CN107109987A - 气体存储结构的制造方法 - Google Patents

气体存储结构的制造方法 Download PDF

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CN107109987A
CN107109987A CN201580059142.8A CN201580059142A CN107109987A CN 107109987 A CN107109987 A CN 107109987A CN 201580059142 A CN201580059142 A CN 201580059142A CN 107109987 A CN107109987 A CN 107109987A
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菲利普·卡拉伯尔
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Nergy Automotive Systems Research SA
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/003—Storage or handling of ammonia
    • C01C1/006—Storage or handling of ammonia making use of solid ammonia storage materials, e.g. complex ammine salts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
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    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/06—Adding substances to exhaust gases the substance being in the gaseous form
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
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Abstract

本发明提出一种制造气体存储结构的方法，该方法包括以下步骤：‑在液体中溶解或分散能够通过吸附存储所述气体的盐，以生成溶液；‑将支撑件插入该溶液中；‑加热该溶液直至液体完全蒸发，以使盐在支撑件上堆结。

Description

气体存储结构的制造方法
技术领域
本发明涉及气体存储结构的制造方法。
这样的存储结构适用于通过吸附来存储气体，例如氨或氢气。
这样的存储结构尤其适用于通过SCR(选择性催化还原)减少机动车排放气体中的NOx的还原系统中。
本发明还涉及存储盒和SCR系统。
背景技术
车辆(尤其是柴油车辆)排放气体中的氮氧化物能够通过选择性催化还原技术(一般称作SCR)去除。根据该技术，一定剂量的氨(NH3)在催化剂上游被注入排放管线中，催化还原反应在该催化剂上发生。
已知这样的氨存储系统，其中氨通过吸附被存储在盐上，该盐通常是碱土金属氯化物。一般性地，这样的存储系统包括其中存储有该盐的一个(或多个)存储盒，和用于加热该盐的加热装置。由此，通过加热该盐释放氨。
文档WO 2006/081824描述了一种用于制造氨存储结构的技术，该技术实施对氨饱和的盐的压实。观察到，简单的对氨饱和的盐的压实不能实现令人满意的存储结构(即存储基质)。实际上，被压实的盐的低的热导率抑制了材料内部的热传递，由此延迟了大体积的盐的氨解吸反应的响应时间。此外，与吸附相关的体积的高度增大可能会导致存储结构中的裂缝。该存储结构因此不能够以令人满意的方式重新达到氨饱和。
因此，期望的是提供这样的存储结构，该存储结构能够既高密度地又可逆地存储氨而不损坏该结构。
还期望的是提供这样的存储结构，该存储结构具有优化的效率，尤其是在热传递方面。
发明内容
为此，本发明的主题特别地在于一种用于制造气体存储结构的方法，该方法包括以下步骤：
-在液体中溶解或分散能够通过吸附存储所述气体的盐，以形成溶液；
-将支撑件插入或浸入溶液中；
-加热溶液直至液体完全蒸发，以使盐在支撑件上堆积、凝结、或粘结(agglomération)。
本发明的存储结构包括其上固着有所述盐的支撑件。更具体地说，提出了通过在真空下蒸发而使盐沉积在支撑件的全部或局部上。根据该实施方式，盐颗粒不会产生变形，并获得具有多孔的颗粒结块。该颗粒结块由此形成盐层或盐壳，该盐层或盐壳能够可逆地存储氨，并具有在气体吸附阶段抵抗盐颗粒膨胀的非常良好的性能。
支撑件起到骨架的作用。这样的支撑件可以具有任意的二维或三维形状。由此，本发明的方法能够容易地制造具有复杂几何形状的存储结构。
根据本发明的方法包括这样的步骤：在液体中溶解或分散粉末状的盐。该步骤可以例如借助于高速均化器类型的或往复式的搅拌器来实施。在一个具体实施方式中，实施接近60℃的放热溶解。
根据一个特别有利的实施方式，在水或能够使盐溶解或悬浮的其它溶剂中溶解粉末状的盐。这样的溶剂可以改善烘干和特殊粘结剂的添加。该实施方式简单且有效。而且，这样的实施方式能够获得受控的多孔性基质。
在另一具体实施方式中，可以在水或其它溶剂与添加剂的混合物中溶解或分散粉末状的盐。例如，该添加剂可以是粘结剂，例如纤维素和衍生物、微晶纤维素、硬脂酸镁、明胶、糖、淀粉或诸如PVDF的聚合物，也可以是一种或多种导通填料，例如石墨、碳黑或碳纤维。
根据本发明的方法还包括这样的步骤：将支撑件插入或浸入液体/盐的混合物(即溶液或分散体)。根据一个特别有利的实施方式，以使得支撑件完全浸没在溶液中的方式插入支撑件。在一个具体实施方式中，让支撑件自由地处于溶液中。在另一具体实施方式中，可以使用被配置为用于在溶液中将支撑件保持在预定位置的装置。
根据本发明的方法还包括这样的步骤：加热溶液。例如在烘箱或在炉子中实施的(在正常压强下、在降低的压强下等)该加热步骤(或烘干步骤)旨在使得全部液体蒸发。例如，在该步骤期间实施的烘干可以在90℃-120℃之间的温度下以渐进的方式实施。例如，以带有空气更新的方式或在能够连续工作的水平或竖直炉子中以动态烘干的方式来加热溶液几个小时。
由此，在加热步骤结束时，获得固着在支撑件上的干燥的盐层或盐壳。
在一个具体实施方式中，该支撑件是栅格式的。由此，获得盐在支撑件上更好的粘结。实际上，盐渗透该栅格的全部或部分网眼，以锁固于其上。在一个具体实施方式中，栅格可以完全被盐包裹(即包覆)。
在一个具体实施方式中，栅格包括纺织纤维。例如，纤维由热塑性材料制成。栅格也可以包括碳纤维，以改善热导率和电导率。
热塑性材料是指任何热塑性聚合物(其中包括热塑性弹性体)及其混合物。术语“聚合物”既指均聚物也指共聚物(尤其是二元或三元共聚物)。非限制性地，这样的共聚物的例子有：无规则分布共聚物、序列共聚物、嵌段共聚物和接枝共聚物。
特别地，可以使用聚烯烃、热塑性聚酯、聚酮、聚酰胺及其共聚物。也可以使用聚合物或共聚物的混合物，同样也可以使用具有无机、有机和/或天然填料的聚合性物质的混合物。
例如，栅格可以包括高密度聚乙烯(PEHD)纤维。
在一个具体实施方式中，栅格包括至少一条金属丝线和/或碳丝线。该(些)金属和/或碳丝线可以被用作加热元件。由此，根据本发明的存储结构可以集成丝线加热器。这样的丝线加热器能够确保热量在盐中良好的扩散。
在一个具体实施方式中，栅格可以集成纺织纤维和金属丝线元件。
在一个具体实施方式中，栅格包括至少一个气体扩散管。由此，根据本发明的存储结构可以集成扩散器。由此使得气体在盐中的扩散更便利。
在本发明中，盐能够通过吸附存储任何类型的气体。优选地，气体是氨或氢气。对于存储氨，碱土氯化物类型的盐相当适合。两种盐是特别有利的：氯化锶(SrCl2)和氯化钡(BaCl2)，这是由于当所述盐氨饱和时具有高压强和结晶密度(大约为0.6kg NH3/L)，由此限制了使氨解除吸附所必需提供的能量(对于使BaCl2或SrCl2从20摄氏度的环境温度达到对应于3bar的氨蒸气压强的温度，所需提供的能量分别为5kJ/kg和20kJ/kg)。其它盐也是合适的：氯化钙(CaCl2)、氯化镁(MgCl2)或氯化镍(NiCl2)。
本发明的主题还在于一种存储盒，该存储盒包括一个或多个通过如上所述的方法获得的存储结构。根据本发明的存储盒尤其适于被安装到机动车上。
在一个具体实施方式中，按一定形状成形存储结构(即实行切割)，然后将其插入盒中。然后，将例如氨引入盒中，以给存储结构充装氨。
在第一实施例中，在盒中叠置多个存储结构。在该第一例子中，每个存储结构都包括金属(或碳)栅格。在该第一例子中，金属栅格彼此连接并连接到同一供电电源。
在第二实施例中，在盒中叠置多个存储结构。在该第二例子中，每个存储结构包括金属栅格。在该第二例子中，金属栅格连接到不同的供电电源。
本发明的主题还在于一种机动车的SCR系统，该系统包括一个或多个如上所述的存储盒。

Claims (10)

1.一种制造气体存储结构的方法，该方法包括以下步骤：
-在液体中溶解或分散能够通过吸附存储所述气体的盐，以生成溶液；
-将支撑件插入所述溶液中；
-加热所述溶液直至所述液体完全蒸发，以使所述盐在所述支撑件上堆结，所述盐形成固着在所述支撑件上的壳或层。
2.如权利要求1所述的方法，其特征在于，所述支撑件是栅格。
3.如权利要求2所述的方法，其特征在于，所述栅格包括纺织纤维。
4.如权利要求2至3中任一项所述的方法，其特征在于，所述栅格包括至少一条金属丝线。
5.如权利要求2至4中任一项所述的方法，其特征在于，所述栅格包括至少一个气体扩散管。
6.如权利要求1至5中任一项所述的方法，其特征在于，所述盐从以下盐中选择：氯化锶(SrCl2)、氯化钡(BaCl2)、氯化钙(CaCl2)、氯化镁(MgCl2)或氯化镍(NiCl2)。
7.如权利要求1至6中任一项所述的方法，其特征在于，所述液体是水。
8.如权利要求1至7中任一项所述的方法，其特征在于，所述气体是氨或氢气。
9.一种气体存储盒，该气体存储盒包括至少一个通过如权利要求1至8中任一项所述的方法获得的存储结构。
10.一种机动车的SCR系统，该系统包括至少一个如权利要求9所述的存储盒。
CN201580059142.8A 2014-11-14 2015-11-13 气体存储结构的制造方法 Pending CN107109987A (zh)

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FR1460993A FR3028556A1 (fr) 2014-11-14 2014-11-14 Procede de fabrication d'une structure de stockage d'un gaz
PCT/FR2015/053069 WO2016075419A1 (fr) 2014-11-14 2015-11-13 Procédé de fabrication d'une structure de stockage d'un gaz.

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