CN1137418A - 去除气流中的二氧化碳 - Google Patents

去除气流中的二氧化碳 Download PDF

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CN1137418A
CN1137418A CN96104114A CN96104114A CN1137418A CN 1137418 A CN1137418 A CN 1137418A CN 96104114 A CN96104114 A CN 96104114A CN 96104114 A CN96104114 A CN 96104114A CN 1137418 A CN1137418 A CN 1137418A
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clinoptilolite
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M·布洛
L·道
F·R·菲奇
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Linde LLC
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Abstract

一种从气流中除去CO2的方法，是将气流通过天然或合成的斜发沸石或其化学改性的衍生物床层吸附除去气流中的CO2。利用本法在高于20℃的温度去除气流中的ppm级的CO2，尤其具有优越性。

Description

去除气流中的二氧化碳
本发明涉及从气流中去除二氧化碳，具体涉及在空气分离前去除其中的CO2进行空气的预净化。
自然界及工业产生的各种气体常含有少量CO2，例如，大气中通常含有约300或300ppm以上的CO2。由于某些方法的制约或是气体的特定最后用途，有时需要从该气体中去除CO2。例如，空气将采取低温蒸馏(深冷空气分离)分离成各种组分产物时，它就必须基本上不含CO2和水汽。低温空气分离需远在二氧化碳和水的凝固点以下的温度进行。所以如果不在空气冷却之前将这些组分预先去除，它们会结冰，最终堵塞空气分离的设备。
可以用多种方法去除气流中的CO2和水汽，例如冷凝，逆热交换冷冻和吸附。一种特别优选的方法是利用一种对CO2(和水汽)吸附作用强于对气流中其它组分的吸附剂进行的吸附。例如，常令气流通过13X分子筛床层来去除有待进行低温分离的空气流中的CO2。1975年5月27日授权于Sherman等的美国专利3,885,927揭示了，利用至少含90％(当量百分率)钡阳离子的X型分子筛，在-40-120°F可由CO2含量不大于1000ppm的气流中去除其CO2。1988年10月4日授权于Rastelli等人的美国专利4,775,396揭示了在-50-100℃利用变压吸附可吸附除去气流中的CO2，该吸附剂为SiO2/Al2O3的摩尔比约2-100，至少含有20％(当量)的选自锌、稀土，氢和铵离子中一种或多种的阳离子，并含有不多于80％(当量)的碱金属或碱土金属离子的一种分子筛。
13X分子筛可在低温下有效去除空气流中的少量CO2(和水汽)，低温指5℃及更低的温度，因为它对上述组分的吸附强于对氮，氧或氩的吸附。但是，在较大的范围内，随被分离气体温度的升高，13X分子筛对CO2的选择性和吸附能力迅速衰减，当温度高于20℃时这个吸附分离的方法就不适用了。由于环境温度常常高于5℃的优选吸附温度，还由于吸附过程中吸附床层会因吸附放热而具有明显升温的倾向，所以常必需用外冷冻法冷却送往以吸附法为基础的空气预净化车间的空气，维持其温度低于20℃。这样做就降低了空气分离过程的总效率，因为为了提供必要的冷冻需要消耗能量。
在以吸附为基础的工业化空气分离预净化过程中，若能完全无需冷冻或是大大减少所需的冷量，这是十分优越的，因为这将增强空气分离过程整体上的经济吸引力。本发明就提供了一种具有此优点的新的CO2吸附方法。
根据本发明，在-50至80℃条件下，将气体通过斜发沸石床去除CO2来净化气体。本发明的方法可用于净化任何在沸石上比CO2吸附弱的气体，其所含CO2杂质不高于1000ppm。可用本发明方法净化的典型气体是空气、氮气、氧气、氩气、甲烷等。
吸附剂可以是天然斜发沸石，或者它可以是与一种或多种选自周期表IA、IIA和IIIA族，镧系离子，铬(III)离子，铁(III)离子，锌(II)离子或铜(II)离子的各种一价，二价，三价离子交换的阳离子。优选吸附剂是其可交换阳离子选自以下一种或多种的斜发沸石：离子态的钠，钾，锂，钙，镁，钡，锶，铝，钪，镓，铟，钇，镧，铈，镨和钕。最优选的阳离子是钠，锂，钙，镁，铝，铈和镧及其混合物。
本发明方法的吸附步骤在约20-80℃进行较有利。在约30-60℃进行吸附，可获得非常好的结果。
CO2净化宜循环进行，最好采用变压吸附(PSA)，变温吸附(TSA)或二者结合。在最优实施方法中，采用TSA法。
用本发明的方法净化的气流中CO2的浓度以不大于600ppm为宜，最好不大于350ppm。
本发明方法可以只有CO2吸附的单一操作，也可以包括CO2吸附和空气分离、氢氧化、CO氧化等中的一种或多种净化操作相结合。在一个优选过程中，是先用前述方法由空气中去除CO2，然后用低温蒸馏法将经上述净化后的空气分离成氮气，氧气、氩气或其中两种或两种以上的混合物。
以斜发沸石吸附剂吸附CO2还可用于去除存在于气流中的水汽，如果存在的话，在一个优选实施例中，例如，将气流通过干燥剂(最好是氧化铝、硅胶或其混合物)在CO2吸附前除湿。
本发明方法特别适用于在约20℃下由气流中去除低浓度(ppm级)的CO2。虽然本发明方法也可成功地用于由气流中去除浓度大于1000ppm的CO2，但当CO2浓度不超过1000ppm时，这种去除更有效。
用于本发明方法的吸附剂是天然的和合成的斜发沸石及其化学改性的衍生物。天然斜发沸石通常带有作为可交换阳离子的钾离子、钠离子、钙离子和镁离子中的一种或多种。阳离子交换的天然或合成的斜发沸石也可用于本发明。可占据斜发沸石吸附剂上可交换阳离子位置的离子，包括周期表中的IA、IIA、IIIA族、IIIB族，镧系元素三价离子，锌(II)离子，铜(II)离子，铬(III)离子，铁(III)离子，铵离子，氢离子或是其中两种或多种的混合离子。优选的IA族离子是钠、钾、锂离子；优选的IIA族离子是镁、钙、锶、钡离子；优选的IIIA和IIIB族离子是铝、钪、镓、铟、钇离子；优选的三价镧系离子是镧、铈、镨、钕离子。最优选的斜发沸石具有选自以下一种或多种的可交换阳离子：钠、钾、锂、钙、镁和钡离子的天然和合成的斜发沸石。
本发明方法可以仅在一个吸附容器内进行，也可以在由两个或多个平行放置且采用吸附和解吸循环操作的床层组中进行。在这样的系统中，两床层一床吸附，另一床解吸，以保证从吸附系统出来的净化气流是准连续的。
本发明方法常以循环法实施，例如变温吸附，变压吸附、真空变压吸附、或其组合。本方法采用变温吸附去除空气中少量的CO2特别有用。此方法的去除CO2过程与某种空气分离过程例如空气的低温蒸馏相结合是尤其理想的，这样就生产出高纯氮、氧、氩或其中两种或多种的高纯气体产品。
吸附步骤的操作温度可在约-50℃(低最)至80℃(最高)的范围内变化。现已发现，升高吸附温度，吸附过程的效率不会象在该过程中使用常规吸附剂时那样迅速下降。这一特点使本方法具有可在吸附过程中温度高于20℃，甚至高于40℃的温热气候中使用的优点。虽然吸附步骤可在高达80℃进行，温度仍以不高于60℃为宜，不高于50℃最佳。
吸附步骤操作的绝对压力通常在约2×104-2×106Pa(0.2-20bar)之间，以约1×105-1.0×106Pa(1-10bar)为佳。
如果吸附过程采用PSA，再生步骤的操作温度一般与吸附步骤温度相近，而其压力低于吸附压力。PSA循环中再生压力一般约在2.0×104-5×105Pa(200-5000mbar)，约以1.0×104-2.0×105Pa(100-2000mbar)为佳。当吸附过程采用TSA时，床层再生温度则高于吸附温度，一般约在50-250℃之间，约以100-200℃为佳。在TSA实例中，压力可与吸附和再生步骤中的压力相同，但通常优选在大气压下解吸。当使用PSA/TSA过程的组合时，床层再生时的温度和压力分别高于和低于吸附时的温度和压力。
本发明循环过程开始时，将有待去除CO2的原料气体流引入其中有前述吸附剂床层的吸附容器中。当气体流过吸附剂床层时，CO2被吸附，基本上不含CO2的不被吸附的产物气体由不吸附气体出口从容器流出。随着吸附过程的进展，吸附剂床层中形成一个含CO2的前沿，该前沿向床层末端的不吸附气体出口缓慢移动。在吸附进行过程中，当被吸附CO2的前沿穿过吸附容器移动至容器中一个预定的合适位置时，即终止该容器中的吸附过程，然后将其转入再生阶段。在再生过程中，对吸了CO2的容器减压(如果吸附循环是变压吸附)；加热(如果采用的是变温吸附)；或同时减压和加热(如果采用的是变压和变温结合的过程)。
吸附床再生的方法取决于所用吸附过程的类型。采用变压吸附时，再生阶段通常包括逆流减压步骤，此时对床层逆流抽气直到达到所需的低压力。如果需要，可以利用抽真空设备，如真空泵，使床内压力降至大气压力以下。
有些时候，除了逆流减压步骤外，可能还需要采用从吸附剂床层排出的不吸附产物气流来逆流吹洗床层的步骤。在这种情况下，床层就可以用不吸附气体逆流吹洗之，而吹洗步骤通常于逆流减压临近结束时，或在其结束之后开始。吹洗过程中，当整个系统只有一个吸附容器时，吹洗气体可由一个中间的储器引入吸附剂床层；而当吸附系统有多个平行布置且异相运作的吸附容器时，吹洗气则可由另一个处于吸附阶段的容器引入。
吸附循环除包括吸附和再生这两基本步骤以外，还可包括其它一些步骤。例如，较有利的做法可以是分步进行吸附床的减压，其中第一减压步骤的产物被部分用于吸附系统中另一床层的加压。这种做法会进一步减少不吸附气体产物中的气体杂质。
根据本发明的一个优选实施方法，一股气流，例如空气，被引入一个内装前述类型的斜发沸石的吸附容器中。该气流的温度可低至-50℃或更低，或者高达80℃。如果气流中CO2浓度不是明显高于1000ppm，气流中的全部CO2即可基本去除，从吸附容器的不吸附气体产物出口排出的气体产物中基本上不含CO2。当CO2吸附前沿到达吸附容器中某个预定点(它通常靠近不吸附气体产物出口)时，即终止该容器中的吸附过程，以前述方式之一对其中的吸附剂床层进行再生。如果吸附车间中的是一多床系统，则此时立即启动第二床层的吸附过程，这样就不会中断净化过程的连续性。对经净化的气体可进一步处理。例如，在低温空气分离操作中，预净化空气被送入低温蒸馏(或吸附)车间，分馏出一种或多种高纯度气体。如果需要，由空气分离车间产生的废气流可再循环至预净化车间，用作床层再生时的吹洗气体。
应该知道，在本发明范围中还包括了使用常规设备监测及自动调节系统中的气流，以令其有效地完全自动而连续地流动。
下面的实施例将进一步说明本发明，其中若非另作说明，份数、百分数和比值皆按体积计。实施例1
对于硅铝原子比为1.25的常规钠X型沸石(NaX)和首先用热水洗涤处理，然后用80℃的氯化钙溶液进行广泛的离子交换的印度尼西亚天然斜发沸石，在5℃、35℃和50℃，取2×102-3.0×104Pa(300mbar)范围内的一系列不同压力，利用Cahn微天平测定了CO2的平衡等温吸附线。斜发沸石样品(印度尼西亚天然斜发沸石)的化学分析显示其重量百分组成为：64.7％SiO2；13.8％Al2O3；3.9％CaO；2.5％K2O；1.0％Fe2O3；0.8％MgO；0.26％TiO2；0.23％Na2O和0.01％MnO。在第一次测定前和每一温度下等温线的测定之间，在Cahn微天平中在350℃对每一份吸附剂样品(约60mg)都抽真空1.5小时使其活化。每一次测定均进行至达到平衡，对最低的CO2分压来说，平衡需长达3小时。实验结果见表。
表
  压力，102Pa(mbar)   2   5   10   50   100   300
  吸附剂 温度，℃     CO2吸附量，mmol/gm吸附剂
    NaX     5   1.24   1.80   2.23   3.53   4.11   4.79
  Ca Clino.1     5   1.13   1.31   1.46   1.89   2.04   2.18
    NaX     35   0.45   0.87   1.26   2.26   2.78   3.73
  Ca Clino.     35   0.81   1.04   1.17   1.47   1.65   1.93
    NaX     50   0.25   0.55   0.87   1.83   2.27   3.14
  Ca Clino.     50   0.64   0.91   1.07   1.34   1.48   1.76
1钙斜发沸石
此表清楚地表明，在较高的CO2分压(例如3.0×104Pa(300mbar))情况下，用于该实施例中的钙型斜发沸石的CO2吸附能力比常规使用的NaX型吸附剂低得多。本发明的这一意外特性可以从小于或等于5×102Pa(5mbar)CO2(1.52MPa(15大气压)的普通空气)且温度高于20℃的测试结果中显示出来。本发明吸附剂的吸附能力在相同情况下比常规X型吸附剂高20％以上，有时高一倍以上。
虽然上面具体根据一定的设备布局，一定的吸附循环和一定的设备对本发明作了叙述，但这些具体特征只是本发明的例证而已，还可以尝试许多变化的方案。例如，吸附循环可用两床以上的均压步骤，还可根据需要，用或不用吹洗和/或不吸附气体产物反馈的步骤。而且，可以改变每一步的延续时间和操作条件。本发明的范围仅由下面的权利要求书限定。

Claims (12)

1.一种从含有CO2杂质的气流中去除CO2的方法，其特征在于，它包括在-20至80℃使用斜发沸石对所述气流进行吸附。
2.根据权利要求1所述的方法，其特征在于，其中的吸附可以是变温吸附、变压吸附或真空变压吸附，也可以是它们的组合。
3.根据权利要求2所述的方法，其特征在于，其中所述吸附剂是斜发沸石，其可交换的阳离子选自1A、2A、3A、3B族、镧系元素的离子及其混合离子。
4.根据权利要求1或2中任何一项所述的方法，其特征在于所述的吸附剂选自天然斜发沸石、合成斜发沸石、钠交换的斜发沸石、钾交换的斜发沸石、锂交换的斜发沸石、钙交换的斜发沸石、镁交换的斜发沸石、钡交换的斜发沸石及其混合物。
5.根据权利要求1或2中任何一项所述的方法，其特征在于所述气流中二氧化碳的浓度不大于1000ppm。
6.根据权利要求1或2中任何一项所述的方法，其特征在于所述气流是氧气、氮气、氩气或其混合物。
7.根据权利要求6所述的方法，其特征在于所述气流为空气。
8.根据权利要求6所述的方法，其特征在于它还包括，在由所述气流中去除CO2之前，令气流通过选自氧化铝，硅胶，及其混合物的吸附剂以除去其中的水汽。
9.一种分离空气的方法，其特征在于，它包括：
(a)以斜发沸石作为吸附剂，对空气进行变温吸附使空气中的CO2被吸附除去来预净化空气，
(b)对预净化空气进行低温蒸馏，由此产生高纯度的氮气和/或高纯度的氧气。
10.根据权利要求9所述的方法，其特征在于所述吸附剂还从所述空气中吸附除去水汽。
11.根据权利要求9所述的方法，其特征在于它还包括，在步骤(a)之前，进行令空气通过选自氧化铝、硅胶及其混合物的吸附剂，从空气中除去水汽。
12.根据权利要求9所述的方法，其特征在于所述的吸附剂选自天然斜发沸石、锂交换的斜发沸石、钙交换的斜发沸石及其混合物。
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