CN1012799B - 从含氮混合气中分离氮的方法 - Google Patents

从含氮混合气中分离氮的方法

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CN1012799B
CN1012799B CN88104710A CN88104710A CN1012799B CN 1012799 B CN1012799 B CN 1012799B CN 88104710 A CN88104710 A CN 88104710A CN 88104710 A CN88104710 A CN 88104710A CN 1012799 B CN1012799 B CN 1012799B
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赵建中
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Abstract

已发现高锂交换的X型沸石，特别是含高于90当量%的锂阳离子的，低二氧化硅的X型沸石显示出的氮吸附容量和选择性均为非凡的。这样的吸附剂在从气流如空气和含有极性较小的物质例如氢、氩和甲烷的氮混合物中分离氮具有意外程度的效益。压力摇摆吸附分离法十分适合利用这些吸附剂的特殊性质。

Description

本发明涉及的方法包括选择性吸附气流中的氮。更具体地讲，它涉及使用具有二氧化硅含量很低的、锂交换量高的X型沸石回收气流如空气中的氮。
从含有其它气体例如氧、氢和氩的混合物中分离氮是重要的工业方法。使用这一方法的目的既可能是为了得到一种增加氮的气体产品，也可能是为除去杂质氮的产品。一个较为重要的工业化方法是分离空气制氮和氧。1985年，仅美国就生产了6470亿立方呎的氮和3800亿立方呎的氧。
大部分来自空气中的氮和氧是用低温精馏法生产出来的，使用这种方法是将空气温度冷却到接近空气成分的正常沸点，并在分馏柱中处理，通常需要大量的液-气接触手段，例如多孔板塔盘。低温分离系统昂贵的成本仅在需要大量产品时才被认为是合理的，例如炼钢业用氧，对需要量较少的生产来说，也可通过变压吸附法（Pressure    Swing    adsorption（PSA）Processes）生产氧和氮。采用PSA法时，将压缩空气用泵打进一个显示优先吸附一种主要成分的吸附剂固定床，借此，获得的气体产品中未被吸附的（或吸附较少的）组分含量提高了。与低温法相比，PSA空气分离法需要的设备较简单，因而维修也较容易。但是PSA法较低温法回收产品率低，而能源消耗高。由于这些原因，吸附法的改进仍然是重要的目标。改进的一个主要手段是发现和研究出更好的吸附剂。
使用结晶沸石分子筛作为氮的，特别是从空气中，选择性吸附剂 是众所周知的技术。在美国3，140，931号专利中，McRobbie建议一般等级的具有孔径至少为4.6埃的沸石可用于分离氧-氮混合物。Mckee在美国3，140，932号专利中建议在氧-氮混合物的分离中，使用至少含有锶、钡或镍组中的一种作为阳离子的特殊X型沸石为氮吸附剂。Mckee在美国3，140，933号专利中论述了各种碱金属阳离子型沸石，包括有关X型沸石的优点，并且还发现锂离子型的对选择性吸附空气中的氮是优越的。然而这一优越性是相对于钠X型沸石吸附剂而言的。这种钠X型沸石吸附剂的吸附性质不如其它的用于氮分离工艺中的钠X型沸石。因此，锂X型沸石到目前为止尚未在氮分离方法中作过工业化的应用。而且作为一种氮吸附剂它的真实潜力还没有被认识到。发现在70°F和5-30Psig压力条件下，对氮和氧的吸附容量锂X型沸石不如同种沸石的钠阳离子型的，这一事实的证据在Mckee的专利发表三年后公开的美国3，313，091（柏林）号专利中可见。最近Sircar等人在美国4，557，763号专利中提出二元离子交换型的X型沸石是吸附空气中氮的最佳吸附剂。根据Sicar等人的发现，有5-40%的可利用的阳离子部位被Ca离子所占，而60-95%是被Sr++阳离子所占。Coe等人在美国4，481，018号专利中提出，适当地维持所规定的活化条件，具有Si/Al骨架比为1-2的多价阳离子型八面体沸石，特别是Mg++、Ca++、Sr++和Ba++阳离子型，是良好的空气中氮的吸附剂。
现已发现骨架Si/Al2摩尔比约为2.0-3.0，最佳的是从2.0-2.5，以及至少有88%，较佳的至少为90%，最佳的至少是95%AlO- 2四面体单元与锂阳离子缔合的锂阳离子X型沸 石，对含有极性较小的或可极化性较小的分子种类，如氧，的气流中氮的吸附显示出一种特殊的容量和选择性。这种LiX吸附剂不仅在氮的分离中而且在纯化方法上，例如PSA空气分离法，以及在从氢、氩等的混合物中分离氮中表现出相当大的改进。这些吸附剂由于对氮的吸附容量在15℃-70℃范围内，特别是20℃-50℃，随着氮分压的增长而例外的增长，因此特别适用于在上述温度以及压力为50-10，000毫米汞柱的条件下进行PSA法的氮分离。
图1表示二元氮载荷（binary    nitrogen    loading）和本发明三种不同的锂X型沸石组合物的分离系数，以及钠X型沸石试样的同种参数。
图2表示在约23℃下，本发明的两种吸附剂和现有技术中的钠X型沸石氮等温线的比较。
本发明是基于发现锂阳离子交换的X型沸石在非常高氮浓度交换时显示出对氮的吸附特性，是完全无法从含锂阳子86当量%或低于此值而其余主要的是钠阳离子的LiX试样获得的数据所能予言的。进一步的发现是X型沸石骨架中的AlO- 2四面体单元的相对比例从TO2单元总量的44.4%增加到50%时，随着Li+的相应增加，即在各种情况下，Li+当量%相同，但沸石对氮的吸附容量和选择性的增长较依据阳离子数目的增加所予期的要大得多。这些改进通过下面所列数据将得以证明。
在制备获取数据的吸附剂主体中，采用两种类型X型沸石原料，一个具有的SiO2/Al2O3）比为2.5，而另一个的比约为2.0。按照1959年4月14日发表的R.M.Milton的美国专利2，882，244号的技术，采用硅酸钠和铝酸钠以及水作为试剂，在大 约100℃的温度下，用水热法合成了2.5NaX，反应混合物具有下列成分，以氧化物摩尔比表示：
3.5Na2O∶Al2O3∶3.0SiO2∶144H2O
按下列所述程序合成X型沸石具有的Si/Al2比为2.0是钠-钾混合型的，合成的程序不是本发明的一部分。在267克50%的NaoH水溶液中，溶解208克Al（OH）3，边加热边搅拌以生成溶液（a）。溶液（b）的制备方法是将287克85.3%的粒状的KoH溶解于1000克的水中，然后将所生成的溶液与671克50%的NaoH水溶液混合。将溶液（a）缓慢地加到溶液（b）中以生成溶液（c），并将溶液C冷却到4-12℃。溶液（d）的制备方法是将453.25克的40一级硅酸钠（9.6%Na2O，30.9%Sio2）用1131.7克的水稀释。然后将冷却的溶液（c）加到盛在捏和机中的溶液（d）中，并慢速混合3分钟。在最后的混合中，冷却并避免产生过量的机械能对生产高质量的产品是至关重要的。大约4分钟之后才出现胶凝作用。凝胶在36℃熟化2-3天，并在70℃中蒸煮16小时。然后通过过滤分离沸石晶体，滤饼用体积为母液体积的7倍NaoH水溶液（PH＝12）漂洗。漂洗过的产品在4升NaoH溶液（pH＝10）中重新制浆，然后过滤回收并用水漂洗。再次制浆的过程要重复两次以上，并将分离的产品在空气中进行干燥。干燥过的产品在100毫升的1%NaoH溶液中制浆，并使浆状物在90℃温度下保持21小时。过滤后的滤饼在60℃下用1000毫升的NaoH溶液（pH＝12）重新制浆30分钟，并过滤。重新制浆的过程要重复两次以上，然后用过滤法回收固体并用NaoH水溶液（pH＝9）洗涤，最后在空气中干燥。
使用上述制备的2.5NaX，按下述程序生产沸石“预成型”（Preform）团块：采用pH＝12的主要是由氢氧化钠和水组成的苛性水溶液洗涤原始沸石晶体，然后用水洗涤至pH＝9。再将洗涤过的沸石晶体与AVery粘土（一种商业上可得到的高岭土类粘土）混合，其混合比为80重量%的沸石和20重量%的粘土。再使沸石-粘土的混合物与足够量的水化合，产生一种具有足够湿强度、用来挤压造粒的挤压块，在后续加热工序中处理。在加热工序中，当温度达到650℃时，在约1小时的时间内，高岭土就转变成一种活性偏高岭土。继续加热后，冷却化学键合团块，于约100℃下的苛性水溶液中浸泡和蒸煮，以使大部分的偏高岭土转变成沸石晶体，主要是X型沸石晶体。蒸煮过的团块从苛性碱蒸煮液中移出，再用新配制的pH＝12的NaoH水溶液洗涤，最后用水洗涤至pH＝9-10，于空气中干燥。把经过干燥的产品颗粒破碎过筛以生成16×40目大小的颗粒。第一部分筛分颗粒在真空中于375℃下加热活化约2.5小时。用这种方法时要仔细地完成活化以使NaX型沸石晶体不致受到由包藏的和/或吸附的水而形成蒸汽造成的过度水热处理。该活化试样在下文称为试样“2.5NaX”。
第二部分未活化的筛分颗粒要经离子交换程序，因此，颗粒在一个玻璃柱中与1.0摩尔的氯化锂水溶液接触，该溶液用LioH调节pH为9.0，温度为80℃。使用大量的氯化锂溶液，以使沸石颗粒与4倍于化学计量的过量锂离子接触约19小时以上。从玻璃柱流出的离子交换溶液不循环。所得到的离子交换产物用LioH将pH调整到9.0的水洗涤，发现经过离子交换的占94%。该种产品在下文中称为试样1″号。
试样2.5NaX的其余部分采用上述使用氯化锂水溶液（用LioH调节pH＝9）的柱技术进行离子交换，Licl使用量既可少于也可大于4倍以使生成的产物锂阳离子的含量不同。通过这一程序，所获得的材料Li+阳离子的含量为全部阳离子总量的72当量%-100当量%。在下文中这些材料分别称为试样1号和2号。
关于表1中的试样3-16号的离子交换沸石组合物，锂阳离子当量%为72-100的LiX组合物的系统（array）是用类似于制备上述试样1和2号的柱离子交换程序产生的。X型沸石的锂离子交换是一个困难的过程。该过程的效率在很大程度上取决于柱的尺寸和填充条件。通常，我们发现3呎的柱和过量12倍化学计量的锂盐是足以能生产出具有94当量%或更多的锂离子含量的产物。在试样3-16号的制备中，未活化的X型沸石颗粒在玻璃柱中进行离子交换，使用浓度为0.1-3.0摩尔的用LioH调整pH值约为9的氯化锂水溶液。在每一种情况下所用Licl溶液的量都在锂离子过量4-12倍之间，时间为3-19小时以上。
通过上述方法制备的低二氧化硅的2.0NaKX试样，采用氯化锂水溶液（用LioH使pH＝9）进行离子交换，使碱金属阳离子被锂阳离子置换所达含量约为99当量%。该物料为粉末状的，在下文称为试样“2.0LiX（99%）”。
以上每一种规定的试样都用一种或多种方法进行检验以确定其对纯氮或对含其它少量极性分子混合物中的氮的吸附性质。
用常规的McBain吸附体系，13种试样均在真空条件下于375℃加热16小时进行活化，在氮压力为700毫米汞柱，室温即23℃下，检验其对纯氮的吸附容量。离子交换的详细资料、团块颗粒的尺寸、测定的每种沸石的阳离子总量以及吸附试验的结果均列于下列表中。
Figure 88104710_IMG2
Figure 88104710_IMG3
具有不同的离子交换容量和不同的Si/Al2摩尔比的锂-交换的NaX试样的二元吸附性质相互进行比较，并与未交换的NaX原料比较。为了这一测定目的，一种合成的空气流（20%氧，80%氮）通过一个含有检验试样的填充床，选择1、2和4个大气压，直至吸附平衡，即流出的气流成分与原料相同。然后用氦气流解吸附床，并用气相色谱仪收集和分析解吸剂（desorbate）。然后用公式计算吸附分离因子α（N/O）：
α(N/O)= (吸附的［N2］×原料［O2］)/(吸附的［O2］×原料［N2］)
式中〔N2〕和〔O2〕表示二种状态下体积浓度。所得数据列于下面的表Ⅱ和图2中。
表Ⅱ
试样，压力，N2载荷，分离系数
No. Atm. mmol/gm ads＊. V（N/O）
2.5NaX    1    0.2    3.2
2.5NaX    2    0.7    3.1
2.5NaX    4    1.2    2.5
2.5LiX（85%）    1    0.55    4.0
2.5LiX（85%）    2    0.80    3.6
2.5LiX（85%）    4    1.1    2.7
2.5LiX（94%）    1    0.93    6.2
2.5LiX（94%）    2    1.20    5.5
2.5LiX（94%）    4    1.62    3.8
2.0LiX（99%）    1    1.03    10.9
2    1.70    6.0
4    2.30    4.9
＊gm.ads.＝吸附剂的克数
使用一种市售的Sartorlus微量天平，测定高交换量的LiX、中等交换量的LiX和NaX原料的室温下纯N2等温线。所获数据以图解形式表示在图1中。这些数据清楚地表明了室温下高交换量的LiX优越于已知的锂阳离子含量为86当量%或更少的锂交换的NaX，这不仅表现在任一给定压力下的氮容量上，而且就是对PSA氮方法是如此重要的δ的载荷也是这样。取自图2的并以重量%计 的在150-1500毫米汞柱之间操作的这些δ载荷值列表如下：
150torr下的    1500torr下的
载荷    载荷
试样    形状    重量%    重量%    △载荷
2.5NaX    16×40目    0.29    2.34    2.05
2.5LiX（94%）    16×40目    0.83    3.81    2.98
2.0LiX（99%）    粉末    1.22    5.31    4.09
上述数据证实LiX的氮吸附载荷和沸石的锂含量具有极不寻常的关系。如图1数据所示，在23℃和700毫米汞柱下，80%锂交换的NaX沸石的氮载荷基本上与不含锂阳离子的具有相同Si/Al2比的NaX沸石相同。但是如果锂交换容量从80%增加到99%，则氮载荷从1重量%提高到2.7重量%。在0℃时，锂交换量为99%的NaX吸附大约为4.0重量%的氮。这一点比NaX沸石提高了120%，而且比已知技术报导的锂交换量为86%的NaX，其氮吸附容量已提高了39%也超出了许多。
与低交换量的LiX相比，高锂X有较高的氮选择性。图2中的二元吸附试验的结果表示在1大气压下，室温，交换量为85%的LiX分离系数为4.2，对比交换量为94%的LiX为6.4。当锂交换容量超过85%以后，LiX与NaX之间的差别开始加大。
更为奇怪的是还发现在700毫米汞柱和室温下，二氧化硅和氧化铝比值为2.0的交换量为99%的LiX，其氮容量比交换量为99%的LiX2.5高32%。这意味着它的氮容量比离子交换量 为80%的LiX2.5（图1）高250%。在0℃和700毫米汞柱下，对比LiX2.5氮吸附容量为4.0重量%，NaX吸附氮为1.8重量%，LiX2.0可吸附氮为5.4重量%。
还发现LiX2.0的氮选择性高于具有相同锂交换容量的LiX2.5。如图2的数据所说明的在室温及1个大气压空气混合物中，LiX2.0的分离系数为11，对比LiX2.5为6.4，NaX为3.2。
一个好的PSA空气分离吸附剂应具有较高的δ载荷（在工艺过程循环中，吸附和解吸压之间的载荷差），在发生吸附现象的压力条件下，氮选择性超过氧。已经发现当温度在约15℃和70℃之间，最好是20℃和50℃之间，压力在约50毫米汞柱和10，000毫米汞柱之间采用PSA吸附法时，特别适合使用本发明的吸附剂。

Claims (7)

1、一种从含极性较小的物质的含氮混合气中选择性吸附氮的方法，包括在50-10000毫米汞柱操作压力和15-70℃操作温度下，使所述气体混合物与具有骨架SiO2/Al2O3摩尔比不大于3.0的并至少具有88%的与锂阳离子缔合的AlO2四面体单元的晶体X型沸石吸附剂接触。
2、根据权利要求1所述的方法，其特征为X型沸石吸附剂的骨架SiO2/Al2O3摩尔比为2.0-2.5。
3、根据权利要求1所述的方法，其特征为X型沸石吸附剂至少有99%的AlO- 2四面体单元与锂阳离子缔合。
4、根据权利要求2所述的方法，其特征为X型沸石吸附剂至少含有95%的AlO- 2四面体单元与锂阳离子缔合。
5、根据权利要求3所述的方法，其特征为含有极性较小的物质的氮混合气的主要成分是氮和氧。
6、根据权利要求5所述的方法，其特征为氮和氧的混合气与X型沸石吸附剂相接触。
7、根据权利要求1所述的方法，其特征为温度从20℃到50℃。
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AU608018B2 (en) 1991-03-21
EP0297542A3 (en) 1989-05-03
FI883102A0 (fi) 1988-06-29
ZA884658B (en) 1989-03-29
CA1312830C (en) 1993-01-19
FI883102A (fi) 1988-12-31
IN171668B (zh) 1992-12-05
BR8803207A (pt) 1989-01-17
FI86512C (fi) 1992-09-10
JPH0525527B2 (zh) 1993-04-13
KR890000342A (ko) 1989-03-14
IL86918A0 (en) 1988-11-30
MX165432B (es) 1992-11-11
FI86512B (fi) 1992-05-29
US4859217A (en) 1989-08-22
EP0297542A2 (en) 1989-01-04
ATE84436T1 (de) 1993-01-15
AU1854588A (en) 1989-01-05

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