CN107366824A - 用于天然气的吸附储存罐 - Google Patents

用于天然气的吸附储存罐 Download PDF

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CN107366824A
CN107366824A CN201710287281.7A CN201710287281A CN107366824A CN 107366824 A CN107366824 A CN 107366824A CN 201710287281 A CN201710287281 A CN 201710287281A CN 107366824 A CN107366824 A CN 107366824A
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CN107366824B (zh
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A·M·戴利
J·沈
F·戴
M·蔡
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Abstract

一种用于天然气的吸附储存罐包括设置在交通工具上容纳天然气的可加压罐。天然气吸附剂设置在罐中。天然气是具有分子长度和动力学直径的成分统计分布的成分的混合物。吸附剂具有孔径的孔径统计分布以吸附和解吸成分的混合物。

Description

用于天然气的吸附储存罐
背景技术
一些内燃机(ICE)被设计为以天然气燃料运行。这种天然气燃料的内燃机可以是专用天然气发动机或多燃料发动机。专用天然气发动机仅以天然气运行。多燃料发动机能够以多种燃料类型运行。例如,双燃料发动机能够以两种不同的燃料类型运行。一种燃料类型可以是液相燃料(包括基本上以液态输送到双燃料发动机的汽油、乙醇、生物柴油、柴油燃料或其组合)。另一燃料类型可包括替代燃料,例如压缩天然气(CNG)、吸附天然气(ANG)、液化石油气(LPG)、氢气等。两种不同燃料储存在分开的罐中,并且双燃料发动机可一次以一种燃料运行,或可选择地以两种不同燃料类型的组合运行。
天然气可以以几种方式储存在交通工具上。一些交通工具将天然气储存在可加压罐中。一些交通工具在天然气罐中具有天然气吸附剂以增加较低压力下可储存在罐中的天然气质量。ANG与CNG不同,CNG储存在无吸附剂的加压容器中。
发明内容
用于天然气的吸附储存罐包括设置在交通工具上容纳天然气的可加压罐。天然气吸附剂设置在罐中。天然气是具有分子长度和动力学直径的成分统计分布的成分的混合物。吸附剂具有孔径的孔径统计分布以吸附和解吸成分的混合物。
附图说明
通过参考以下详细说明和附图,本公开的示例的特征将变得显而易见,其中相同的附图标记对应相似但可能不相同的组件。为了简洁,具有前述功能的附图标记或特征可以结合其出现的其他附图进行说明或可以不进行说明。
图1是根据本公开的可加压罐的示例的横截面半示意图;
图2是美利坚合众国典型管道天然气成分表;
图3为饼状图,示出了与管道天然气平均样品中成分的摩尔百分比相匹配的孔径的具体统计分布;
图4是描述根据本公开的与碳颗粒共结晶的Cu-BTC(铜苯-1,3,5-三甲酸)的示意图;
图5是描述根据本公开的现有HKUST-1以及与碳纳米管和碳气凝胶共结晶的HKUST-1的孔体积相对孔宽度的曲线图;
图6是描述以克/克计的过量甲烷吸收相对用于重复填充UHP(超高纯度)甲烷至带有现有HKUST-1吸附剂的罐中的以巴计的压力的曲线图;
图7是描述以克/克计的过量天然气混合物吸收相对用于重复填充天然气混合物至带有现有HKUST-1吸附剂的罐中的以巴计的压力的曲线图;以及,
图8是描述根据本公开的HKUST-1和共结晶吸附剂的最大过量天然气吸附相对填充循环数的曲线图。
具体实施方式
内燃机(ICE)燃烧发动机内的燃料进行工作。一些ICE用于交通工具以向交通工具提供动力。如本文所使用的,交通工具指传送乘客或货物的自行式移动机器。根据本公开的交通工具的示例为:机动车辆(摩托车、汽车、卡车、公共汽车、火车)和船舶(轮船、汽艇)。
在一些情况下,ICE由该ICE设计用来消耗的燃料的类型来限定。例如,一些柴油发动机可以以1-D级柴油或2-D级柴油运行。汽油发动机可通常以汽油运行。双燃料发动机可兼容两种类型的燃料,例如汽油和天然气。
最初作为美国汽车工程师协会(SAE)成立的国际汽车工程师协会(SAEInternational),是总部位于美国的全球活跃的各行业工程专业人士的专业协会和标准组织。
1994年2月发布的《SAE地面车辆推荐操作规程J1616,压缩天然气车辆燃料推荐操作规程》描述天然气如下:天然气主要包括甲烷(一般为88~96mol%),余量为比例减少的非甲烷烷烃(即乙烷、丙烷、丁烷等)。在天然气中发现的其他组分是氮气(N2)、二氧化碳(CO2)、水、氧气和微量润滑油(来自压缩机)以及作为硫化氢(H2S)和其他硫化合物发现的硫。在进入商业天然气传输系统之前,对天然气进行处理以满足对硫化氢、水、较重烃的可冷凝物、诸如CO2和N2的惰性气体以及能量含量的限制。本地配送公司(LDC)加入硫醇增味剂(例如叔丁基硫醇)以增加天然气的人体可检测气味,否则将会无气味。
如本文所使用的,天然气指主要包括甲烷的成分的气体混合物。天然气可包括不同量的其他高级烷烃和较少量的二氧化碳、氮气和硫化氢。在一种示例中,天然气成分按质量分数可约为:甲烷81.55%,乙烷6.79%,丙烷4.98%,己烷0.97%,氢气0.01%,一氧化碳0.16%以及惰性气体(氮气)5.4%。取决于来源,天然气中的甲烷量可以不同。在另一示例中,天然气成分按质量可约为:甲烷75%,乙烷15%,其他烃约5%。
在一种示例中,天然气可包括甲烷、乙烷、丙烷、己烷和氢气。天然气可包括约78mol%至约96mol%的甲烷,和随非甲烷烷烃的摩尔质量增加而比例减少的非甲烷烷烃。
现在参考图1,描述了用于天然气的吸附储存罐15的示例。该吸附储存罐15包括设置在交通工具10上容纳天然气的可加压罐20。天然气可作为燃料被交通工具10消耗。
可加压罐20包括容器12。天然气吸附剂24可操作地设置在罐20中。更具体地,该天然气吸附剂24可操作地设置在可加压罐20的容器12内。天然气是具有分子长度和动力学直径的成分统计分布的成分的混合物。成分统计分布是指天然气样品将具有特定成分的概率。吸附剂24具有孔径的孔径统计分布以吸附和解吸成分的混合物。孔径统计分布是指吸附剂的随机样品将具有特定孔径的孔的概率。如本文所使用的,物理分布是指孔的空间位置。在本公开的示例中,吸附剂孔径的物理分布在可加压罐20中可以是均匀的。这不同于在罐的开口处建立过滤器或缓冲吸附剂,其被设计为捕获较大分子并从气流中提取较大分子使得相对纯的甲烷达到罐中吸附剂的体积。还可以将吸附剂布置成具有各种层或薄层,其中每层具有特定的孔径。本公开的发明人已经发现,不需要通过孔径将吸附剂分离成层。本公开的发明人已经认识到,天然气的每一成分对特定尺寸的孔具有亲和力,并且将倾向于在其他尺寸的孔之前吸附到该特定尺寸的孔上。
如本文所公开的,天然气吸附/解吸不同于纯甲烷的吸附/解吸。在本公开的示例中,针对天然气的不同成分来调节吸附剂的孔径分布,不仅用于性能,而且用于动力学和热力学。动力学是指在特定时间段内被吸附和解吸的气体分子量。
本文公开了带有分级和定制的孔径的吸附剂。并且根据本公开,合成带有分级和定制的孔径的吸附剂的方法包括共结晶。如本文所使用的,分级孔隙率指在相同结构中发现两个或多个不同长度尺度(例如孔直径)的孔。该结构可以是共结晶吸附剂的颗粒。分级孔隙率使多孔结构能够执行一个以上的功能,并因此扩大其能力。例如,一种结构可具有增加该结构比表面积的微孔,导致更高的储存或净化能力,同时还具有提供有效的介质传送以及结构完整性的中孔(孔直径大于约20埃且小于约500埃)。在本公开的示例中,吸附剂的分级孔隙率与天然气成分的摩尔百分比相匹配。
图1所示的容器12的形状为圆柱形罐,应当理解,容器12的形状和尺寸可至少部分地取决于天然气燃料交通工具10中可加压罐20的可用包装套而不同。例如,尺寸和形状可以改变以装配到交通工具行李箱的特定区域。
在图1所示的示例中,容器12是具有单个开口18或入口的单个单元。该开口18可以可操作地装配有阀构件19,用于向容器12充入气体或用于从容器12排出气体。应当理解,在本公开的示例中可使用手动和/或螺线管致动的罐阀。阀构件19通过限定于容器12的壁中的开口18可操作地连接到容器12并且与容器12流体连通,容器壁具有例如约3mm至约10mm的厚度范围。应当理解,开口18可以是螺纹的,用于典型的罐阀(例如,3/4x 14NGT(国家天然气锥螺纹))。此外,应当理解,开口18可位于容器壁的任何区域并且不一定位于如图1所示的端部。
尽管未示出,但应当理解,容器12可配置有其他容器,使得多个容器通过歧管或其他合适机构流体(例如气体)连通。
如图1所示,天然气吸附剂24定位于容器12内。天然气吸附剂24重复吸附和解吸天然气的能力取决于天然气吸附剂24吸附/解吸天然气成分的适用性。现有的吸附储存罐在以几乎纯的甲烷测试时可进行许多吸附/解吸循环。然而,可商购的天然气引入现有的吸附储存罐时,孔径统计分布对天然气的天然气成分统计分布的不匹配导致吸附剂混合物中的孔被较大分子成分堵塞。较大分子被卡在较小的孔中。最终,现有的吸附剂不能完全释放较大分子成分,并且在若干吸附/解吸循环后,现有吸附剂中吸附和解吸天然气的能力下降。每一循环使得更多的吸附剂作为吸附剂无效,因为每当现有的吸附储存罐填充天然气时,较大分子与更多的孔接合。
在本公开的示例中,选择吸附剂中孔的孔径统计分布以匹配天然气中成分的混合物。图2描述了美利坚合众国管道天然气的典型组成。如图2所示,管道天然气的成分21可在摩尔百分比25的范围中找到。由于成分21分子的统计分布由成分21的摩尔百分比25限定,所以使用摩尔百分比25。在本公开的一种示例中,吸附剂中的孔具有与图2描述的管道天然气成分21的摩尔百分比25相匹配的孔径统计分布。在示例中,吸附剂孔的孔径统计分布可包括:约70%至约90%的具有10至12埃孔径的总孔;约0.1%至约20%的具有12至13埃孔径的总孔;约0.1%至约1.5%的具有13至14埃孔径的总孔;约0.1%至约8%的具有15至17埃孔径的总孔;以及大于约17埃的剩余百分比,剩余百分比中平均孔径为约20埃。
图3描述了基于平均摩尔百分比的管道天然气成分的孔径统计分布。在图3描述的示例中,80mol%的天然气是甲烷;并且80%的孔具有10-12埃的孔径。甲烷对孔径为10-12埃的孔具有亲和力。10mol%的天然气是乙烷;并且10%的孔具有12-13埃的孔径。乙烷对孔径为12-13埃的孔具有亲和力。1mol%的天然气是丙烷;并且1%的孔具有13-14埃的孔径。丙烷对孔径为13-14埃的孔具有亲和力。4mol%的天然气是二氧化碳;并且4%的孔具有15-17埃的孔径。二氧化碳对孔径为15-17埃的孔具有亲和力。5mol%的天然气是其他成分气体;并且5%的孔具有大于17埃的孔径。其他气体对孔径大于17埃的孔具有亲和力。
通常,吸附剂24具有高表面积并且是多孔的。孔的孔径统计分布与天然气各成分的有效分子直径通常一致。“通常一致(Generally aligned)”指较大有效分子直径的摩尔百分比与较大孔径的孔的百分比大致相同。然而,没有有效分子直径与孔径的特定比例。在一种示例中,孔径分布使得存在具有被吸附的最小成分的有效分子直径的孔和具有被吸附的最大成分的有效分子直径的孔。在一种示例中,吸附剂24具有大于约50平方米/克(m2/g)和高达约3000m2/g的Brunauer-Emmett-Teller(BET)表面积,并且包括具有约10埃至约25埃孔径的多个孔。
合适的吸附剂24的示例包括碳(例如活性炭、超活性碳、碳纳米管、碳纳米纤维、碳分子筛等)、金属-有机骨架(MOF)材料、多孔聚合物网络(例如PAF-1或PPN-4)及其组合。合适的金属-有机骨架的示例包括通过连接四面体簇与有机连接体(例如羧酸酯连接体)而构建的HKUST-1、MOF-74、ZIF-8和/或类似物。
吸附剂24在容器12中所占体积将取决于吸附剂24的密度。在一种示例中,吸附剂24的密度可在约0.1g/cc至约0.9g/cc的范围内。填充好的吸附剂24可具有约0.5g/cc的体积或床密度。在一种示例中,100L的容器可包括占约50L的吸附剂量。例如,占约50L的吸附剂量指吸附剂将填充50L的容器。然而,应当理解,在吸附剂的孔中和吸附剂颗粒之间存在可用空间,并且在100L的容器中具有占50L的吸附剂不会减少天然气容器的容量50L。
本公开包括制备用于可释放地储存天然气的吸附剂的方法,包括在预定质量比的第二吸附剂的存在下共结晶第一吸附剂以产生带有分级扩散路径的共结晶吸附剂。在本公开的示例中,第一吸附剂可以是金属有机骨架(MOF),而第二吸附剂可以是碳填料。在一种示例中,MOF可以是Cu-BTC(铜苯-1,3,5-三甲酸),而填料可以是碳气凝胶和碳纳米管。BTC也被称为均苯三甲酸。
MOF是一类具有广泛应用的多孔、结晶材料。MOF由金属离子或簇组成,其用作接头,通过多向有机配体(用作网络结构中的连接体)结合。这些网络可以是1-D、2-D或3-D延伸的周期性结构。接头和连接体以这样的方式组装,形成规则阵列,从而产生类似于沸石的坚固(通常多孔)材料。基于材料显示出的气体吸附等温线的类型,一些现有的MOF是由IUPAC定义的微孔(孔径小于2nm(20埃))。通过改变有机单元,MOF可为给定应用提供定制材料。例如,有机连接体的长度可限定给定材料所得孔的尺寸。此外,有机单元的官能化可以提供官能化的孔。MOF通过组合不同的金属(例如Al、Cu、Fe和Zn)和不同的有机连接体(例如BDC(双-(9-辛氨基(2-二甲基氨基乙基)吖啶-4-甲酰胺)和BTC)来提供不同孔形状和尺寸的选择。
Cu-BTC是一种铜基MOF,也被称为HKUST-1和MOF-199。在溶剂热条件下形成蓝色立方晶体。在这些条件下,CuII叶轮二聚体很容易形成为方形平面构造块,并且通过用作三角平面构造块的均苯三甲酸三阴离子连接。然后将这些晶体交换到低沸点溶剂并在真空、高温下抽空以产生多孔材料。在抽空前,溶剂分子(通常为水)填充CuII叶轮的轴向配位位置。Cu-BTC的Langmuir表面积可以是约2200m2/g。
在本公开的一种示例中,上述制备Cu-BTC的方法通过在溶剂热结晶过程中加入碳填料颗粒(例如粉状碳气凝胶和碳纳米管)而改变。上述Cu-BTC结晶改性为共结晶过程,其中Cu-BTC结构围绕碳气凝胶和碳纳米管生长。碳填料颗粒因此被插入到Cu-BTC晶体中。与碳填料颗粒的共结晶改变了如图4示意性示出的Cu-BTC晶体的孔径。
在本公开的示例中,共结晶可包括连接体酸与结构构造单元源的溶剂热反应。该结构构造单元源可以是例如金属硝酸盐或金属硫酸盐。该连接体酸是共结晶吸附剂有机配体的来源。因此,共结晶吸附剂可包括如本文所公开的MOF。在示例中,溶剂热反应可以在帕尔(Parr)酸浸高压容器中,于约85℃至约105℃下在N,N’-二乙基甲酰胺或水中进行约24小时。
图4是描述根据本公开的与碳颗粒29共结晶的Cu-BTC 27的示意图。该共结晶的Cu-BTC碳30限定分级孔。除了由典型Cu-BTC晶体限定的孔之外,共结晶的Cu-BTC碳30限定小微孔31、较大微孔32和中孔33。
根据本公开,通过共结晶合成的吸附剂可混合在一起以形成带有孔径统计分布的吸附剂的均匀混合物。在本公开的另一示例中,共结晶可以同时用一种以上的填充材料进行。以这种方式,吸附剂中的分级孔将具有通过改变填充材料的量和种类来定制的统计分布。
为进一步说明本公开,本文给出了示例。应当理解,提供这些示例是为了说明的目的,而不应解释为限制本公开的范围。
示例1:进行测试以验证HKUST-1的吸附/解吸性能。图6描述了当用超高纯度(UHP)甲烷加压可加压罐时,以克/克计的过量甲烷吸收37相对以巴计的压力38。UHP甲烷的最低纯度为99.99%。图6示出,在9次试验(T1-T9)过程中,过量甲烷吸收在约5%以内是可重复的。图7描述了当用典型天然气混合物成分加压可加压罐时,以克/克计的过量天然气混合物吸收39相对以巴计的压力38。图7描述的示例中使用的天然气特定混合物为己烷0.1032mol%、丙烷2.4mol%、CO2 3.06mol%、乙烷4.16mol%以及甲烷余量。图7示出,在20次试验(t1-t20)中,过量天然气吸收减少了约50%。因此,使用纯甲烷而非具有除甲烷以外的成分的天然气来测试吸附剂,可能无法检测到吸附剂的吸附/解吸性能可在重复的再填充后衰减。
示例2:HKUST-1与碳填料共结晶。对照试样44是带有无共结晶填料合成的HKUST-1吸附剂的罐。试样A 45是与带有HKUST-1吸附剂(与10重量%平均孔径为10nm的碳气凝胶共结晶)的对照罐相似的罐。试样B 46是与带有HKUST-1吸附剂(与10重量%的10nm直径的多壁碳纳米管(MWCNT)共结晶)的对照罐相似的罐。图5是微孔孔径分布49的曲线图,描述了对照试样44、试样A 45(HKUST-1+碳气凝胶)以及试样B 46(HKUST-1+MWCNT)的孔体积34(以mL(毫升)每克每埃为单位)相对孔宽度36(以埃为单位)。对照试样44具有大量约5埃孔宽度的孔和更大数量的约7埃孔宽度的孔。试样A 45(HKUST-1+碳气凝胶)在约6.5埃处具有峰值,在约10埃处和约11.5埃处具有较小峰值。试样B 46(HKUST-1+MWCNT)具有集中在约7埃处的峰值,在约12埃处具有较大峰值,并且在约17埃处具有小峰值。
图8是描述根据本公开的对照试样44HKUST-1、共结晶吸附剂45(HKUST-1+碳气凝胶)和46(HKUST-1+MWCNT)的最大过量天然气吸附41相对填充循环数42的曲线图。图8描述了天然气吸附循环稳定性48。图8示出,通过对照试样44的20次试验,过量天然气吸附持续下降。约6次试验后,试样A 45(HKUST-1+碳气凝胶)稳定。试样B 46(HKUST-1+MWCNT)似乎在11次试验中稳定或甚至增加,但在试样B 46(HKUST-1+MWCNT)第11次试验后未再进行试验。
整个说明书中对“一个示例(one example)”、“另一示例(another example)”、“一种示例(an example)”等的引用指,结合该示例描述的特定元素(例如特征、结构和/或特性)被包括在本文描述的至少一个示例中,并且可以存在或可以不存在于其他示例中。此外,应当理解,除非上下文另有明确规定,任何示例的所述元素可以以各种示例中任何合适的方式组合。
应当理解,本文提供的范围包括给定范围和给定范围内的任意值或子范围。例如,约85℃至约105℃的范围应被解释为不仅包括明确表述的约85℃至约105℃的界限,而且包括个别值(诸如85℃、98℃、102.5℃等)以及子范围(诸如约88℃至约100℃、约90℃至约101℃等)。此外,当“约(about)”用于描述值时,这意味着包括与给定值的微小变化(高达+/-10%)。
对本文公开的示例进行描述和要求权利保护时,除非上下文另有明确规定,单数形式“一种(a)”、“一种(an)”和“该(the)”包括复数指示物。
虽然已经详细描述了几个示例,但应当理解,所公开的示例可修改。因此,前面的描述被认为是非限制性的。

Claims (8)

1.一种用于天然气的吸附储存罐,包括:
设置在交通工具上容纳所述天然气的可加压罐;和
设置在所述罐中的天然气吸附剂,其中,
所述天然气是具有分子长度和动力学直径的成分统计分布的成分的混合物;
所述吸附剂具有孔径的孔径统计分布以吸附和解吸成分的所述混合物;以及
所述天然气可作为燃料被所述交通工具消耗。
2.如权利要求1所述的吸附储存罐,其中所述吸附剂的孔径的物理分布在所述可加压罐中是均匀的。
3.如权利要求1所述的吸附储存罐,其中所述天然气包括甲烷、乙烷、丙烷、己烷和氢气。
4.如权利要求1所述的吸附储存罐,其中所述天然气包括约78mol%至约96mol%的甲烷,和随所述非甲烷烷烃的摩尔质量增加而比例减少的非甲烷烷烃。
5.如权利要求4所述的吸附储存罐,其中所述吸附剂中所述孔的孔径的所述孔径统计分布包括:
约70%至约90%的具有10至12埃孔径的所述总孔;
约0.1%至约20%的具有12至13埃孔径的所述总孔;
约0.1%至约1.5%的具有13至14
埃孔径的所述总孔;
约0.1%至约8%的具有15至17
埃孔径的所述总孔;
以及大于约17埃的剩余百分比,所述剩余百分比中平均孔径为约20埃。
6.如权利要求1所述的吸附储存罐,其中所述吸附剂选自碳、金属-有机骨架(MOF)材料、多孔聚合物网络及其组合组成的所述组。
7.如权利要求6所述的吸附储存罐,其中所述吸附剂包括带有分级扩散路径的MOF。
8.如权利要求1所述的吸附储存罐,其中所述吸附剂为与碳气凝胶和碳纳米管共结晶的Cu-BTC。
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