CN107709608A - 再生冷却方法和设备 - Google Patents

再生冷却方法和设备 Download PDF

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CN107709608A
CN107709608A CN201680018733.5A CN201680018733A CN107709608A CN 107709608 A CN107709608 A CN 107709608A CN 201680018733 A CN201680018733 A CN 201680018733A CN 107709608 A CN107709608 A CN 107709608A
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R·W·泰勒
A·F·赫尔曼
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Boulder Materials
Monolith Materials Inc
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Abstract

一种冷却等离子体室中的内衬的方法。使再循环气体与内衬接触或经过内衬，以冷却所述内衬并预热再循环气体。然后使被预热的气体经过等离子体室再循环，以成为等离子体形成工艺的一部分。该方法还包括：内衬为石墨，再循环气体经过存在于内衬中的至少一条冷却通道，冷却通道中的至少一条冷却通道被至少一个能够移除的内衬/通道盖覆盖，碳沉积物由存在于再循环气体中的烃形成，至少一条通道被形成为螺旋的冷却通道样式，至少一条通道被形成为基本上直的冷却通道样式，以及充气室，其用于协助在通道中产生均匀分布的冷却气体。

Description

再生冷却方法和设备
相关申请的引用
本申请要求2015年2月3日递交的临时专利申请序号No.62/111,341的优先权，通过引用将其公开内容并入本文。
技术领域
本发明总体上涉及使用电能来引起化学变化的方法和设备的技术领域。
背景技术
多年来有很多工艺可以被用于并已经被用于生产炭黑。多年来用于生产该炭黑的能源已经在很大程度上与用于将含烃材料转化成炭黑的原材料密切相关。剩余炼油和天然气一直是用于生产炭黑的资源。在诸如炭黑生产等的化学工艺中，能源随时间推移而演变，例如，从简单的火焰到油炉再到等离子体。与所有制造业一样，在不断探求更有效率和有效果的方式来生产这些产品。改变能源的流速和其它条件、改变原材料的流速和其它条件、提高生产速度、增加产量、降低制造设备磨耗特性等，多年来均是并仍将是该探求的一部分。
本文所说明的系统应对了上述挑战，并且额外地获得了更有效率和有效果的制造工艺。
发明内容
所说明的一种冷却等离子体室中的内衬的方法，包括使待用于在等离子体室中生成等离子体的至少一种再循环气体与内衬接触或经过内衬，以冷却等离子体室的内衬并预热再循环气体，并且使被预热的再循环气体返回到等离子体室，以生成等离子体。
额外的实施方式包括：根据上述方法，内衬为石墨；根据上述方法，再循环气体经过存在于内衬中的至少一条冷却通道；根据上述方法，冷却通道中的至少一条冷却通道被至少一个能够移除的内衬/通道盖覆盖；根据上述方法，移除盖，以去除通道中的碳沉积物；根据上述方法，碳沉积物由存在于再循环气体中的烃形成；根据上述方法，至少一条通道被形成为螺旋的冷却通道样式；根据上述方法，至少一条通道被形成为基本上直的冷却通道样式；根据上述方法，包括多于一条的通道；根据上述方法，包括充气室，用于协助在通道中产生均匀分布的冷却气体；根据上述方法，包括向再循环气体中添加氧化气体，以减少或消除存在于再循环气体中的烃和/或减少碳沉积物的形成；根据上述方法，氧化气体为蒸汽和/或二氧化碳；根据上述方法，包括使氧化气体经过通道中的至少一条通道，以去除该通道中的碳沉积物；根据上述方法，氧化气体为蒸汽和/或二氧化碳；根据上述方法，碳沉积物由存在于再循环气体中的烃形成；根据上述方法，内衬包含多个穿孔，用于为被预热的再循环气体提供入口；根据上述方法，穿孔沿着等离子体室包括一组至六组共面穿孔；根据上述方法，等离子体室为筒状，并且穿孔沿着等离子体室的筒体的弯曲部分；根据上述方法，穿孔允许吸气冷却；根据上述方法，等离子体室包含等离子体炬环，并且气体在等离子体炬环的内部和/或外部再循环；根据上述方法，使用AC电源来生成等离子体；根据上述方法，使用DC电源来生成等离子体；根据上述方法，包括将烃原料注入室，使得在注入的第一个1秒内，进入系统的以焦耳计的能量输入中的超过30％的能量输入转移到烃原料；根据上述方法，烃原料为天然气；根据上述方法，在等离子体生成部的下游注入烃原料；并且根据上述方法，在等离子体生成部的上游注入烃原料。
通过以下说明，这些实施方式和额外的实施方式将是明显的。
附图说明
图1、图2和图3示出了本文所说明的典型方法和设备的示意图。
具体实施方式
本文所示出的详细情况仅作为本发明的各实施方式的示例且为了本发明的各实施方式的说明性讨论的目的，并且为了提供被认为是本发明的原理和概念方面的最有用且最易于理解的说明而给出。就这点而言，未作出示出比对从根本上理解本发明所必需的更详细的本发明的细节的尝试，说明书使本领域技术人员清楚可以在实践中如何实施本发明的多种形式。
现在将参照更详细的实施方式说明本发明。然而，本发明可以以不同形式实施且不应被理解成限于本文阐述的实施方式。而是，提供这些实施方式使得本公开充分和完整，并且将会把本发明的范围完全传达给本领域技术人员。
除非另有定义，本文所使用的所有技术和科技术语具有与本发明所属领域技术人员通常理解的含义相同的含义。本发明的说明中使用的术语仅用于说明特定的实施方式而不意在限制本发明。除非上下文另有清楚的指示，在本发明的说明书和所附权利要求书中使用的，未被数量词限制的名称和被“所述”限制的名称也意在包括复数形式。本文提到的所有出版物、专利申请、专利和其它参考文献的全部内容通过引用而明确地并入。
除非另有指示，说明书和权利要求书中使用的表示组分的数量、反应条件等的所有数字在所有情况下应被理解成被术语“大约”修饰。因此，除非有相反的指示，在以下说明书和所附权利要求书中阐述的数值参数是近似值，可以根据待通过本发明得到的所探寻的期望性能而改变。至少，不试图应用等同原则对权利要求的范围进行限制，各数值参数应被理解成考虑到了有效位数和普通的四舍五入的方法。
尽管阐述本发明的宽泛范围的数值范围和数值参数是近似值，但是特定示例中阐述的数值被尽可能精确地报告。然而，任何数值固有地包含由在各个数值的试验测量中发现的标准偏差所必然导致的一定误差。遍及本说明书给出的每个数值范围将包括落在该较宽数值范围内的每个较窄的数字范围，就像这些较窄的数字范围全都明确地在本文写出的那样。
本发明的另外的优点将部分地在以下说明中阐述、将部分地从说明中明显获知、或可以从本发明的实践得知。应理解的是，前述总体说明和以下详细说明两者均仅是示例性和说明性的而不是如权利要求地限制本发明。
典型地，传热机构或冷却机构在过去是在等离子体室的外部。对于炉法而言，因为与等离子体法相比具有的较低固有温度，所以燃烧器无需过度冷却。能够在公开的专利申请US 2014/190,179中找到可以被认为是再循环气体的冷却/预热无效率的示例。热交换器位于等离子体室的外部，会导致等离子体室中的冷却无效率或冷却不足，并且会产生加热不充分的再循环/等离子体气体。
如本文所说明的，使用再生冷却能够在化学工艺中使用较高的等离子体温度，而不产生过高的等离子体室内衬温度。例如，以前使用等离子体制造炭黑，限制可以被使用的等离子体温度，或者使用水冷来限制在作为例如内衬使用于工艺中的例如石墨发生升华的损耗。如本文所说明的，使用再循环等离子体气体来冷却例如石墨的内衬，其中该气体将最终使用在等离子体室中。
随着被预热的气体使用在等离子体室中，在冷却内衬时吸收的能量会返回到工艺，这对于整个工艺而言能够表现出显著的能量成本节约。如前所述，在专利申请US2014/190,179的公开内容中，传热机构位于等离子体室的外部。通过将冷却机构设计并集成在内衬自身的内层板(inner skin)，本文所说明的系统被设置成同时冷却等离子体室内衬和加热再循环/等离子体气体。通过与内衬传热接触，气体沿着内衬中或内衬上的各个部位对内衬进行冷却。在一个实施方式中，气体流入被在内衬中切出的通道。在另一实施方式中，被切出的通道被可移除的盖或密封件覆盖。该可移除的内衬盖或密封件的使用能够使内衬在例如内衬过热时容易更换，并且还允许为了清洁或任何其它可能需要的维护而使通道容易进入。代替使用如本文所说明的再循环等离子体气体和降低室内的温度，可选方案将是使火炬在较高的功率密度(利用相同的气流提高的功率)下运行。利用如本文所说明的再循环等离子体气体系统会得到如下结果：室的温度将与不使用如本文所说明的再循环等离子体气体系统的较低功率密度情况相似。优点是气体以较高的温度离开室，消耗每单位功率给予其更多的可用焓，从而带来更有热效率的工艺。
虽然在图3中将穿孔示出为规则地间隔开的圆形孔，但是应注意的是，能够使用供被预热的再循环气体(诸如氢气等)注入等离子体室而设置的任意开口，例如无规孔或穿孔、曲折样式、缝状穿孔等。类似地，等离子体室能够具有诸如筒状等的任意形状，因此穿孔将沿着筒状等离子体室的弯曲部分。
冷却再循环气体包含痕量烃或其它污染物，这会导致碳或其它沉积物在冷却通道中的形成，该沉积物能够被以不限制或干涉将要实现的内衬中的冷却的方式容易地移除。还能够向再循环气体添加蒸汽、二氧化碳和/或其它氧化气体，以有助于减少可能存在于再循环冷却气体中的烃或其它污染物的量，进而减少或消除碳或其它污染物在冷却通道中的沉积。另外，如果在通道中沉积有任何积碳或其它污染物，则向通道中供送蒸汽、二氧化碳和/或其它氧化气体还能够协助从通道消除任何这样的沉积物。
在内衬中获得尽可能均匀的冷却是有利的，例如，可以避免在内衬中或内衬上形成“热点(hot spot)”。因此，使内衬在外部和/或内部与冷却气体尽可能均匀且连续的接触是有益的。尽管用于实现冷却气体更均匀分布的一个实施方式是在内衬中使用一条或多条螺旋的冷却通道，但是还能够与螺旋的通道组合或代替螺旋的通道地使用一条或多条直的、弯曲的或非螺旋的通道。如果使用多条通道，则使用充气室(plenum)以帮助在通道内提供均匀分布的冷却气体也是有益的。
当然，通道的尺寸和间隔将取决于等离子体室和/或反应室中产生的温度以及所期望的冷却物的量。等离子体室中的典型温度在从大约2500℃至大约6000℃的范围，反应室中的典型温度在从大约1200℃至大约3000℃的范围。典型地，使用例如传统的石墨切割技术和设备将通道加工为槽，并且典型地，通道的截面为正方形或矩形，并且通道能够为用于容纳所期望的冷却物的量的任意尺寸，例如15毫米(mm)至30mm宽、50mm至100mm深。
典型地，使用在大约2兆瓦和大约20兆瓦之间的功率来生成等离子体。首先使用以焦耳计的能量来生成等离子体，然后该能量随后被反应器的壁吸收、转移到未穿过环(annulus)或等离子体区的等离子体气体、从壁或等离子体气体被烃立即吸收或转移到注入的烃。以焦耳计，在注入后的第一个1秒中由烃吸收的能量的量为至少20％、30％或40％或更大。该能量能够吸收自电极、等离子体气体、反应器的壁等。
还能够使用穿孔的内衬，以使内衬的吸气冷却(aspirational cooling)成为可能。这不仅可以允许冷却气体更均匀地经过内衬，而且还可以使气体在最热的区域中加速经过以更快地散热，进而协助获得更均匀的冷却。存在于内衬中的气孔可以是在内衬中钻出的，或者气孔的形成是并入用于形成内衬的(多孔)石墨的制造工艺中的。
取决于等离子体组件的形状，冷却气体还能够使用在炬环中和/或炬环外。在通道中被加热的气体能够被添加到等离子体室或被添加到随后流过位于电极之间的环的等离子体气体，即，因为并非所有的火炬均具有环，所以能够在电弧之后将再循环气体添加到等离子体或混入到等离子体。炬环被定义为两个嵌套的同轴中空筒体之间的空间，这两个筒体用作火炬的正极和负极。
如本文所说明的，冷却气体与用于等离子体室的气体一起被用于冷却内衬，并且在这种情况下，会对用在室中的气体进行预热，由此减少了加热等离子体室气体至给定温度所需的能量的量。
参照示意性地示出了本文所说明的系统的图，将诸如氧气、氮气、氩气、氦气、空气、氢气等(单独使用或以两种以上的混合物进行使用)的传统等离子体气体11、21和31注入包含传统等离子体形成电极10、20和30(典型地，由铜、钨、石墨、钼、银等制成)的等离子体形成区12、22和图3中穿孔37以下。然后，如此形成的等离子体进入反应区13、23和33，在反应区13、23和33中等离子体与含碳原料14、24和34反应/相互作用，以生成炭黑制品。内衬16、26和36可以是能够经受得住等离子体形成温度的任意传统上使用的材料，其中优选的为石墨。还可以使用仅能够利用冷却经受住等离子体形成温度的材料。如所示的，再循环冷却气体流过冷却通道15、25和35，从而冷却内衬16、26和36并使冷却气体被加热。然后，被加热的气体(作为气流11的全部或部分)如图1所示地流入等离子体电弧和/或如图2所示地利用在等离子体区22中进行的混合而混入等离子体气体(由气流21形成)，或者被加热的气体穿过图3所示的穿孔37。然后，混合物流入反应区13、23和33，以与原料气体14、24和34接触。
因为将被加热的冷却气体加入等离子体气流11可能会潜在地对形成在电极10之间的电弧导致问题，所以在一些情况下可能是不期望的。在这些实例中，冷却气体的全部或部分能够代替地添加到等离子体区22(和穿过穿孔37)，优选地沿着内衬的内侧添加，使得气体为内衬提供免受热等离子体气体影响的额外保护。然后，混合物流入反应区23和33，以与原料气体24和34接触。还应注意，所示出的冷却气体的流向(在图1中为15)还能够为与所示方向相反的方向。期望的流向将取决于内衬上的辐射通量，其相应地取决于内衬的实际几何形状。因而，流可以是等离子体气流的逆流、并流和/或错流。能够通过穿孔的共面组或多组共面穿孔注入被预热的气体。图3中的穿孔段的上段38的形状可以为筒状，下段39为会聚的锥形。尽管图3中未示出，但是还应注意，穿孔还能够在等离子体室中的由电极占据的空间的上方延伸。
附图展示出了内部包含弯曲通道的内衬。然而，应理解，内衬的冷却能够通过如下而进行：通过简单地使冷却再循环等离子体气体经过内衬的一个或多个表面(取决于内衬设计)，或者借助于一条或多条直的、弯曲的、螺旋的或其它形状的通道的存在而经过内衬。由于存在与使内衬附近和/或内衬内部冷却的均匀性相关联的许多优点，所以如果内衬中存在多条通道，则能够使用充气室来协助使进入各条通道的流平稳，以有助于在内衬内产生更均匀的热分布。内衬还可以包含气孔，或者能够是多孔的，使得冷却能够作为吸气冷却进行。内衬、气孔和冷却面或冷却通道的尺寸和形状将取决于等离子体形成区和反应区的尺寸和形状、各区中所期望的温度、所期望的冷却的量和速度、所使用的具体等离子体气体等。例如，在超过1000℃的温度下生成和使用等离子体是常见的，这是温度控制对工艺而言重要的原因之一。
附图示出了变窄的等离子体室，然后等离子体室在等离子体生成部的下游扩展成较大区域。可选的构造可以含有不变窄、但能或不能在等离子体生成部的下游扩展的等离子体室。再生冷却将仍然在等离子体生成部的附近(等离子体室)进行。另外，烃的注入可以在等离子体生成部的上游或下游发生，并且可以是中央注入，而非图1、图2和图3所绘出的侧方注入。
可接受的烃原料包括具有通式CnHx或CnHxOy的任意化学品，其中n是整数，x在1和2n+2之间，y在0和n之间。例如，可以使用简单的烃以及芳香族原料，烃为诸如甲烷、乙烷、丙烷、丁烷等，芳香族原料为诸如苯、甲苯、甲基萘、热解燃油、煤焦油、煤、重油、油、生物油、生物柴油、其它生物衍生的烃类等。另外，还能够使用不饱和烃原料，诸如乙烯、乙炔、丁二烯、苯乙烯等。氧化烃诸如乙醇、甲醇、丙醇、苯酚、乙醚等也是可接受的原料。这些示例作为可接受的烃原料的非限制性示例提供，可以进一步与用于生产的其它可接受的组分组合和/或混合。本文所提及的烃原料是指原料中的大部分实质上是烃。用于该工艺的优选的烃原料为天然气。
再循环等离子体气体流过内衬中的通道，这除了降低等离子体和/或反应室中的温度以外，还升高了冷却气体的温度。在被加热之后，然后使用再循环等离子体气体作为正在注入等离子体区的等离子体气体或与正在注入等离子体区的等离子体气体混合。如能够领会的，对等离子体气体的该预热能够对工艺提供显著的能量成本节约。
在一个实施方式中，通道是开放的且可进入的，但是在使用期间是被覆盖的或密封的。该可进入性使诸如内衬的维修和更换和/或通道的清洁等事项变得容易。例如，等离子体气体可以包含烃或其它污染物。在典型的等离子体法中所经受的高温下，碳或其它沉积物可能会落在内衬上或者落在通道或气孔中。可移除的盖或密封件能够使该沉积物的清洁变得容易。典型地，盖由与内衬相同的材料制成，但是也可以由多孔材料(例如，碳纤维、石墨泡沫等)制成。
即使不具有上述盖或密封件，用于从通道减少或消除该沉积物的另一方式是在等离子体形成气体进入冷却通道之前向等离子体形成气体添加氧化气体。类似地，出于相同的目的，可以使氧化气体简单地行进经过通道。示例性氧化气体可以是例如蒸汽和/或二氧化碳。
在一些情况下，等离子体形成区可以包含如图1示意性所示的传统等离子体炬环，例如，具有阴极11、阳极12、等离子体或运载工作气体10和等离子体喷射区域13的等离子体炬环。在这样的情况下，冷却再循环等离子体气体可以在等离子体炬环内部或外部流动，即等离子体再循环气体能够添加到运载工作气流10，或者添加到等离子体喷射区域13。
在另一组情况下，能够使用AC或DC电源来形成等离子体。能够在例如美国专利No.7,452,514中找到AC等离子体系统的示例。AC系统能够利用多个电极，这具有更有效率的能源消耗以及降低电极表面处的热负荷的优点。能够在例如美国专利No.7,462,343及其参考文献中找到适当的DC等离子体系统的示例。
实施例1
使氢气行进经过等离子体形成区中的传统等离子体火炬电极组件。具有冷却通道的石墨内衬划分出等离子体形成区。如能够在下表中看到的，等离子体室壁的平均温度为2640K，最高温度为3210K。通过导流(diversion)大于90％H2的总再循环气体的10％、20％和30％，以下实施例B、实施例C和实施例D示出了等离子体壁温度的显著降低。对于导流总再循环气体的30％而言，等离子体壁处的平均温度从2640K降低到2450K，最高温度从3210K降低到3040K。这些实施例均通过750KW(千瓦)的等离子体火炬而具有热输入，并且均具有氢气的340Nm3/hr(标准立方米/小时)的等离子体气体流速。
表
实施例 氢气占总量的％ 平均温度(K) 最高温度(K)
A 0 2640 3210
B 10 2490 3140
C 20 2470 3090
D 30 2450 3040
因而，本发明的范围应包括可以落在所附权利要求的范围内的所有修改和变型。从本文所公开的本发明的说明书和实践考虑，本发明的其它实施方式对于本领域技术人员将是明显的。意在仅将说明书和示例视为示例性的，本发明的真正范围和主旨由权利要求指出。

Claims (26)

1.一种冷却等离子体室中的内衬的方法，所述方法包括使待用于在所述等离子体室中生成等离子体的至少一种再循环气体与所述内衬接触或经过所述内衬，以冷却所述等离子体室的内衬并预热所述再循环气体，并且使被预热的所述再循环气体返回到所述等离子体室，以生成所述等离子体。
2.根据权利要求1所述的方法，其特征在于，所述内衬为石墨。
3.根据权利要求1所述的方法，其特征在于，所述再循环气体经过存在于所述内衬中的至少一条冷却通道。
4.根据权利要求3所述的方法，其特征在于，所述冷却通道中的至少一条冷却通道被至少一个能够移除的内衬/通道盖覆盖。
5.根据权利要求4所述的方法，其特征在于，移除所述盖，以去除所述通道中的碳沉积物。
6.根据权利要求5所述的方法，其特征在于，所述碳沉积物由存在于所述再循环气体中的烃形成。
7.根据权利要求3所述的方法，其特征在于，至少一条通道被形成为螺旋的冷却通道样式。
8.根据权利要求3所述的方法，其特征在于，至少一条通道被形成为基本上直的冷却通道样式。
9.根据权利要求3所述的方法，其特征在于，包括多于一条的通道。
10.根据权利要求9所述的方法，其特征在于，包括充气室，用于协助在所述通道中产生均匀分布的冷却气体。
11.根据权利要求3所述的方法，其特征在于，包括向所述再循环气体中添加氧化气体，以减少或消除存在于所述再循环气体中的烃和/或减少碳沉积物的形成。
12.根据权利要求11所述的方法，其特征在于，所述氧化气体为蒸汽和/或二氧化碳。
13.根据权利要求3所述的方法，其特征在于，包括使氧化气体经过所述通道中的至少一条通道，以去除该通道中的碳沉积物。
14.根据权利要求13所述的方法，其特征在于，所述氧化气体为蒸汽和/或二氧化碳。
15.根据权利要求13所述的方法，其特征在于，所述碳沉积物由存在于所述再循环气体中的烃形成。
16.根据权利要求1所述的方法，其特征在于，所述内衬包含多个穿孔，用于为被预热的所述再循环气体提供入口。
17.根据权利要求16所述的方法，其特征在于，所述穿孔沿着所述等离子体室包括一组至六组共面穿孔。
18.根据权利要求16所述的方法，其特征在于，所述等离子体室为筒状，并且所述穿孔沿着所述等离子体室的筒体的弯曲部分。
19.根据权利要求16所述的方法，其特征在于，所述穿孔允许吸气冷却。
20.根据权利要求1所述的方法，其特征在于，所述等离子体室包含等离子体炬环，并且所述气体在所述等离子体炬环的内部和/或外部再循环。
21.根据权利要求1所述的方法，其特征在于，使用AC电源来生成所述等离子体。
22.根据权利要求1所述的方法，其特征在于，使用DC电源来生成所述等离子体。
23.根据权利要求1所述的方法，其特征在于，包括将烃原料注入所述室，使得在注入的第一个1秒内，进入系统的以焦耳计的能量输入中的超过30％的能量输入转移到所述烃原料。
24.根据权利要求23所述的方法，其特征在于，所述烃原料为天然气。
25.根据权利要求23所述的方法，其特征在于，在等离子体生成部的下游注入所述烃原料。
26.根据权利要求23所述的方法，其特征在于，在等离子体生成部的上游注入所述烃原料。
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