500℃。
16.根据权利要求1至4中任一项所述的方法，其中在所述反应器的所述高温区内水解所述前体材料，从而使所述前体材料与富含活性氢H+离子和氢氧根OH-离子的所述蒸汽等离子体化学反应。
17.根据权利要求2至4中任一项所述的方法，其中用法兰将待处理的所述前体材料直接引入到等离子体流中。
18.根据权利要求17所述的方法，其中所述法兰是水冷的，由耐酸材料制成，并且适于促进所述前体材料与高温粘性的蒸汽的等离子体流均匀混合。
19.一种用于实施权利要求1至14中任一项所述的方法的设备，其包括：非转换直流蒸汽等离子体炬、包含耐腐蚀耐火材料衬里的外部冷却的三区域蒸汽等离子体反应器、用于将所述等离子体炬附接到所述反应器的装置、用于将所述前体材料以或气体涡流或以细小的液体喷雾或以固体颗粒的形式引入到所述等离子体炬的等离子体流中的装置、用于将助燃空气或氧气引入到所述反应器的所述燃烧区内的装置、用于使反应混合物排出所述反应器的装置和用于骤冷位于所述反应器出口端的所述反应混合物的装置。
20.根据权利要求19所述的设备，其中所述等离子体炬包含间隔开布置一组金属电极，即阴极、点火阳极和工作阳极，从而使得直流电弧存在于所述阴极和所述工作阳极之间，所述等离子体炬使用惰性气体作为保护气体，并使用蒸汽作为主等离子体形成气体，并且具有在所述工作阳极的端部处排出的等离子体流。
21.根据权利要求20所述的设备，其中所述惰性气体为氦气、氮气、氩气或它们的混合物。
22.根据权利要求19所述的设备，其中所述用于骤冷的装置位于所述反应器的所述出口端，并且产生冷水喷雾，离开所述反应器的工艺流经过所述冷水喷雾。
23.一种用于破坏前体材料的设备，其包括含高温区和燃烧区的反应器，所述高温区适合于水解所述前体材料，所述燃烧区适合于对注入助燃氧气或空气的反应物流实施中温氧化，在所述反应器的出口端设置有骤冷装置，用于骤冷所得气体流以避免不需要的副产物的形成。
24.根据权利要求23所述的设备，其中所述反应器的所述高温区包括锥形收敛的高温蒸汽水解区，其为完全水解所述前体材料提供必要的停留时间，其中在所述高温区与燃烧区之间设置有狭窄的管状区，用于为反应提供必要的湍流和另外的停留时间，并且其中所述反应器的所述燃烧区包括锥形发散的中温燃烧区，其为完全燃烧工艺流提供停留时间。
25.根据权利要求23所述的设备，其中设置有：非转换直流蒸汽等离子体炬、用于将所述等离子体炬附接到所述反应器的装置、用于将所述前体材料或以气体涡流或以细小的液体喷雾或以固体颗粒的形式引入到所述等离子体炬的等离子体流中的装置、用于将助燃空气或氧气引入到所述反应器的燃烧区的装置、用于使反应混合物排出所述反应器的装置和用于骤冷位于所述反应器的所述出口端的所述反应混合物的装置。
26.根据权利要求25所述的设备，其中所述反应器包括三区域蒸汽等离子体反应器，所述三区域蒸汽等离子体反应器是外部冷却的，并且包括耐腐蚀耐火材料衬里。
27.根据权利要求25至26中任一项所述的设备，其中所述等离子体炬包括间隔开布置一组金属电极，即阴极、点火阳极和工作阳极，从而使得直流电弧存在于所述阴极和所述工作阳极之间，所述等离子体炬使用惰性气体作为保护气体，使用蒸汽作为主等离子体形成气体，并且具有在所述工作阳极的端部处排出的等离子体流。
28.根据权利要求27所述的设备，其中所述惰性气体为氦气、氮气、氩气或它们的混合物。
29.根据权利要求23至26中任一项所述的设备，其中所述骤冷装置产生冷水喷雾，离开所述反应器的工艺流经过所述冷水喷雾。
30.根据权利要求19至22和25至26中任一项所述的设备，其中所述用于将所述前体材料引入到所述等离子体炬的等离子体流中的装置包括法兰，其中所述前体材料被直接引入到所述等离子体流中。
31.根据权利要求30所述的设备，其中所述法兰是水冷的，由耐酸材料制成，并且适于促进所述前体材料与高温粘性的蒸汽的等离子体流均匀混合。
32.根据权利要求22至26中任一项所述的设备，其中所述反应器包括三个区，即，锥形收敛的高温蒸汽水解区，其为完全水解所述前体材料提供必要的停留时间；之后是狭窄的管状区，其为反应提供必要的湍流和另外的停留时间；和锥形发散的中温燃烧区，其为完全燃烧工艺流提供停留时间。
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