CN109641194B - 包含小的10-环沸石微晶的催化剂和通过使含氧化合物经由所述催化剂反应来制备烃的方法 - Google Patents
包含小的10-环沸石微晶的催化剂和通过使含氧化合物经由所述催化剂反应来制备烃的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000010457 zeolite Substances 0.000 title claims abstract description 32
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title claims abstract description 28
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- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及催化剂材料，例如TON(ZSM‑22)和MTT(ZSM‑23)，该催化剂材料包括具有一维非交叉通道的10‑环沸石微晶，其中微晶的平均长度为小于150nm。该催化剂可用于通过使含氧化合物经由所述催化剂反应而制备烃的方法中。
Description
甲醇制烃(MTH)反应是经由多孔酸性沸石和类沸石催化剂将富含碳的原料(如煤、天然气或生物质)转化为烃类物质如轻质烯烃或汽油燃料的一系列工序中的重要工序。在过去的40年中已经进行了大量研究以获得具有特殊选择性和具有工业感兴趣的寿命的新型沸石。
本发明涉及特别是MTT拓扑结构的纳米级沸石催化剂在将含氧化合物(特别是甲醇或二甲醚，以及低级烯烃，特别是乙烯、丙烯或丁烯)转化为C5至C10的且基本上不含(低于5wt％)芳族分子的高级烃中的用途。
特别感兴趣的是中孔沸石(由10个氧定义孔周长)，例如商业上使用的ZSM-5催化剂(10-环非交叉通道，其形成三维多孔网络)。该催化剂用于美孚甲醇制汽油(MobilMethanol to Gasoline)(MTG)和
改进的汽油合成TIGAS工艺(
ImprovedGasoline Synthesis TIGAS)，并显示出对于富含芳族化合物的C5-C6+产物的高选择性。
因为MTH反应发生在分子尺寸的孔内，所以产物选择性对通道系统的尺寸和排列高度敏感；这称为产物形状选择性。
最近，已经证明一些具有非交叉一维通道的10-环沸石，如TON(ZSM-22)和MTT(ZSM-23)也显示出对C5-C6+产物的高选择性，但是其产生非常少量的芳族化合物。在没有通道交叉的情况下，芳族化合物的形成，特别是反应性，受到限制，但是由于一维孔系统，由孔堵塞引起的快速失活是一个问题。因此，这种一维沸石的循环寿命从未高于1-10小时。
在本发明的第一方面，提供了一种催化剂材料，所得催化剂具有显著延长的寿命。
在本发明的第二方面，提供了一种制备催化剂材料的方法，该方法提供对重要的催化剂材料参数的控制。
通过催化剂材料提供这些和其它优点，该催化剂材料包括具有一维非交叉通道的10-环沸石微晶，其中微晶的平均长度为小于150nm。
申请人已经表明，例如在甲醇转化为烃的方面，微晶长度与催化剂材料的寿命直接相关。实验表明，对于150nm和更短的微晶，其对于寿命有明显的影响。
特别是如果微晶的平均长度小于110nm，例如10-100nm，则与具有更长微晶长度的类似材料相比，催化剂材料具有显著改善的寿命。
在一些实施方案中，Si/Al比为15-200，例如20-120，优选20-70，由此通常实现较低的氢化物转移反应，并因此降低芳族产物产率和较长的寿命。然而，太低的值可能由于缺乏酸性位点而导致活性降低。
优选地，长/宽比<3。可优选L/W<2且其中10-环通道沿长轴延伸的球形颗粒或近球形颗粒。
优选地，沸石是ZSM-23。
根据本发明的催化剂材料和催化剂可有利地用于在1-50巴，例如1-20巴，例如5-20巴和在350-600℃，例如400-450℃下进行的商业方法中。
示例性制备
通过修改文献中描述的合成程序制备了具有不同微晶尺寸的ZSM-23催化剂。调节所报告的凝胶组成以获得具有相似Si/Al比(其为20-40)的产物。关键信息见表1。催化剂材料根据所用的结构导向剂(SDA)进行标记：对于使用N,N-二甲基甲酰胺作为SDA的，标记为ZSM-23 DMF；对于比咯烷，标记为ZSM-23 Pyrr；对于异丙胺，标记为ZSM-23 iPA；对于N1,N1,N3,N3-四甲基丙烷-1,3-二胺(TMPD)和N1,N1,N3,N3,2,2-六甲基丙烷-1,3-二胺(HMPD)的混合物，标记为ZSM-23 T/HMPD；对于溴化七甲基铵(N,N,N,N',N',N'-六甲基庚烷-1,7-二铵二溴化物)，标记为ZSM-23 C7二季铵。
作为代表性实例，用C7二季铵化合物模板剂七甲基二溴化铵的合成如下进行：
-在Teflon衬里中，在搅拌下将1.60g 50wt％的NaOH与0.74g Al(NO3)3·18H2O和30g水混合，直至完全溶解；
-在搅拌下将3.24g的C7二季铵模板剂加入到溶液中；
-在搅拌下加入3.45g气相二氧化硅(Aldrich)，直至形成致密凝胶；
-将剩余的10g水加入凝胶中。
然后将凝胶混合物在磁力搅拌下搅拌3小时，然后将Teflon衬里放入不锈钢高压釜中。在预热至160℃的温度的转炉(转速30rpm)中进行合成。14天后，将高压釜在冷水中淬灭，过滤收集产物，用蒸馏水洗涤数次。
然后将粉末在80℃下干燥过夜，并在马弗炉中煅烧，在煅烧过程中，经6小时使温度从室温升至550℃，然后在该温度下保持8小时，以除去捕集在孔中的所有有机化合物。然后将样品用1M的NH4NO3溶液在80℃下在3-5小时内进行3次离子交换。然后以与前述相同的条件再次煅烧铵形式的样品。
转化反应
在连续流动的U形固定床反应器(内径为10mm)中进行甲醇向烃的转化反应。在反应之前，将催化剂在10mL/min的纯He流下从室温加热至550℃。在达到预处理温度后，将流动的气体转换为纯O2并保持1小时以原位煅烧催化剂并除去所有被吸附的物质。在预处理之后，将反应器在纯He流下冷却至用于反应的温度(400℃)。
甲醇至烃的反应在大气压和400℃下进行。使用100mg催化剂(筛分级分250至420μm)。将19.5mL min-1的He流在20℃的温度下鼓泡通过填充有MeOH的饱和器(BDHLaboratory，纯度>99.8％)，产生130mbar的甲醇分压。得到的重时空速(WHSV)为2gMeOHg催化剂 -1h-1。
使用配备有SPB-5毛细管柱(长60m，内径0.530mm，固定相厚度为5μm)和火焰离子化检测器(FID)的在线Agilent 6890A气相色谱仪分析反应产物。
通过对GC-FID色谱图中的区域进行积分来获得甲醇转化率，产物选择性和产物收率。甲醇(MeOH)和二甲醚(DME)都被认为是反应物，其余的化合物在GC中被检测为反应产物。测量的响应因子用于MeOH和DME，并且认为该响应与烃产物分子中的碳原子数成比例。
研究了本文所述的7种材料在低的进料速率下在甲醇至烃的转化中的催化剂性能。显然，催化剂的稳定性和寿命存在巨大差异。通过总转化能力进一步量化该差异，总转化能力定义为直至完全失活时，被转化为烃的甲醇的总量，其列于表2中。
申请人已经表明，寿命与颗粒尺寸有关，特别是在通道系统方向上的尺寸。
因此，根据本发明选择合适的催化剂制备方法，可以使所得微晶的寿命延长数个数量级。
对于使用DMF制备的材料，转化能力非常小，因此将其作为甲醇和酸性位点之间的化学计量过程进行讨论可能更合适。使用C7二季铵SDA制备的催化剂可产生优异的催化剂。使用此SDA获得了大量催化剂，转化能力范围为60至180的g甲醇/g催化剂。
之前对ZSM-23和结构相关的ZSM-22的研究报告，转换能力在400℃时不高于16gg-1，在450℃时略高[S.Teketel,W.Skistad,S.Benard,U.Olsbye,K.P.Lillerud,P.Beatoand S.Svelle,ACS Catal.,2012,2,26–37]；[J.Wang,S.Xu,J.Li,Y.Zhi,M.Zhang,Y.He,Y.Wei,X.Guo and Z.Liu,RSC Adv.,2015,5,88928–88935]。因此，与已知方法和催化剂材料相比，本发明所述的方法和催化剂材料显然代表了对重要参数的显著改进。
申请人已经表明，根据本发明，限定为晶体尺寸小于100nm的小晶体ZSM-23(MTT拓扑结构)的寿命可比目前报告的最长寿命提高至少四倍[J.Wang,S.Xu,J.Li,Y.Zhi,M.Zhang,Y.He,Y.Wei,X.Guo and Z.Liu,RSC Adv.,2015,5,88928–88935]。
图1示出了在400℃，1atm和2的WHSV下，经由ZSM-23催化剂的MeOH转化率的曲线图。从图中可以清楚地看出，小晶体导致显著提高的寿命。还可以看出，老化时间是微晶生产中的一个相关参数，因为老化时间越长，晶体越小，寿命越长。
图2示出了五种ZSM-23催化剂的低分辨率扫描电子显微镜图像(左列)，高分辨率图像(中间列)和粉末X射线衍射图：从上到下依次为ZSM-23 DMF、ZSM-23比咯烷、ZSM-23 H/TMPD、ZSM-23异丙胺和ZSM-23 C7二季铵#3。电子显微图像显示，晶体的形态从微米尺寸的针状(ZSM-23 DMF)变化到数十纳米尺寸的几乎球形晶体(ZSM-23 C7二季铵#3)。
图3示出了ZSM-23二季铵#3(左侧)和ZSM-23 DMF(右侧)的代表性晶体分布的SEM图像，其中突出显示了一些晶体的宽度(W)和长度(L)。
Claims (28)
1.一种催化剂的用途，用于将含氧化合物转化为烃，所述催化剂包括催化剂材料，所述催化剂材料包括具有一维非交叉通道的10-环沸石微晶，其中所述微晶的平均长度为小于50nm，且长/宽比为低于3，其中所述10-环沸石微晶的Si/Al比为15-200。
2.根据权利要求1所述的用途，其中所述10-环沸石微晶的Si/Al比为15-100。
3.根据权利要求1所述的用途，其中所述10-环沸石微晶的Si/Al比为20-50。
4.根据权利要求1所述的用途，其中所述10-环沸石微晶的长/宽比为低于2。
5.根据权利要求1所述的用途，其中所述10-环沸石微晶的沸石是ZSM-23。
6.根据权利要求1-5中任一项所述的用途，其中所述含氧化合物包括甲醇和/或DME。
7.根据权利要求1-5中任一项所述的用途，其中所述烃包含小于5wt％的芳族化合物。
8.根据权利要求7所述的用途，其中所述烃包含小于2wt％的芳族化合物。
9.一种生产烃的方法，其中含氧化合物经由催化剂转化为烃，所述催化剂包括催化剂材料，所述催化剂材料包括具有一维非交叉通道的10-环沸石微晶，其中所述微晶的平均长度为小于50nm，且长/宽比为低于3，其中所述10-环沸石微晶的Si/Al比为15-200。
10.根据权利要求9所述的方法，其中所述10-环沸石微晶的Si/Al比为15-100。
11.根据权利要求9所述的方法，其中所述10-环沸石微晶的Si/Al比为20-50。
12.根据权利要求9所述的方法，其中所述10-环沸石微晶的长/宽比为低于2。
13.根据权利要求9所述的方法，其中所述10-环沸石微晶的沸石是ZSM-23。
14.一种生产烃的方法，所述方法包括使含氧化合物的物流经由催化剂反应由此生成烃产物的步骤，所述催化剂包括催化剂材料，所述催化剂材料包括具有一维非交叉通道的10-环沸石微晶，其中所述微晶的平均长度为小于50nm，且长/宽比为低于3，其中所述10-环沸石微晶的Si/Al比为15-200。
15.根据权利要求14所述的方法，其中所述10-环沸石微晶的Si/Al比为15-100。
16.根据权利要求14所述的方法，其中所述10-环沸石微晶的Si/Al比为20-50。
17.根据权利要求14所述的方法，其中所述10-环沸石微晶的长/宽比为低于2。
18.根据权利要求14所述的方法，其中所述10-环沸石微晶的沸石是ZSM-23。
19.根据权利要求14所述的方法，其中所述烃产物包含小于5wt％的芳族化合物。
20.根据权利要求19所述的方法，其中所述烃产物包含小于2wt％的芳族化合物。
21.根据权利要求14-20中任一项所述的方法，其中所述烃产物包含C5至C10的高级烃。
22.根据权利要求14-20中任一项所述的方法，其中所述含氧化合物的物流包含甲醇和/或二甲醚。
23.根据权利要求14-20中任一项所述的方法，其中所述方法在1至5g含氧化合物g催化剂 -1h-1的重时空速下进行。
24.根据权利要求23所述的方法，其中所述方法在2g含氧化合物g催化剂 -1h-1的重时空速下进行。
25.根据权利要求14-20中任一项所述的方法，其中所述方法在1-50巴下进行。
26.根据权利要求25所述的方法，其中所述方法在1-20巴下进行。
27.根据权利要求14-20中任一项所述的方法，其中所述方法在350-600℃下进行。
28.根据权利要求27所述的方法，其中所述方法在400-450℃下进行。
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| US4490342A (en) | 1983-04-29 | 1984-12-25 | Mobil Oil Corporation | Synthesis of ZSM-23 zeolite |
| CA1270005A (en) * | 1985-10-07 | 1990-06-05 | Mobil Oil Corporation | Catalytic conversion of propane to ethylene over zsm- 23 |
| US5063038A (en) | 1985-10-21 | 1991-11-05 | Mobil Oil Corp. | Zeolite synthesis using an alcohol or like molecule |
| US4870038A (en) | 1987-10-07 | 1989-09-26 | Mobil Oil Corporation | Olefin oligomerization with surface modified zeolite catalyst |
| US5157194A (en) | 1991-12-20 | 1992-10-20 | Mobil Oil Corporation | Highly selective n-olefin isomerization process using microcrystalline ZSM-22 |
| US5332566A (en) | 1993-07-16 | 1994-07-26 | Mobil Oil Corp. | Synthesis of crystalline ZSM-23 |
| WO1999028031A1 (en) * | 1997-12-03 | 1999-06-10 | Exxon Chemical Patents Inc. | Catalyst comprising a zeolite partially coated with a second zeolite, its use for hydrocarbon conversion |
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| US7119245B1 (en) * | 2001-10-25 | 2006-10-10 | Sandia Corporation | Synthesis of an un-supported, high-flow ZSM-22 zeolite membrane |
| CN1325613C (zh) | 2004-10-29 | 2007-07-11 | 中国石油化工股份有限公司 | 馏分油加氢处理催化剂及其制备方法 |
| US7824658B2 (en) | 2006-12-28 | 2010-11-02 | Chevron U.S.A., Inc. | Method of making ultrasmall crystal MTT molecular sieves |
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| US9186659B2 (en) * | 2014-01-09 | 2015-11-17 | King Fahd University Of Petroleum And Minerals | Controlled growth of MTT zeolite by microwave-assisted hydrothermal synthesis |
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