CN1310827C - 使用非热放电等离子体的化学处理 - Google Patents
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Abstract
使用非热毛细管放电(NT-CDP)装置或非热槽放电(NT-SDP)装置(统称为“NT-CDP/SDP”)激励化学反应的方法。所述NT-CDP/SDP装置包括设置于两个绝缘层(8、9)之间的第一电极,其中第一电极和两个绝缘层有至少一个穿过它们的开口(例如,毛细管或槽)。***所述开口的绝缘套(3)和至少一个第二电极(2)(例如,形状为销、环、金属线或锥形叶片)设置在与相关的开口流体连通。在第一与第二电极之间施加电压差时,从所述开口产生非热等离子体放电。随后把要处理的化学进料暴露于非热等离子体。这种处理适合于下面列举的化学反应:(i)对化学进料进行部分氧化,产生起功能作用的有机化合物;(ii)对聚合物纤维(例如,碳纤维生产中的聚丙烯腈纤维前驱物)进行化学稳定;(iii)对较长链长的石油烃预改造以产生适合于改造的进料;(iv)在化学还原气氢(例如氨或脲)中的天然气改造以生产一氧化碳和氢气;或者(v)等离子体加强的水煤气转变。
Description
技术领域
本发明涉及等离子体辅助化学处理,具体地说,涉及使用非热毛细管放电等离子体(NT-CDP)或非热槽放电等离子体(NT-SDP)(统称“NT-CDP/SDP”)以比传统的放电技术(例如,电弧、绝缘障碍放电和电晕放电)更均匀地给特定的化学物质增能,以便获得更高的产量和更大能量效率的化学转变。非热毛细管或槽放电(NT-CDP/SDP)装置不像往往导致一时的和空间不均匀的丝状放电的传统放电技术,它产生稳定的漫射等离子体,有助于保证在同等容积内最经济有效地进行处理。这种装置还能专门调整,有选择地启动决定化学反应的一定速率,这种化学反应很容易级联以得到所需的产品。以这种特定的方法给***加能就能使一般只会在更高温度和压力下才发生的化学反应在环境条件下发生。调整是以改变以下内容达成的:功率;反应物的成分和浓度;载气的成分和流速;温度;压力和/或反应器的外形尺寸。
背景技术
使用放电引起化学反应在工业上的重要性早已是众所周知的并已被使用了很长时间。在放电下发生化学反应的最古老也是最有效的例子是臭氧的产生。产生的臭氧可与不饱和烃反应以合成臭氧化物、醛和酮。正如亨利·德博埃恩爵士在1960年伦敦查普曼和霍尔出版社出版的《电弧放电;将其用于功率调整》中所说的那样,典型的早期气体放电装置是把不同的反应气体暴露在电弧(热等离子体)下而操作的。
近来的进展是在化学处理中既使用热等离子体也使用非热等离子体。授予Paulauskas等人的美国专利6,372,192号说明了碳纤维制造中使用等离子体的一种方法。该专利方法中,处理碳纤维的第一步是用在低压无氧气氛内使用10亿赫兹频率的等离子体把聚丙烯腈(PAN)纤维转变为碳石墨纤维。可是,此专利并不公开或建议在方法的初始步骤中使用富氧等离子体稳定聚丙烯腈纤维,此专利是要教人们使用非热等离子体吗?
近年来,主要由于又对氢燃料电池感兴趣,在等离子体辅助燃料改良和燃料转换领域的研发也取得了重要进展。例如,科恩等人获得的美国专利6,322,757号及其中引用的资料公开了诸如用等离子管改造烃以生产富氢气体的等离子体燃料转换器。授予Detering等人的美国专利6,395,197号公开了把轻质烃(天然气)热转变为所需终端产品特别是双原子氢和元素碳的高温装置和方法。另一个获得专利的发明是授予伊莱亚森等人的美国专利6,375,832号,该专利教导把富氢气体(例如甲烷)和富碳气体(例如二氧化碳)用化学方法转变为一般的液态燃料的方法。这种等离子体辅助的费-托合成是使用绝缘阻挡层放电与固体氟石催化剂相结合的方法进行的。
等离子体处理颇受注意的另一领域是对聚合材料进行等离子体激励表面处理以提高湿性能和/或表面附着力,例如,这正如L·A·Rosenthal和D·A·戴维斯在电器与电子工程师学会的《工业应用论文集》1A-11第三卷328-335页(1975年5、6月)发表的题为《电晕放电表面处理的电特征》,S·Han、Y·李、H·金、G·金、J·李、J·Yoon、G·金在《表面与表面处治层技术》93卷262-264页(1997年)发表的题为《用等离子源离子注入法改进聚合物表面》及授予格雷斯等人的美国专利6,399,159号中所说明的那样。
因此,需要如2000年12月15日申请的美国专利号为09/738,923的专利和2002年2月9日申请的美国专利号为60/358,340的专利所说明的用非热-毛细管放电等离子体或非热-槽放电等离子体使化学处理最优化。上述两个专利均结合作为本发明的参考。
发明内容
本发明涉及增强化学处理的方法。具体地说,本发明涉及用非热-毛细管放电等离子体/槽放电等离子体装置激励化学反应的方法。根据本发明的非热-毛细管放电等离子体/槽放电等离子体装置包括设置于两个绝缘层之间的第一电极,其中第一电极和两个绝缘层有至少一个穿过它们的开口(例如,毛细管或槽)。还设置至少一个与所述开口液体连通的第二电极(例如,形状为销、环、金属销、金属线或锥形金属叶片)。非热等离子体放电是在所述第一和第二电极之间施加电压差时从所述开口辐射出来的。这时把要处理的化学进料暴露于所述非热等离子体。这种处理适合于下面列举的化学反应:(i)对烃进料进行部分氧化,产生起功能作用的有机化合物;(ii)对聚合物纤维(例如,碳纤维生产中的聚丙烯腈纤维前驱物)进行化学稳定;(iii)对较长链长的石油烃预改造以产生适合于改造的进料;(iv)在化学还原气氛(例如氨或脲)中的天然气改造以生产一氧化碳和氢气;或者(v)等离子体加强水煤气的转变。
附图说明
从下面的示出本发明实施例的详细说明和图可以更容易地看清楚本发明的上述特点和其它特点。上述图中类似的元件用类似的标号标注,附图中:
图1a是根据本发明的对聚丙烯腈纤维进行化学稳定处理(氧化)的环形非热一毛细管等离子体处理装置实施例的侧视透视图;
图1b是与图1a的装置的纵轴线垂直的方向的侧视断面图;
图1c是图1b的装置的一个毛细管环形电极的放大纵向断面图;
图2a是根据本发明的气相非热毛细管放电等离子体辅助化学处理装置实施例的断面图;
图2b是图2a中装置的一个毛细管的放大图;
图3a是表示从NH3中形成H2的时间与氢探测器读数之间关系的曲线示例图;
图3b是时间与氢气浓度之间关系的曲线示意图;
图4a是根据本发明的对聚丙烯腈纤维进行化学稳定处理(氧化)的环形非热-槽放电等离子体处理装置实施例的侧视透视图;
图4b是与图4a的装置的纵轴线垂直的方向的侧视断面图;
图4c是图4b中装置的一个纵向丝状电极的放大纵向断面图。
具体实施方式
本发明涉及激励(催化)化学反应的方法。把化学进料暴露于等离子体的体积中的放电可以提高特定化学转变的产量和/或能量效率。可以处理气态、液态、含水的和/或固态先驱物。下面提供一些暴露于非热-毛细管放电等离子体或槽放电等离子体增强的化学反应的说明性示例,其中,每一过程都伴有专门的实例反应。
(i)烃进料部分氧化产生诸如醇、醛、酮和羧酸之类的起功能作用的有机化合物。
例如
(ii)聚丙烯腈先驱物变为碳纤维生产过程中的化学稳定“氧化”。
实例
(iii)更长的链长的石油烃的预处理(“裂化”)以产生适于改造的进料。
实例
(iv)在化学上为还原的(氨或脲)的气氛中改造天然气以生产一氧化碳和氢气。
实例
(v)用等离子体增强水煤气转换反应。
实例
在上述过程(i)和(ii)中,烃进料的非热氧化(“冷燃烧”)是用非热-毛细管放电等离子体或非热-槽放电等离子体激励的。所述等离子体从周围空气中产生以下氧化物质进入气流:氧原子(O(1D))、氢氧基(OH)、臭氧(O3)和过氧化基(HO2)。这些高活性物质有选择地氧化烃分子以便从反应中产生所需的产品。在实例(i)的情况下,所需的产品是CH3(CH2)nCH2OH。
上述(iii)中的反应优选地是在化学中性的等离子体环境内进行的。“化学中性”这一术语指的是具有诸如(但不限于)氦之类的化学上惰性载气的环境,并是电子直接撞击分解的结果。上述过程(iv)和过程(v)优先地发生于化学还原的等离子体中,即,趋向于增加目标化学制品的电子数量的等离子体。(还原与氧化相反。)可以把氨或脲加入气流以产生适于增强甲烷(过程(i))和水(过程(ii))内的氢还原为氢气的富电子等离子体。
图1a-1c示出的都是特别适于对诸如聚丙烯腈纤维之类的聚合物纤维进行化学稳定(氧化)的环形非热-毛细管放电等离子体处理装置的实例的不同视图。这种装置包括一个第二电极,设置于两个绝缘层8、9之间,所述两个绝缘层形成一个空心管子。选择第二电极2具有所需的膨胀系数。虽然所示出与说明的处理装置是圆管形的,但其它形状也是可以设想的,并在本发明的范围之内。设置于外绝缘层9周围的是高压总线5,例如,线网或金属外套。
图1b是与图1a内处理装置的纵轴线垂直的侧视断面图。如图1b清楚地显示的那样,多个毛细管4径向向外穿过绝缘层8、第二电极2和相对的绝缘层9。例如用石英制造的绝缘套3***各个毛细管4,和销电极1埋入各个绝缘套3内,从而销电极1是与第二电极2是绝缘的。所述高压总线5把销电极1阵列连接于一个共同的高压电源(HV)。在替换结构中,只要所述电极是与毛细管流体连通的,电极的几何形状可以不同并且不一定需要***毛细管。美国专利申请号为09/738,923中示出并说明了一些其它形状的毛细管放电结构。图1c是图1b中一个毛细管的放大图。
操作中,聚丙烯腈纤维6穿过所述管子内的通道并经受产生的非热-毛细管放电等离子体的处理。聚丙烯腈纤维6在处理装置10内经受非热-毛细管放电等离子体处理的同时,从相对端出来的就是稳定的聚丙烯腈纤维7。
图2a和图2b是根据本发明的非热-毛细管放电等离子体气相化学处理装置的两个视图。参看图2a中的断面图,有一组毛细管20穿过绝缘板11。绝缘套12插于各个毛细管20内,形成高绝缘限流毛细管。埋入各个毛细管20的是销或针电极10。把一组销或针电极与共同的高压电源电连接起来的是例如线网或金属外套之类的高压总线13。例如用石英、玻璃或陶瓷制造的绝缘板14用于绝缘电极板15。进、出转换导管16、17使经受处理的气体与一排毛细管等离子喷嘴横交地穿过反应器容积21。封闭的总管18使气态化学反应物在经过针电极10和毛细管20直接穿过等离子体喷嘴后喷入处理气流。元件19是辅助反应气体入口。在一个优选实施例中,***可以很容易地把等离子功率从大约500瓦升到10千瓦。处理装置优选地选择使用射频电源。根据载气所需越过反应器间隙的优选的峰间电压在大约5千伏到大约50千伏之间。
图3a和图3b是在氮载气内非热-毛细管放电等离子体辅助从异辛烷和氨蒸汽产生氢气的试验结果的图解。在300秒的平衡时间之后开始放电,以保证还原状态稳定。具体地说,图3a以图解的方法表示从NH3中形成H2的试验期间时间与氢探测器读数(mA)之间的关系。所述试验是在功率为200W,NH4OH的浓度为15M,N2
的流速为11L/min的情况下进行的。图3b示出的是试验结果的时间-氢气浓度(单位为ppM)的曲线。这种试验是在功率为2000W,NH3(aq)OH的浓度为15M,N2的流速为11L/min的情况下进行的。
这些试验结果证实,使用根据本发明的非热-毛细管放电等离子体结构时,仅仅由于等离子体(N2的轨迹)和在化学上为中性的等离子体(异辛烷轨迹)内仅有最少量的氢从异辛烷改良中形成,干扰即使有,也是非常小的。氨的轨迹表明由于氨的自动催化不均有大量(~1000ppmV)的氢形成。在存在氨的情况下使用异辛烷时发现由于协同效应产生最大量的氢(~1500ppmV)。产品流的气体色谱与质谱测定分析还表明大量等离子体辅助预改造(裂解)是与这种氢形成是结合的。在最佳化时,这些结果可以提供一种花钱少效益好的从冷凝燃料中产生氢气的方法。
根据本发明的非热-毛细管放电等离子体化学处理方法,因为大量降低功耗并减小催化剂随时间的消耗,而优越于惯用的热和/或催化方法。功耗降低是因为不必为了发生转变对大量气体加热。此外,非热-毛细管放电等离子体化学处理与诸如绝缘障碍放电(DBD)和电晕放电(CD)之类的其它等离子体处理相比也是有利的。原因是用非热-毛细管放电等离子体获得的比较大量的扩散等离子体有利于基本均匀有效地进行化学处理。说明的化学处理只是为了说明这一目的,丝毫不意味把本发明的范围用于其它化学处理的限制。
图4a-4c示出的是根据本发明的非热-毛细管放电等离子体气相化学处理装置的示范实施例。本实施例除了使用槽放电结构而不是毛细管放电结构外与图2a-2c所示出和说明的处理装置相同。图4a-4c内的槽放电结构特别适合于对诸如聚丙烯腈纤维之类的聚合物纤维进行化学稳定。与图2a-2c内作用相同的元件用类似的数字标注。图4a中示出的槽4基本与纵轴线平行设置。此外,槽4也可以与所述反应器的纵轴线成螺旋方向或基本垂直方向设置。电极***各个槽。作为举例,所述电极可以是金属线,形状与相关的槽相补并可部分地***、埋入或紧靠所述槽。在再一实施例中,这种电极可以是锥形叶片。美国专利申请60/358,340号内说明这种槽放电结构的其它形状,该专利完全结合作为本发明参考。这种槽放电结构的等离子体辐射的表面积比毛细管放电结构更宽广些。
虽然已在优选实施例里示出、说明并指出了本发明的基本的新特点,但要了解,本专业技术人员可以不脱离本发明的精神和范围作出各种各样的省略、替换和改变。例如可以很容易地预料到,把基本起相同作用的元部件和/或步骤用基本相同的方法作各种组合以取得相同的结果就全在本发明的范围内。用说明过的实施例中的一个中的元部件替换另一个中的元部件也是可以预料和设想的。还要了解附图不一定是按比例绘制的,附图只是表示某种概念而已。因此,本发明的范围以所附权利要求的范围来限制。
包括本文提到的所有资料、公开物和专利都结合作为本发明的参考。
Claims (11)
1.一种使用非热放电装置激励化学反应的方法,所述化学反应是烃进料的部分氧化,以生产具有功能作用的有机化合物、或是聚合物纤维的化学稳定、或是增加石油烃链长的预改造,以产生适合于改造的进料、或是化学还原气氛中的天然气改良,以生产一氧化碳和氢气、或是等离子体加强的水煤气转变,所述装置包括设置于两个绝缘层之间的第一电极,所述第一电极和两个绝缘层有至少一个穿过它们的开口,还设置至少一个与所述的开口流体连通的第二电极,所述方法包括以下步骤:
在第一和第二电极之间施加电压差,从所述开口产生非热等离子体放电;
把化学进料暴露于从所述开口辐射出来的非热等离子体。
2.根据权利要求1的方法,其特征为所述开口是毛细管,而且所述装置还包括***所述毛细管内的绝缘套。
3.根据权利要求2的方法,其特征为所述开口径向向外穿过所述第一电极和两个绝缘层。
4.根据权利要求2的方法,其特征为所述第二电极是金属销或环。
5.根据权利要求1的方法,其特征为所述开口是槽。
6.根据权利要求5的方法,其特征为所述开口设成沿纵向、成螺旋方向或基本与纵轴线成垂直方向的。
7.根据权利要求5的方法,其特征为所述第二电极是金属线或锥形金属叶片。
8.根据权利要求1的方法,它还包括把第二电极连接于电压源的电压总线。
9.根据权利要求8的方法,其特征为所述电压总线是线网或金属外套。
10.根据权利要求1的方法,其特征为所述聚合物纤维是碳纤维生产中使用的聚丙烯腈先驱物。
11.根据权利要求1的方法,其特征为所述化学还原气氛是氨或脲。
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PCT/US2002/024477 WO2003040027A1 (en) | 2001-08-02 | 2002-08-02 | Chemical processing using non-thermal discharge plasma |
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CA2516499A1 (en) * | 2005-08-19 | 2007-02-19 | Atlantic Hydrogen Inc. | Decomposition of natural gas or methane using cold arc discharge |
JP4724537B2 (ja) * | 2005-11-16 | 2011-07-13 | キヤノン株式会社 | 露光装置 |
CA2787979A1 (en) * | 2010-01-29 | 2012-07-19 | EVOenergy, LLC | Plasma reactor for gas to liquid fuel conversion |
KR101236210B1 (ko) * | 2010-11-21 | 2013-02-22 | 위순임 | 탄소섬유 가공장치 |
DE102012201942B8 (de) | 2012-02-09 | 2015-02-26 | Ewe-Forschungszentrum Für Energietechnologie E. V. | Verwendung eines aktivierten kohlenstoffhaltigen Materials, Verfahren zur Herstellung einer kohlenstoffhaltigen Elektrode, kohlestoffhaltige Elektrode, deren Verwendung sowie Vanadium-Redox-Flow-Zelle |
CN104831519A (zh) * | 2015-05-21 | 2015-08-12 | 嘉兴市产品质量检验检测院 | 一种连续处理纱线材料的等离子体*** |
CN106973481A (zh) * | 2017-03-10 | 2017-07-21 | 浙江理工大学 | 一种用于管状材料表面连续改性的常压等离子体*** |
CN109962209A (zh) * | 2017-12-22 | 2019-07-02 | 中国电子科技集团公司第十八研究所 | 一种高效氧催化活性碳纤维电极的制备方法 |
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