CN101257972A - 在甲醇向烯烃的转化中对轻质烯烃具有高选择性的分子筛 - Google Patents
在甲醇向烯烃的转化中对轻质烯烃具有高选择性的分子筛 Download PDFInfo
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Abstract
本发明涉及一种用于甲醇向烯烃转化的催化剂，并提出了一种用于鉴别该催化剂的结构的方法，其用于确定该催化剂对于产生高的轻质烯烃产率的选择性的质量。
Description
发明背景
本发明涉及一种催化剂，其在含氧物质向烯烃的转化中对于低分子量烯烃显示出高选择性。
烯烃制备的传统方法是将石油原料裂解为烯烃。石油原料裂解通过催化裂化、蒸汽裂化或该两种工艺的某些结合进行。制得的烯烃通常为轻质烯烃，如乙烯和丙烯。乙烯和丙烯的轻质烯烃产物有着很大的市场。随着来自于原油的石油原料面临着日益增加的价格，有利的是提供其它的乙烯和丙烯源。还已知烯烃可以由含氧物质制备。含氧物质向烯烃最常用的转化是由甲醇制备轻质烯烃，其中甲醇可以由其它来源(包括生物质和天然气)制备。
含氧物质转化为烯烃的方法是一种重要的方法，用于利用含氧物质如甲醇，并将它们转化成更高价值的产物如制备塑料(如乙烯和丙烯)的单体。将含氧物质转化为烯烃的方法是催化方法，催化剂通常是分子筛催化剂。用于催化方法的分子筛催化剂包括ZSM-型分子筛，但更特别地，已经发现硅铝磷酸盐(SAPO)分子筛在该方法中非常有效。
SAPO是通过如下合成的：形成含硅、铝和磷源的混合物，与有机模板混合，然后在阿反应条件下使分子筛结晶。许多因素影响分子筛采取的形式，包括不同组分的相对量、混合顺序、反应条件，例如温度和压力以及有机模板的选择。
提高含氧物质转化率的方法提供节约和经济的优点。用于提高含氧物质向烯烃的转化率的一个方面是晶体结构和晶体尺寸。催化剂的制备是相当复杂而昂贵的，使得在晶体的结构和尺寸方面具有明显不足的晶体的制备轮次从钱和时间损失来说是昂贵的。开发测试催化剂质量的方法将是有利的。该测试可用于改善制备的操作条件并且可以节约时间和节约损失的材料的费用。
发明概述
本发明提供一种用于甲醇向烯烃转化的催化剂。该催化剂包含具有SAPO-34结构的硅铝磷酸盐分子筛，并且特征在于X-射线衍射图在30.7°2θ和31.0°2θ处有峰，其中在30.7°2θ和31.0°2θ处的峰高度比大于0-75。
本发明的另一方面是一种在分子筛的制备中使用分子筛的X-射线衍射图用于质量控制的方法。测定该X-射线衍射图，找到30.7°2θ和31.0°2θ处的峰高度，计算峰高度比，并摒弃峰高度比低于0.75的分子筛。
本发明另外的目的、实施方案和细节可以由本发明下面的详细描述获得。
图1是显示倾斜的双六环各层的示意图；
图2是SAPO-34样品在不同制备条件下的X-射线衍射图的对比；
图3是不同水平的AEI结构型缺陷的X-射线衍射图的模拟；和
图4是所观察到的商购样品的XRD图案与具有不同水平的缺陷的模拟的比较。
发明详述
含氧物质向烯烃的转化率的提高可来自于在该转化工艺中使用的催化剂的改进。改进的一方面在于对于优选的催化剂在结构的均一性上的改进。SAPO-34是甲醇向烯烃(MTO)转化工艺中使用的一种该类催化剂，并且该结构上的改进可以在烯烃产率上产生大的回报。
使用硅酸铝和硅铝磷酸盐分子筛用于不同的方法取决于该分子筛的结构和组成。分子筛的结构用X-射线衍射(XRD)进行分析，其产生相应于已知结构的X-射线衍射图。发现在甲醇转化为烯烃的工艺中对于乙烯和丙烯的选择性与SAPO-34材料的物理性能相关，这可以通过XRD进行检验分析。目前，甲醇转化为烯烃的工艺常常使用SAPO-34作为催化剂的主要活性组分进行。SAPO-34的形貌和制备方法在2001年3月27日颁布的US6,207,872B1中进行了教导，并将其全文引入作为参考。SAPO-34的形貌对于用于实现高的乙烯和丙烯产率、或高的烯烃选择性是重要的。
SAPO-34是具有倾斜的双六环(D6R)框架结构层的硅铝磷酸盐分子筛。该D6R层是构成分子筛的周期性结构单元，并且每层都有取向。该结构是沿着晶体结构的<100>方向的片层的堆叠体，其中各层含有倾斜的双六环。当各层堆叠时，它们可以在相同的方向取向，或者在相反的方向取向，其中该倾斜片层的取向是颠倒的。当各层以相同方向取向时，各层具有AAAA堆叠排列，当它们以相反方向取向时，各层具有ABAB堆叠排列。通过AAAA堆叠排列，分子筛具有CHA型结构，而通过ABAB堆叠排列，分子筛具有AEI型结构。在制备SAPO-34的过程中，分子筛通常在晶体内部具有结构类型的混合物，因此该晶体含有CHA型结构区域和AEI型结构区域。显示说明CHA结构和AEI结构的倾斜D6R各层的示意图示于图1中。
SAPO-34的许多制备物显示了不同的衍射图，常有的是与纯的CHA型结构所期望的不相类似的特征。例如，图2显示了商购样品A(顶部)、由单晶结构模拟的具有CHA型结构的样品(底部)和具有相当纯的CHA型结构的样品(中间)的X-射线衍射图。对于差异的解释是商购样品含有杂质，或无序区域，也称作缺陷。当存在混合的D6R层堆叠顺序时产生有缺陷的结构。
研究缺陷材料的衍射图需要考虑堆叠顺序对于结构的发生可以有不同的可能性。使用软件模拟衍射图对衍射图进行研究。最常用的软件是DIFFaX，一种用于计算含有平面缺陷如堆叠缺陷的衍射强度的计算机软件程序。对于SAPO-34材料，具有纯的CHA型结构的晶体相当于0％缺陷，具有纯的AEI结构的晶体相当于100％缺陷。显示具有0-100％AEI型结构缺陷的CHA型结构的预期XRD图案的DIFFaX模拟示于图3中。随着缺陷水平的增加，许多衍射峰保持相对不变，然而其它峰变宽、位移，然后锐化。另外，某些峰消失，同时其它峰出现，显示图案的变化是复杂的。
商购SAPO-34材料的XRD图案与模拟图案比较可以提供对于商购材料中缺陷程度的评价。然而已经发现，当实际对比模拟结果和实际材料的图案时，模拟拟合得不是非常好。
但是，需要更复杂的模拟图案的结合以获得与所观察到的实际材料的图案的合理匹配。复杂的结合常常需要使用将SAPO-34材料与已知的缺陷水平的结合和更重要的XRD图案分析。已知没有单一的模拟与实际样品拟合良好并获得合理的拟合，需要至少两种具有不同缺陷水平的模拟。如图4所示，将商购样品A(底部)与具有40％AEI缺陷的CHA结构的模拟(中间)和具有5％AEI缺陷的CHA结构的模拟相比较。可以看出需要一种模拟，该40％模拟，以拟合商购样品的XRD的一部分，同时需要其它模拟，该5％模拟，以拟合商购样品的XRD的另一部分。这样存在的问题是需要知道在模拟中使用的缺陷的水平以产生用于与商购样品比较的结果。还不太可能的是SAPO-34具有均匀分布在整个晶体中的缺陷，但是将具有低缺陷区域和高缺陷区域，由此使得与模拟的比较甚至更加复杂和困难。
问题是鉴别和使用SAPO-34材料用于MTO工艺。SAPO材料的简单探求没有产生直接的技术，使用DIFFaX用于得到缺陷的评价是复杂的。初步认为AEI缺陷百分比的确定太复杂，不能容易地作为质量控制程序使用。
无论如何，已经发现一些具有高的CHA结构化区域比例的SAPO-34样品呈现在30.7°2θ和31.0°2θ处产生峰的XRD图案。没有这些峰的样品不能总是提供用于含氧物质向烯烃的转化的好的催化剂，或者具有这些峰和低的峰高度比的样品对于烯烃制备具有较差的选择性。但是，当峰高度比大于0.75时，对于具有SAPO-34结构的分子筛，对于甲醇向低分子量烯烃的转化的选择性大于80％。发现该比值越大，SAPO-34样品出现峰的选择性越大。优选峰高度比为大于0.9，更优选峰高度比为大于1.1，最优选峰高度比为大于1.3。
尽管具有差异，也有许多类似性。SAPO-34的制备在本领域是已知的，如1984年4月3日颁布的、UOP LLC的US 4,440,871中所举例说明的那样，并且其全文引入作为参考。一般，SAPO-34在此称作硅铝磷酸盐材料。其具有PO2 +、AlO2 -和SiO2四面体单元的三维微孔晶体结构，并且其基于无水的基本实验组成为：
(SixAlyPz)O2
其中”x”、”y”和″z″分别表示硅、铝和磷的摩尔份数，并且其中x+y+z＝1。该硅铝磷酸盐还特征在于具有如表1所示的至少六个峰的X-射线粉末衍射图。
表1
| 2θ | d-间隔 | 相对强度 |
| 9.45-9.65 | 9.36-9.17 | s-vs |
| 16.0-16.2 | 5.54-5.47 | w-m |
| 17.85-18.15 | 4.97-4.89 | w-s |
| 20.55-20.9 | 4.32-4.25 | m-vs |
| 24.95-25.4 | 3.57-3.51 | w-s |
| 30.5-30.7 | 2.931-2.912 | w-s |
如本领域技术人员所理解，参数2θ的确定既有人为误差又有机械误差，其结合可以对每个报告的2θ值产生±0.4的不确定性。此不确定性也在d-间隔的值上得以证明，该d值是由2θ计算的。d-间隔的相对强度用符号vs、s、m、w和vw表示，其分别表示非常强、强、中等、弱和非常弱。
此结构的分子筛具有以三元图解表示的硅(Si)、磷(P)和铝(Al)的组成，其中硅的量为0.01-0.98的摩尔份数x；铝的量为0.01-0.6的摩尔份数y；磷的量为0.01-0.52的摩尔份数y。
虽然该组成可以包括更大的范围，但优选硅、铝和磷的摩尔份数落入较小的范围内。硅的摩尔份数x的优选范围为0.02-0.25；铝的摩尔份数y为0.37-0.6；磷的摩尔份数z为0.27-0.49。
SAPO-34分子筛样品的测试可以用样品的XRD分析进行。不是通过使用DIFFaX进行全分析，而是可以进行30.7°2θ和31.0°2θ处的峰高度分析。可以测量峰高度，计算比值和决定样品是否满足可接受的预选值。峰高度比最小的预选值为0.75，其中优选的值为0.9，更优选的值1.1，最优选的值为1.3。当样品具有的峰高度比低于预选的值时，将该分子筛摒弃。
对于满足或超过预选的峰高度比的样品，进行快速检查以确保样品的XRD在表1列出的范围内显示峰，从而确保样品满足SAPO-34标准。
来自样品的XRD的信息在制备SAPO-34的过程中可用于反馈，其中加工温度的变化、硅、铝和磷的相对量、以及有机模板的相对量都可用来提高SAPO-34的质量。
实施例
优选的催化剂是对于乙烯和丙烯的制备具有最大选择性的SAPO-34。将该选择性与计算的每个SAPO-34样品的峰比进行比较。
表2
| 样品 | 选择性，％ | 峰比 |
| 1 | 84.9 | 1.41 |
| 2 | 83.6 | 1.29 |
| 3 | 83.1 | 1.14 |
| 4 | 82.9 | 1.10 |
| 5 | 82.2 | 1.06 |
| 6 | 80.9 | 0.92 |
| 7 | 80.0 | 0.76 |
| 8 | 74.4 | 0.32 |
由表2可见，对于大于82％的理想选择性值，催化剂显示大于1.06的峰比。
尽管本发明通过目前被认为是优选的实施方案进行了描述，应当理解的是本发明并不局限于所公开的实施方案，而是旨在覆盖包括在所附权利要求书的范围内的各种改变和等价安排。
Claims (7)
1.一种硅铝磷酸盐分子筛，具有SAPO-34结构，其特征在于X-射线衍射图中该硅铝磷酸盐在30.7°2θ和31.0°2θ处的峰的峰高度比，其中该比值大于0.75。
2.权利要求1所述的分子筛，其中该比率大于0.9。
3.权利要求1或2所述的分子筛，其中该比率大于1.1。
4.权利要求1、2或3所述的分子筛，其中该比率大于1.3。
5.权利要求1、2、3或4所述的分子筛，其中该分子筛进一步特征在于具有X-射线衍射图，该图案至少具有如表1所示的d-间隔和相对强度：
表1
6.权利要求1、2、3、4或5所述的分子筛，其进一步包含硅铝磷酸盐，该硅铝磷酸盐基于无水和煅烧具有下面实验式表示的结构组成：
(SixAlyPz)O2
其中“x”是Si的摩尔份数，具有0.01-0.98的值，“y”是Al的摩尔份数，具有0.01-0.6的值，“z”是P的摩尔份数，具有0.01-0.52的值，并且x+y+z＝1，并且其中分子筛是包含具有AEI结构和CHA结构的SAPO的产物。
7.权利要求6所述的分子筛，其中摩尔份数“x”为0.02-0.25，摩尔份数“y”为0.37-0-6，摩尔份数“z”为0.27-0.49。
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| US11/222,619 US20070059236A1 (en) | 2005-09-09 | 2005-09-09 | Molecular sieves with high selectivity towards light olefins in methanol to olefin conversion |
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| CN101711992B (zh) * | 2008-09-29 | 2012-05-30 | 宁夏大学 | 甲醇或二甲醚选择性制丙烯的催化剂及其制备方法 |
| CA2787926A1 (en) | 2009-01-23 | 2010-07-29 | Signa Chemistry, Inc. | Catalytic dehydration of alcohols using phase pure, calcined single-and multi-site heterogeneous catalysts |
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| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| US5279810A (en) * | 1990-12-20 | 1994-01-18 | Mobil Oil Corporation | Method of preparing silicoaluminophosphate compositions using a reagent containing both phosphorus and silicon reactive sites in the same molecule |
| NO174341B1 (no) * | 1991-12-23 | 1994-04-21 | Polymers Holding As | Fremg for fremst av krystallinske mikroporose SiAl-fosfater med kontrollert Si-innh, krystallinske mikroporose SiAl-fosfater med forbedret stabilitet mot deaktivering og en anv av disse ved fremstilling av olefiner fra metanol |
| NO304108B1 (no) * | 1996-10-09 | 1998-10-26 | Polymers Holding As | En mikroporos silikoaluminofosfat-sammensetning, katalytisk materiale som omfatter denne sammensetningen og fremgangsmate for fremstilling derav, og bruken av disse for a fremstille olefiner fra metanol |
| RO114524B1 (ro) * | 1997-10-02 | 1999-05-28 | Sc Zecasin Sa | Procedeu de fabricare a oleofinelor cu greutate moleculara mica prin conversia catalitica in strat fluidizat a metanolului |
| JP4174634B2 (ja) * | 1997-12-26 | 2008-11-05 | 三菱瓦斯化学株式会社 | シリカ変性シリコアルミノホスフェート触媒、その製造方法及びそれを用いるメチルアミン類等の製造方法 |
| US20050096214A1 (en) * | 2001-03-01 | 2005-05-05 | Janssen Marcel J. | Silicoaluminophosphate molecular sieve |
| US6812372B2 (en) * | 2001-03-01 | 2004-11-02 | Exxonmobil Chemical Patents Inc. | Silicoaluminophosphate molecular sieve |
| JP4212287B2 (ja) * | 2001-10-11 | 2009-01-21 | 三菱化学株式会社 | ゼオライトの製造方法 |
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