CN1014587B - 二氧化碳在沸石上的选择性吸附 - Google Patents

二氧化碳在沸石上的选择性吸附

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CN1014587B
CN1014587B CN88108824A CN88108824A CN1014587B CN 1014587 B CN1014587 B CN 1014587B CN 88108824 A CN88108824 A CN 88108824A CN 88108824 A CN88108824 A CN 88108824A CN 1014587 B CN1014587 B CN 1014587B
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亨利·拉斯泰利
德什·拉治·加格
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Union Carbide Corp
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Abstract

在一个固定吸附床上采用压力变化吸附工艺使二氧化碳选择性吸附，从而与如氮、氢和甲烷这样的非酸性气体分离，该吸附床含有一种八面沸石型的铝硅酸盐沸石，该沸石含有至少20当量百分数的选自锌、稀土、氢和铵中的至少一种阳离子，并含有不大于80当量百分数的碱金属或碱土金属阳离子。

Description

本发明总的来说是涉及从非酸性气体，如氮和甲烷中排除大部分二氧化碳，而特别是涉及使用特定的阳离子型的、有八面沸石型结晶结构的沸石作为选择性吸附剂，以在一个循环工艺中吸附二氧化碳。在该工艺中，解吸是通过降低床压完成的。
迄今为止，已提出了一些从气体混合物中回收或排除二氧化碳的方法，并在工业规模上应用。这些方法差别很大，但一般包括某些形式：溶剂吸收、吸附在多孔吸附剂上或通过半透膜渗滤。这种膜技术主要应用于增强油的回收。在这一方法中，需要将二氧化碳再次注入产油构成物中以从甲烷中就地分离二氧化碳。在这种情况下，低的基建投资和设备费用弥补了较低的CO2纯度和回收率。溶剂吸收方法既可使用化学溶剂，也可使用物理溶剂，并且可有选择性地、有效地排除大量CO2，虽然能耗是一个越来越需要考虑的原因。对于提纯过程，可用钙离子交换型的沸石A从含有CO2的气体混合物中将之有效地排除。但是，由于吸附剂和吸附质之间有很强的亲和力，为有效地解吸CO2就需要热能。为从气体混合物中分离出大部分CO2，最近已提出使用碱金属和/或碱土金属阳离子型的、八面沸石型的沸石，即沸石X和沸石Y。这种工艺被揭示于1986年3月5日出版的欧州专利申请说明书No.0173501中，并且该工艺既可利用压力变化解吸，也可利用不易吸附的清洗气体型再生吸附剂。
现已发现，对于将CO2从其与非酸性气体，如甲烷、氢和氮的混合物中大量分离，锌、稀土、氢或铵阳离子型的、具有八面沸石结构的沸石优于前面提到的碱金属和碱土金属型的沸石。在所说的气体混合物中，CO2含量至少是0.5摩尔百分数，而更可取的是至少5摩尔百分数。这一优势归于在固定床上的变压吸附循环中提高了的CO2产率;并且，尽管前面提到的沸石类型显示出更大的对二氧化碳的选择性，这一优势仍存在。八面沸石型的，具有SiO2/Al2O3摩尔比为2-100，最好是2-20的，并且含有至少为20，而最好至少是40当量百分数的上述阳离子类物质中的一种或一种由两种或多种上述阳离子组成的混合物，及不大于80，最好是不大于40当量百分数的碱金属或碱土 金属阳离子的沸石可被用于吸附温度约-50℃至100℃，吸附压力约0.2至约1000磅/英寸2的固定床过程。低于该吸附压力，并在0.1至500磅/英寸2范围内的压力对吸附剂的解吸是合适的。
洼地垃圾气（Landfill gas）是被覆盖的洼地垃圾中有机物分解的天然产物。该气体主要含有CO2、CH4、H2S、水、氮和氧，并以类似于从天然地质构造中获得天然气的方式在洼地垃圾中掘井而回收。所回收的气体大部分是甲烷和二氧化碳，除去水、硫化氢、氮和其它杂质后，该气体由大致等体积的CO2和甲烷组成。用变压式固定床吸附工艺，完成甲烷与二氧化碳的分离。在本发明之前最广泛使用的吸附剂是钠阳离子型的沸石X，即工业上已知的人工合成的13X。一种典型工艺是在室温下，将原料气体加压到450磅/英寸2用于吸附-提纯阶段。二氧化碳被吸附剂优先吸附，而流出的产物是甲烷。当CO2开始穿透过吸附剂时，通过使床减压至约60磅/英寸2而完成再生。
在含氢气流，如纯氢或含氮混合物（氨合成气）的生产中，一般是用含碳原料与蒸气和/或氧反应，首先生成一氧化碳和氢，接着通过一个催化转变反应，将大部分一氧化碳转化成二氧化碳并产生附加氢，从而得到含氢原料气流。在这些情况下，空气或富氧空气用作氧源，即一种辅助的或不完全的氧化阶段的氧源，该原料气流中含有氮和其它惰性气体，如氩。氨合成气的制造通常使用这样一种将氮引入原料气体的辅助变换阶段。在蒸汽重整过程中的含碳原料气是天然气时，产品气体混合物的约1-5%是氮。在从这种原料气体中除去二氧化碳时，有人建议使用活性炭。有人提出了使用钙离子交换型的沸石A和沸石X来排除氮。G·Reiss（美国专利US4，477，267）发现，沸石X远优于沸石A。
现已发现，可用变压型的分离工艺将CO2从如洼地垃圾气这样的气体混合物或从其它非酸性气体混合物中与甲烷大部分地分离出来，其结果较好。如果温度保持在-50℃至+100℃，最好是20至50℃的范围内;吸附压力为2-1000磅/英寸2，解吸压力低于吸附压力，在0.1-500磅/英寸2的范围内;所用的沸石吸附剂具有八面沸石型的结构，其SiO2/Al2O3摩尔比为2-100，并且含有至少20当量百分数的一种选自锌、稀土、氢和铵的阳离子或一种由两种或多种这些阳离子组成的混合物，而且还含不超过80当量百分数的碱金属或碱土金属阳离子。
所用的八面沸石型的沸石既可是X型的，又可是Y型的。X型沸石及其制备方法已在美国专利US2，882，244（1959，4，14授权于R.M.Milton）中进行了描述。沸石X的SiO2/Al2O3摩尔比是约从2最大到3。在如人工合成的型式中，沸石Y的SiO2/Al2O3摩尔比为大于3最大到6。美国专利US3，130，007（1964，4，21授利于D.W.Breck）详细公布了合成沸石Y的方法。BiO2/Al2O3摩尔比大于6的Y型沸石可用几种本技术领域熟知的脱铝酸盐的方法制备。如P.K.Maher等在“分子筛沸石”（Advan.Chem.Ser.101，American Chemical Socie-ty，Washington，D.C.，1971，P.266）中曾报导过用高温蒸汽处理脱铝酸盐的方法。最近报导，一种对提高沸石Y的SiO2/Al2O3特别适用的方法，包括脱铝酸盐及用硅取代其晶格位置。这工艺公布于美国专利US4，503，023（1985，3，5授权于Skeels等）中。这里所用的术语“八面沸石型结构”指的是其框架结构，不管其化学组成、不同T-原子的分布、晶胞尺寸及对称性。这在“沸石结构类型图谱”（W.M.Meier and D.H.Olsen.Structure Commission of the Interna-tional Zeolite Association出版，1978）中称为“FAU”。
在将CO2大部分地与CH4分离时，选择性和产率是两个重要的判断标准。选择性是吸附剂从两种或多种组分的混合物中优先地吸附一种组分的程度，用分离系数α来定量表示。在一个二组分气体混合物中分离系数可由二元平衡吸附值得出。如果吸附相的组成与气相组成相同，则该吸附剂对每个组分都没有选择性，其由下式定义的分离系数为1。
α＝（Ma×Mg）/（Mg×Na）
其中Na和Ma是吸附相中两种吸附质N和M的摩尔分数，Ng和Mg是气相中N和M的摩尔分数。当α值大于1时，Ma代表优先吸附组分，α值越大则吸附剂对M组分的选择性就越大。产率可用优先吸附组分在吸附阶段结 束时和解吸阶段结束时吸附量之差，即在吸附剂上选择性吸附组分在一个吸附-解吸压力变化循环过程中，在其最高分压和最低分压时吸附量的差来确定。
本技术领域熟知，目前不可能从气体混合物纯组分的等温吸附线预测气体混合物的吸附特征。按Langmuir方程式假设的理想状态（即吸附剂表面在能量上是均匀的）计算的结果，由于实际状态与理想状态之间的差异是不能应用的。按照Langmuir方程式，分离系数必然是与气体的压力和浓度无关的，但已充分证明，吸附相的组成会随压力的变化而发生很大的变化，如氮和氧的混合物在沸石吸附剂上吸附时。因此，有必要通过实验手段为任何一个具体的分离过程寻找良好的吸附剂。
在本发明的实验过程中，实验是在模拟目前实际应用的把CO2从气体混合物中与CH4分离这一变压吸附循环中的吸附剂的性能下进行的，这种气体混合物既对经初步提纯后的从洼地垃圾场得到的气体混合物是典型的，又对经与本发明过程一致的适当处理所得其它气体混合物是有代表性的。所用的设备由一个不锈钢圆柱形试样管构成，该管约长1.5英寸，直径0.375英寸，可容纳1-2克试验用吸附剂，在管的每一端有关闭装置以便在实验过程需要的时候隔绝管内物料。在管的每一端还有与导管相连的装置，以便在试样活化和吸附过程中将气流引入管内，并导出由管内流出的气体进入收集和分析装置。有一个适于密封该管并控制试验吸附剂温度的加热室，以及一个采用硅胶柱的气相色谱仪。在试验过程中，试样管中装入20至50目的粒状试验吸附剂，并接入试验装置系统，以便温度为350℃的氦气流通过该管除去水以及原始试样中存在的其它吸附质（使用硅胶试样时，活化温度为200℃）。这种清洗活化过程持续大约16小时，在此期间，试样管冷却到室温。通过测量管中氦气压由50磅/英寸2下降到15磅/英寸2期间自试样管流出的氦气的体积来确定试样管中的空隙体积。此后，通过调节加热室的温度将试样管及其内部物料的温度调到实验所需要的温度，并将二氧化碳和甲烷的原料混合物在约300磅/英寸2的压力下，在约30分钟内通过该管。通过比较试样管流出物组成与原料组成可确定达到吸附平衡的时间。当达到平衡时，通过将试样管加热到300℃并使氦清洗气流通过该管，然后将流出物收集在一个2000cc的由Hamilton Syringe公司制造的Syringe收集器中，从而试样管空隙中的物料以及试样吸附剂的吸附相得以收集。然后使收集器中的物料穿过气相色谱仪的硅胶柱以确定吸附质的组成。然后在约30磅/英寸2压力下重复这一侧量过程。最后用带物料的试样管重量与空试样管重量之差来确定活化的试样吸附剂的重量。
按前述工艺测试的吸附剂组成如下：
试样A：钠沸石X，SiO2/Al2O3摩尔比为2.6，用约20%（重量）的粘土粘接成直径约为1/16英寸的圆柱状;
试样B：Davison    Chemical公司制造和销售的商品硅胶，用常规方法在200℃活化;
试样C：锌交换钠沸石，Zn+2阳离子含量为77当量百分数，SiO2/Al2O3摩尔比为2.4;
试样D：稀土交换型的沸石X，R.E.+3阳离子含量为91当量百分数;
试样E：氧化铝粘结的沸石Y，活化前80%铵离子交换的沸石Y含量为80%（重量），SiO2/Al2O3摩尔比为4.9，用20%（重量）的氧化铝粘结;
试样F：锌交换型的沸石Y，Zn+2阳离子含量为67当量百分数，SiO2/Al2O3摩尔比为5.2;
试样G：一种市场上可得到的氧化铝粘结的稀土交换的沸石Y。其沸石Y含有约50当量百分数的R.E.+3阳离子，氧化铝粘结组分约占全部组成重量的20%。样品颗粒为直径1.16英寸的挤出的小丸。
试样H：锌交换沸石×，Zn+2阳离子含量为84当量百分数，SiO2/Al2O3摩尔比为3.0，试样在真空中于350℃活化。
钠沸石X试样对目前处理洼地垃圾气流应用最普通的以沸石X为基础的吸附剂是有代表性的。对于市场上可得到的与CH4相比对CO2有优先吸附的非沸石型吸附剂，硅胶试样也是有代表性的。所得试验结果列于表A中。
从表A的数据可看出一些有意义的事实。钠沸石X吸附剂（试样A）有大的选择系数（30磅/英寸2时α＝98，300磅/英寸2时α＝46），但CO2的δ吸附量较低（4.03%，重量）。钠沸石X吸附剂在目前处理洼地垃圾气的压力变化吸附装置 中是最常选用的。CO2在30磅/英寸2和300磅/英寸2时有高的吸附量表示吸附剂具有直角形的等温线。硅胶试样（试样B）在200℃活化，CO2δ吸附量较好，但CH4吸附量高。与其它的所有被测试的吸附剂相比，CH4的δ吸附量（0.40%，重量）是相当高的，这在本工艺的应用中可能是一个很大的缺点。然而，就本发明的吸附剂而言，可很容易地看出，至少在一个方面它们都优于硅胶和钠沸石X的混合物，并且大部分在不止一个方面上是优越的。ZnX（试样C）的CO2δ吸附量明显地高于NaX，且具有较低的CH4吸附量。ZnX（试样H，经真空活化）具有极低的CH4δ吸附量，其CO2δ吸附量而言，虽然试样D的REX混合物优于NaX，但是其CO2δ吸附量比试样B的硅胶低。REX的CH4δ吸附量仅约为硅胶吸附量的1/3。REX的CO2绝对吸附量优于硅胶，很容易看出，就CO2的δ吸附量而言，铵-氢阳离子型的沸石Y（试样E）大大地优于所有其它被测试的吸附剂，锌交换型沸石Y（试样F）优于除试样E之外的所有其它被测试的沸石试样，而且其CH4的δ吸附量比硅胶的一半还低。试样G的REY混合物具有非常低的CH4δ吸附量及远优于钠沸石X的CO2δ吸附量。
由于上述原因，八面沸石型的SiO2/Al2O3摩尔比大于3的沸石对本工艺而言是较好的，而铵一氢阳离子型的这类沸石则特别好。
表A
压力 α 吸附的CO2吸附的CH4CO2+CH4的 δ吸附量（%重量）
试样 (磅/英寸2) (CO2/CH4) （克/100克（克/100克 总吸附量
吸附剂） 吸附剂） CH4CO2
A    30    98.07    17.22    0.06    17.28
0.11    4.03
A.    300    46.03    21.25    0.17    21.42
B    30    10.36    4.93    0.17    5.10    0.40    10.77
B    300    9.92    15.70    0.58    16.28
C    30.1    21.14    11.13    0.19    11.32    0.04    6.92
C    300    28.83    18.04    0.23    18.27
D    30    15.90    8.37    0.19    8.56    0.14    7.95
D    300    17.90    16.32    0.33    16.65
E    30.3    12.50    11.00    0.32    11.32    0.16    12.02
E    300    17.27    23.02    0.48    23.50
F    30.1    21.43    11.79    0.20    11.99    0.16    10.06
F    300    21.96    21.85    0.36    22.21
G    30    10.34    8.05    0.28    8.83    0.04    8.60
G    300    19.14    16.65    0.32    16.97
H    30.1    21.88    12.07    0.20    12.27    0.0    5.88
H    300    32.77    17.95    0.20    18.15

Claims (9)

1、通过对CO2的选择性吸附，从含有非酸性气体的混合物中选择性地分离CO2的循环工艺，它包括下面几步：
(a)提供一个含有八面沸石型的沸石分子筛的固定吸附床，其分子筛的SiO2/Al2O3摩尔比为2-6，并含有至少20当量百分数的选自锌、稀土、氢和铵阳离子中的一种离子，
(b)让上述的气体混合物进入上述的床，温度为-50℃-100℃，压力为0.2-1000磅/英寸2，这样CO2选择性地吸附在上述的混石上，并得到消耗了CO2的气体混合物，
(c)在CO2从出口端穿透之前，让上述的气流停止进入上述的床，
(d)让上述的床内的压力降到低于步骤(b)的吸附压力，并降到0.1-500磅/英寸2的范围内而使CO2解吸，使该吸附床再生，及
(e)重复(a)到(d)的步骤。
2、根据权利要求1的工艺，其中CO2和非酸性气体的混合物含CO2和CH4。
3、根据权利要求1的工艺，其中CO2和非酸性气体的混合物含CO2和H2。
4、根据权利要求1的工艺，其中CO2和非酸性气体的混合物含CO2和N2。
5、根据权利要求1的工艺，其中被处理的气体混合物中CO2含量至少为5摩尔百分数，沸石分子筛框架中SiO2/Al2O3比值为2-6，而该沸石分子筛至少含20当量百分数的选自锌、稀土、氢和铵阳离子中的一种离子。
6、根据权利要求5的工艺，其中沸石分子筛至少含40当量百分数的选自锌、稀土、氢和铵阳离子中的一种离子，及小于40当量百分数的碱金属或碱土金属阳离子。
7、根据权利要求6的工艺，其中CO2和非酸性气体的混合物含CO2和CH4。
8、根据权利要求6的工艺，其中CO2和非酸性气体的混合物含CO2和H2。
9、根据权利要求6的工艺，其中CO2和非酸性气体的混合物含CO2和N2。
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