CN102439123A - 具有rho结构的沸石性质微孔晶体材料在天然气加工过程中的应用 - Google Patents
具有rho结构的沸石性质微孔晶体材料在天然气加工过程中的应用 Download PDFInfo
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Abstract
本发明公开了具有与RHO沸石结构同构的沸石在天然气的各种组分的吸附和分离方法中的应用。
Description
发明技术领域
本发明涉及用于天然气加工过程的沸石性质(zeolitic nature)微孔晶体材料的技术领域。
背景技术
天然气的分离和提纯主要包括将甲烷与伴随其的氢气和具有酸性质的气体例如CO2和SH2[J.Phys.Chem.C 2008，112，5048-5056]分离的步骤。酸性气体导致天然气储罐中的腐蚀问题以及用于运输其的气体管线的堵塞问题。氮气的存在减少了传递的体积单位的热量，以及极大增加了浓缩压力。因此，这些气体必须在其运输之前从天然气流中除去。目前，氮气的分离通过低温蒸馏甲烷和N2实现，由此必须首先除去其它在低温下浓缩的气体。因而，CO2通过在适当的溶剂的存在下与胺的化学反应从天然气流中除去。目前该技术广泛用于甲烷从天然气中的提纯和分离。然而，该技术具有很多缺陷。一方面，低温蒸馏去除氮气从能量的角度看非常耗能，另一方面，通过胺的俘获除去CO2意味着天然气必须减压至再重新加压，因而使其可以通过气体管线运输。涉及高能耗的所有这些过程都促使很多公司开发基于膜或吸附方法的新技术。
已有使用致密的有机膜从天然气流中分离甲烷的报道，因为CO2可以透过该膜而甲烷不能。可高选择性地分离N2/CH4混合物、但对甲烷具有低渗透性的高密度有机聚合物也已经被报道了。
同样地，已经有微孔材料，特别是沸石，在甲烷/CO2混合物中选择性吸附CO2的报道。因而，已有报道钛硅酸盐微孔材料(titanosilicatos microporosos)作为分子门(puertas moleculares)根据吸附剂承受的热处理条件用于从CO2中分离甲烷或从CO2中分离氮气(NATURE，2001，412，720-723；US Pat.6068682(2000))。最近，ERS-7沸石作为从包含氮气和CO2的气体混合物中分离甲烷的有效材料已经被报道(WO2008/000380)。该沸石在包括2到25bar的压力范围内呈现比对甲烷的吸附容量高约三倍的对CO2的吸附容量，在0℃时每克沸石的最大吸附容量约为175mgCO2。人们期待得到更高吸附容量和在CO2/CH4混合物中针对CO2甚至更有选择性的微孔材料。另一方面，该ERS-7沸石在分离N2/CH4混合物时选择性很低，据报道在1bar，273K条件下N2和CH4的最大吸附容量的摩尔比一般小于1.5。
在本发明专利中描述了RHO沸石的同构沸石材料用于从天然气流或从包含CO2和甲烷的流中提纯和分离甲烷的方法，CO2被优选地以及选择性地吸附，在该流中只留下甲烷。这些沸石可适用于利用现有技术中描述为所谓的“变压吸附(PSA)”、“热变压吸附(TSA)”或“压力真空变压吸附(PVSA)”的技术的气体分离方法中，其中，该所吸附的气体(在此情况中为CO2)通过在PSA方法中未被吸附的气流(在本发明所描述的方法中优选N2，CH4)中的洗涤、通过TSA处理中的热处理以及通过在真空中(PVSA)所吸附气体的清除而使吸附循环和脱附循环交替进行。在所有情况下，沸石能在短时间内以及在与吸附循环中所用的那些温度和压力尽可能接近的温度和压力下恢复其吸附容量是被期待的。
RHO沸石，其显示出具有0.36×0.36nm的晶体学开口的窗口，这准许进入到直径为1.15nm的大的“准球形”腔室，满足了所有这些允许CO2分子进入的条件，但阻止了甲烷，因此可用于天然气流中甲烷的分离或提纯方法中。
发明详述
沸石可根据其孔道(channels)开口可分为超大孔、大孔、中孔或小孔沸石。因而，这些小孔沸石具有由8个四面体构成开口的孔道，而中孔沸石为10个四面体，大孔沸石为12个，以及最后超大孔沸石具有的孔道具有多于12个四面体构成的开口。
RHO沸石是小孔沸石，其具有0.36×0.36nm开口的三向孔道系统、它们相关贯穿形成直径为1.15nm的准球形超级腔室，并具有14.7个四面体/nm3的净密度。此多孔系统赋予该沸石高的吸附容量，但只有小的动力学直径的分子例如水、氮气、氧气和直链烃等可以进入其内。
本发明涉及使用与RHO沸石同构的沸石材料对存在于天然气流中的烃进行分离或提纯的方法以及其回收，至少包括以下步骤：
(a)将该天然气流与该沸石材料接触，
(b)回收该未吸附的组分。
RHO沸石的特征在于在热力学平衡中，对于CO2和甲烷等具有非常不同的吸附容量，这就使得其应用于存在于天然气流中的甲烷和其它烃类的分离和提纯方法中成为可能。当吸附量在固定的吸附压力和温度条件下不随着时间而增加时就达到了平衡条件。在分离过程中吸附剂的热力学效率由在平衡条件下其对待分离的产物的吸附容量的比值，RA决定。
原则上，沸石的吸附容量越大，分离指定量的甲烷-CO2混合物所需的量越少。因而，对于在操作水平可行的一定的分离方法而言，需要具有高的RA值以及高或者中等吸附容量的沸石。
本发明所描述的方法可以在-100至200℃，优选在-25至150℃，更优选0至100℃的温度下，以及在0.1至30bar，优选在0.5至25bar之间，更优选在1至10bar之间的压力下实施。
根据特定的实施方式，CO2优选被吸附，甲烷不优选被吸附。
根据另一特定的实施方式，CO2优选被吸附，甲烷和氮气不优选被吸附。此外，未被吸附的气体、甲烷和氮气的混合物，可再次与沸石材料接触，相对于甲烷，氮气优选被吸附。
根据另一特定的实施方式，CO2优选被吸附，具有四个或更少的碳的轻质烃的混合物作为组分不优选被吸附。
根据另一特定的实施方式，CO2优选被吸附，氮气和具有四个或更少的碳的轻质烃的混合物不优选被吸附。此外，未被吸附的气体、氮气和轻质烃的混合物，可再次与沸石材料接触，相对于轻质烃，氮气优选被吸附。
如上所述，已知酸性气体被指认为天然气的以下组分的组：CO2和SH2。
根据另一特定的实施方式，该混合物包含作为优选被吸附的组分的酸性气体和不优选被吸附的甲烷。
根据另一特定的实施方式，该混合物包含作为优选被吸附的组分的酸性气体和作为不优选被吸附的组分的甲烷和氮气。此外，未被吸附的气体、氮气和甲烷的混合物，可再次与沸石材料接触，相对于甲烷，氮气优选被吸附。
根据另一特定的实施方式，该混合物包含作为优选被吸附的组分的酸性气体和作为不优选被吸附的组分的具有四个或更少的碳的轻质烃的混合物。
根据另一特定的实施方式，该混合物包含作为优选被吸附的组分的酸性气体以及作为不优选被吸附的组分的氮气和具有四个或更少的碳的轻质烃的混合物。另外，未被吸附的气体、氮气和轻质烃的混合物，可再次与沸石材料接触，氮气相对于轻质烃被优选吸附。
在本发明中，RHO沸石显示出了十分不同的对CO2和甲烷的吸附容量，CO2吸附容量高。根据本发明的一特定的实施方式，该RHO沸石在1000mbar和10至60℃温度范围内具有高于100mg/g的CO2吸附容量，以及在这些相同条件下低于10mg/g的对甲烷的吸附容量。因此，RHO沸石是非常合适的用于实施对天然气流中的甲烷进行分离或提纯方法的吸附剂。
本发明的分离方法意味着一定量的RHO沸石与包含尤其CO2和甲烷的气体的混合物(天然气)相接触，其中CO2优选被吸附到RHO沸石内。CO2和甲烷混合物以及RHO沸石保持一定时间的接触以保证吸附过程进行和最后，去除未被吸附的气体混合物。沸石中吸附的气体通过技术例如用其它气体牵引(dragging)、升温、抽空或上述方法的结合进行回收。
该分离过程也可在柱中进行，在这种情况下，取决于保留在RHO沸石床中的强度大小，可得到不同组分(different fronts)的CO2和甲烷，。
分离条件取决于欲被分离的包含甲烷和CO2的气体混合物的精确组成。因此，分离的压力和温度的下限对应于浓缩CO2的条件。因此，本发明的方法可在-100至200℃之间，优选在-25至150℃之间，更优选在0至100℃之间，和在0.1至30bar之间，优选在0.5至25bar之间，更优选在1至10bar之间的压力下实施。
遍及说明书和权利要求，词语“包括”及其变形并不意在排除其他技术特征、添加剂、组分或步骤。对本领域技术人员而言，除了本发明的说明书以及实施例以外的本发明的其它目的、优势以及特征都是显而易见的。提供下列实施例以进行说明，但不意在限制本发明。
实施例
实施例1：制备RHO沸石的同构体材料。
将0.98g冠醚18-6，其结构示于图1，0.705g Cs(OH)，0.45g NaOH和6.04g蒸馏水混合。将混合物进行搅拌至完全溶解。然后，加入1.32g铝酸钠(54％Al2O3，32.8％Na2O，13.2％H2O)并搅拌至获得均匀的溶液。最后，加入10.5g二氧化硅悬浮液(Ludox AS-40)，将混合物搅拌24小时。凝胶的组成为：
1.8Na2O∶0.3Cs2O∶Al2O3∶10SiO2∶0.5(18-冠-6)∶100H2O
将所得混合物放入内衬为聚四氟乙烯的高压釜中，并置于预热后的炉中，在125℃下搅拌5天。所得固体的X射线衍射图显示已经得到所述材料。在600℃下于空气中煅烧3小时以除去吸着的(occluded)有机物并得到可用于吸附和分离方法中的RHO材料。
实施例2：在5000mbar、10℃条件下在RHO材料中CO2的吸附。
根据实施例1制备的RHO材料在10℃，5000mbar下测定的CO2吸附容量为244mg/g。同样地，在进行20个吸附/脱附循环后的值为235mg/g，这表明该RHO材料保持了其吸附容量。
实施例3：在5000mbar，10℃条件下在RHO材料中甲烷的吸附。
根据实施例1制备的RHO材料在10℃，5000mbar下测定的CO2吸附容量为4mg/g。
实施例4：在5000mbar，25℃条件下在RHO材料中CO2的吸附。
根据实施例1制备的RHO材料在25℃，5000mbar下测定的CO2吸附容量为234mg/g。
实施例5：在5000mbar，25℃条件下在RHO材料中甲烷的吸附。
根据实施例1制备的RHO材料在25℃，5000mbar下测定的CO2吸附容量为5mg/g。
实施例6：在5000mbar，45℃条件下在RHO材料中CO2的吸附。
根据实施例1制备的RHO材料在45℃，5000mbar下测定的CO2吸附容量为206mg/g。
实施例7：在5000mbar，45℃条件下在RHO材料中甲烷的吸附。
根据实施例1制备的RHO材料在45℃，5000mbar下测定的CO2吸附容量为6mg/g。
实施例8：在5000mbar，60℃条件下在RHO材料中CO2的吸附。
根据实施例1制备的RHO材料在60℃，5000mbar下测定的CO2吸附容量为180mg/g。
实施例9：在5000mbar，60℃条件下在RHO材料中甲烷的吸附。
根据实施例1制备的RHO材料在60℃，5000mbar下测定的CO2吸附容量为7mg/g。
实施例10：在1000mbar，10℃条件下在RHO材料中甲烷的吸附。
根据实施例1制备的RHO材料的甲烷吸附动力学(kinetic)显示在30分钟内吸附了0.5mg甲烷。
实施例11：在1000mbar，10℃条件下在RHO材料中氮气的吸附。
根据实施例1制备的RHO材料的甲烷吸附动力学显示在30分钟内吸附了3mg氮气。
附图说明：
图1：显示了在为合成与RHO沸石同构的材料的实施例1中所用的有机添加剂的结构。
图2：显示了在不同压力和不同温度下，根据实施例1制备的RHO材料在CO2和CH4平衡中的吸附容量的值。可以看出，由于RHO沸石低的吸附容量，相对于CO2，甲烷在任何温度和/或压力下的等压吸附线彼此难以区分。
图3：显示了10℃，1000mbar气压下在根据实施例1制备的RHO材料中甲烷和氮气吸附动力学。可以看出，在这些条件下氮气比甲烷扩散地更快。
Claims (13)
1.使用与RHO沸石同构的沸石材料对存在于天然气流中的烃进行分离或提纯以及回收的方法，其特征在于，该方法包括至少以下步骤：
(a)将该天然气流与该沸石材料接触，
(b)回收该未吸附的组分。
2.根据权利要求1所述的分离或提纯方法，其特征在于在-100至200℃温度下进行。
3.根据权利要求1所述的分离或提纯方法，其特征在于在0.1至30bar压力下进行。
4.根据前述任一权利要求所述的分离或提纯方法，其特征在于CO2优选被吸附，甲烷不优选被吸附。
5.根据权利要求1至3任一项所述的分离或提纯方法，其特征在于CO2优选被吸附，和甲烷和氮气不优选被吸附。
6.根据权利要求1至3任一项所述的分离或提纯方法，其特征在于CO2优选被吸附，和具有四个或更少碳的轻质烃的混合物作为组分不优选被吸附。
7.根据权利要求1至3任一项所述的分离或提纯方法，其特征在于CO2优选被吸附，以及氮气和具有四个或更少碳的轻质烃的混合物作为组分不优选被吸附。
8.根据权利要求1至3任一项所述的分离或提纯方法，其特征在于该混合物包含作为优选被吸附的组分的酸性气体和不优选被吸附的甲烷。
9.根据权利要求1至3任一项所述的分离或提纯方法，其特征在于该混合物包含作为优选被吸附的组分的酸性气体和作为不优选被吸附的组分的甲烷和氮气。
10.根据权利要求1至3任一项所述的分离或提纯方法，其特征在于该混合物包含作为优选被吸附的组分的酸性气体和作为不优选被吸附的组分的具有四个或更少碳的轻质烃的混合物。
11.根据权利要求1至3任一项所述的分离或提纯方法程，其特征在于该混合物包含作为优选被吸附的组分的酸性气体和作为不优选被吸附的组分的氮气和具有四个或更少碳的轻质烃的混合物。
12.根据权利要求5，7，9和11中任一项所述的分离或提纯方法，其特征在于在所述方法中还包括将该不优选被吸附的气体混合物与该沸石材料接触。
13.根据权利要求12所述的分离或提纯方法，其特征在于该氮气优选被吸附。
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| US5557030A (en) * | 1995-03-23 | 1996-09-17 | Uop | Process for rejecting heavy hydrocarbons from light hydrocarbons gases |
| US20060116430A1 (en) * | 2003-04-15 | 2006-06-01 | Paul Wentink | Method for the production of hydrocarbon liquids using a fischer-tropf method |
| WO2008000380A1 (en) * | 2006-06-26 | 2008-01-03 | Eni S.P.A. | Process and zeolitic materials for the separation of gases |
| WO2008140788A1 (en) * | 2007-05-11 | 2008-11-20 | The Regents Of The University Of California | Adsorptive gas separation of multi-component gases |
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| CN102897787A (zh) * | 2012-10-22 | 2013-01-30 | 天津工业大学 | 一种窄粒度分布的ρ型分子筛的合成方法 |
| CN105452168A (zh) * | 2013-08-05 | 2016-03-30 | 三菱化学株式会社 | 沸石以及其制造方法和用途 |
| CN105452168B (zh) * | 2013-08-05 | 2018-02-27 | 三菱化学株式会社 | 沸石以及其制造方法和用途 |
| US9919297B2 (en) | 2013-08-05 | 2018-03-20 | Mitsubishi Chemical Corporation | Zeolite, and production method and use therefor |
| CN110961075A (zh) * | 2018-09-28 | 2020-04-07 | 气体产品与化学公司 | Rho沸石及其制备方法 |
| CN110961075B (zh) * | 2018-09-28 | 2023-04-18 | 气体产品与化学公司 | Rho沸石及其制备方法 |
| CN114749145A (zh) * | 2022-04-28 | 2022-07-15 | 东北石油大学 | 吸附分离氮气与甲烷的分子筛及制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2010238431B2 (en) | 2016-03-17 |
| EP2420551A1 (en) | 2012-02-22 |
| US20120067216A1 (en) | 2012-03-22 |
| ES2346627B1 (es) | 2011-08-08 |
| ES2346627A1 (es) | 2010-10-18 |
| AU2010238431A1 (en) | 2011-12-01 |
| CN102439123B (zh) | 2015-09-16 |
| JP5732451B2 (ja) | 2015-06-10 |
| JP2012524048A (ja) | 2012-10-11 |
| US8337594B2 (en) | 2012-12-25 |
| EP2420551B1 (en) | 2020-11-18 |
| WO2010119163A1 (es) | 2010-10-21 |
| EP2420551A4 (en) | 2013-01-30 |
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