CN1055030C - 甲烷非氧化催化脱氢芳构化催化剂 - Google Patents
甲烷非氧化催化脱氢芳构化催化剂 Download PDFInfo
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- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
甲烷非氧化催化脱氢芳构化催化剂，为H2SO4-WOx-AOY/HZSM-5负载型催化剂，以HZSM-5分子筛为载体，AOY中A选自Zn，Nb，Mo等过渡金属或La等稀土元素，各组份含量(重量百分比)中AOY以A折合量计0.2%～2.0%，H2SO40.5%～8%，WOx以W折合量计0.6%～5%，余量为HZSM-5。催化剂采用浸渍法制备。本发明提供的催化剂耐热性能好，在高温的反应条件下催化剂稳定性高，不挥发，不分解，且甲烷转化率高达23%，苯的选择性～97%，具有较好的工业应用前景。
Description
本发明涉及一种甲烷非氧化催化脱氢芳构化制芳烃催化剂。
国内外有关甲烷非氧化条件下催化脱氢芳构化方面的研究报道近几年来略有增加。有些学者把担载有Pd，Pt，Re，Mo，W等的负载型催化剂用于非氧化气氛下甲烷催化转化制芳烃，取得了一些有意义的结果。美国专利US4507517(1985)公开了采用BN催化剂进行甲烷非氧化条件下催化合成芳烃的反应，得到低收率的芳烃产物。苏联学者Bragin等[IZV，Akad.，Nauk SSSR，Ser.Khim.，1989，750]报道了用脉冲反应器，在担载贵金属及Zn，Ga的高硅沸石型催化剂上分别在873K和1023K的反应温度下，实现了非氧化条件下甲烷转化为苯；他们在Pt-CrO3/HZSM-5上，反应温度为1023K，脉冲反应甲烷转化率达到18％，苯的收率为14％。王冬杰等(高等学校化学学报，1996 17(11)：1776)报导了以Ni改性的Mo/HZSM-5催化剂在非氧化条件下及973K下，甲烷转化率达11.3％，芳烃选择性为97％。陈元来等(天燃气化工，1994 19(6)：1)报导了HZSM-5担载的过渡金属如Re，W，Mo和V等的高价态氧化物对甲烷芳构化有催化活性，在3％W/HZSM-5催化剂上甲烷转化率为3.7％，苯选择性为63.6％。本申请人在CN97100978.3号专利申请中提供一种SO4 2--MoO4 2--AOX/HZSM-5负载型催化剂，用于非氧化条件下甲烷脱氢芳构化反应，其甲烷转化率22％，苯选择性92％，但其组份中Mo在高温下易挥发，因此，催化剂的稳定性较差。
本发明的目的旨在提供一种耐热性能好、甲烷转化率高的甲烷非氧化催化脱氢芳构化催化剂。
本发明为一种用于非氧化条件下甲烷催化脱氢芳构化制芳烃的负载型催化剂H2SO4-WOX-AOY/HZSM-5。所说的催化剂以HZSM-5分子筛为载体，HZSM-5中Si/Al比为10～50，最好是18～38；AOy是金属氧化物，AOy中的A选自Zn，Nb，Mo等过渡金属或La等稀土元素，AOy中y为A的价数的1/2，A含量(重量百分比，下同)为0.2％～2.0％，最好是1.0％～1.5％；所说的H2SO4的含量为0.5％～8％，最好是1％～5％；WOX中x为W价数的1/2所说的WOX的含量以W折合量计为0.6％～5％，最好是1.5％～3.0％，余量为HZSM-5。
本发明所说的催化剂采用浸渍法制备：首先把计量的HZSM-5分子筛载体于373～393K预处理2小时，后将计量的钨酸铵溶液浸渍于HZSM-5分子筛载体上，该物料先后在373～393K烘干2小时，673～873K焙烧4～12小时，继将含计量A的硫酸盐或硝酸盐或氟化物的溶液浸渍于其上，后于373～393K烘干2小时，673～873K焙烧4～12小时，再以计量的H2SO4或(NH4)2SO4浸渍或以过量的14N NH4OH浸渍之，然后依次在373～393K烘干2小时，673～873K焙烧4～12小时，即得负载型H2SO4-WOX-AOY/HZSM-5催化剂。
甲烷非氧化催化脱氢芳构化制芳烃试验在一常压气体连续流动固定床反应器-气相色谱仪组合系统上进行，每次实验的催化剂用量为0.6g，原料气CH4纯度99.9％，空速1500ml/h-g-catal.，反应系统压力为120kPa，反应温度1123K。较佳的实验结果为甲烷转化率(由色谱分析数据按工作曲线法计算)达23％，在含碳产物中苯选择性为～97％，甲苯选择性～2.5％。
从热力学角度出发，甲烷转化成苯的平衡转化率随着反应温度的提高而提高。但实际使用的反应温度则受到催化剂的性能等诸多因素所制约。在我们已早请过的专利中所提供的SO4 -2-MoO4 -2-AOX/HZSM-5非氧化条件下甲烷脱氢芳构化催化剂，只适于在低于1023K的反应温度下使用，过高的温度将引起Mo的大量流失和催化剂结炭的急增而导致催化剂的很快失活。本发明以W/HZSM-5基催化剂替代Mo/HZSM-5基催化剂，催化剂可以在1123K的温度下使用，不会引起活性组份W的流失，同时催化剂具有较强的抗结炭能力，因而在1123K反应温度下进行甲烷非氧化催化脱氢芳构化反应，不仅能使甲烷转化率达到23％(比Mo系提高2％)，而且芳烃选择性高于97％，催化剂的稳定性好。另外，本发明提供的催化剂，可以使甲烷通过非氧化催化脱氢芳构化转化为芳烃。这个过程具有一些独到的优点，诸如：技术上较少复杂性，不存在象氧化过程用空气作氧化剂而带来的反应产物受CO或N2稀释的问题；主要产物芳烃与未转化的CH4及副产物H2很容易分离；副产物H2可作为油品精制工业所需大量H2的来源。
下面由实施例对本发明作进一步说明。
实施例1：
将经折算含0.1g W的钨酸铵溶液浸渍于4g经383K预处理2小时的HZSM-5分子筛上，该物料于383K烘干2小时，773K焙烧4小时，即得催化剂前驱物，将其置于干燥器中备用。将经折算含0.06g Zn的硫酸锌溶液，浸渍于以383K预处理的上述催化剂前驱物上，于383K烘干2小时，随后将2.5ml的14N氢氧化铵溶液浸渍于其上，于383K烘干2小时，673K焙烧4小时，即得负载型H2SO4-WOX-ZnO/HZSM-5催化剂。
甲烷非氧化催化脱氢芳构化制芳烃试验在一常压气体连续流动固定床反应器-气相色谱仪组合系统上进行。每次实验催化剂用量为0.6g，粒度40～60目；反应体系压力为120kPa，空速1500ml/h-g-catal.；在升温过程中，催化剂处于N2气氛保护下，当温度达到1123K时直接导入纯度为99.9％的原料气CH4；反应物和产物由一在线气相色谱仪(102GD型)热导检测器和氢焰检测器联合作现场分析，色谱柱真料为DNP，柱长2米，以N2作为色谱载气；催化剂活性数据取自反应开始45min体系达到稳态后，甲烷转化率由色谱分析数据按工作曲线法计算，XCH4达22.9％，在含碳产物中苯的选择性为97％，甲苯选择性为2.7％。
实施例2：
保持硫酸锌浸渍液中Zn含量(经折算含Zn量为0.06g)不变，调变钨酸铵浸渍液中W的含量，按照实施例1制备程序制得一系列不同W含量的负载型H2SO4-WOX-ZnO/HZSM-5催化剂。
甲烷非氧化催化脱氢芳构化制芳烃试验同实施例1，结果示于表1。
表1W(重量)％ 0.4 0.8 1.4 2.0 2.5 3.5 4.5CH4转化率(％) 9.7 16.1 22.5 23.6 23.0 23.5 23.8苯选择性(％) 96.2 96.2 97.3 97.1 97.7 97.2 97.5甲苯选择性(％) 3.8 3.8 2.7 2.9 2.3 2.8 2.5
实施例3：
按照实施例1制备含钨催化剂前驱物，将折算含有0.03g Mo的钼酸铵溶液，浸渍于4g经383K预处理2小时的上述催化剂前驱物上，将浸渍好的物料于383K烘干2小时，673K焙烧4小时，后降温到383K，浸渍以经折算含0.12g H2SO4的硫酸铵溶液，后于383K烘干2小时，673K焙烧4小时，即得负载型H2SO4-WOX-MoO3/HZSM-5催化剂。
甲烷非氧化催化脱氢芳构化制芳烃试验同实施例1。甲烷转化率达21.9％，苯选择性为96.2％，甲苯选择性为2.9％。
实施例4：
按照实施例1制备含钨催化剂前驱物，将折算含有0.008g Nb的氟化铌溶液，浸渍于4g经383K预处理2小时的上述催化剂前驱物上，将浸渍好的物料于383K烘干2小时，随后将过量的14N氢氧化铵浸渍于其上，于383K烘干2小时，673K焙烧4小时，后降温至383K，浸渍以经折算含0.08g H2SO4的硫酸铵溶液，后于383K烘干2小时，673K焙烧4小时，即得负载型H2SO4-WOX-Nb2O5/HZSM-5催化剂。
甲烷非氧化催化脱氢芳构化制芳烃试验同实施例1。甲烷转化率达18.3％，苯选择性为94.5％，甲苯选择性为3.5％。
实施例5：
按照实施例1制备含钨催化剂前驱物，将折算含有0.08g La的硝酸镧溶液，浸渍于4g经383K预处理2小时的上述催化剂前驱物上，于383K烘干2小时，673K焙烧4小时，后降温到383K，浸渍以经折算含0.12g H2SO4的2N硫酸铵溶液，后于383K烘干2小时，673K焙烧4小时，即得负载型H2SOx-WOX-La2O3/HZSM-5催化剂。
甲烷非氧化催化脱氢芳构化制芳烃试验同实施例1。甲烷转化率达22.1％，苯选择性为96.5％，甲苯选择性为3.2％。
实施例6：
按照实施例1制备负载型H2SO4-WOX-ZnO/HZSM-5催化剂。
甲烷非氧化催化脱氢芳构化制芳烃试验同实施例1。在不同反应温度下对催化剂活性进行评价，结果示于表2。
表2
反应温度K 1023 1123 1173
CH4转化率(％) 21.2 22.9 23.2
C6H6选择性(％) 96.8 97.7 97.2
C7H8选择性(％) 3.2 2.3 2.8
Claims (3)
1.甲烷非氧化催化脱氢芳构化催化剂，为H2SO4-WOX-AOY/HZSM-5负载型催化剂，催化剂以HZSM-5分子筛为载体，HZSM-5中Si/Al比为10～50，AOY为金属氧化物，A选自Zn，Nb，Mo或La，催化剂中各组份含量(重量百分比)为AOY以A折合量计为0.2～2.0％，H2SO4含量0.5％～8％，WOX以W折合量计为0.6％～5％，余量为HZSM-5。
2.如权利要求1所述的甲烷非氧化催化脱氢芳构化催化剂，其特征在于催化剂各组份含量(重量百分比)为AOY以A折合量为1.0％～1.5％，H2SO4为1％～5％，WOX以W折合量为1.5％～3.0％，余量为HZSM-5。
3.如权利要求1所述的甲烷非氧化催化脱氢芳构化催化剂，其特征在于AOY中y为A的价数的1/2，WOX中X为W价数的1/2。
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| CN97113358A CN1055030C (zh) | 1997-07-24 | 1997-07-24 | 甲烷非氧化催化脱氢芳构化催化剂 |
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| CN1055030C true CN1055030C (zh) | 2000-08-02 |
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| CN110327967A (zh) * | 2019-07-26 | 2019-10-15 | 山东达民化工股份有限公司 | 催化剂及其制备方法及应用该催化剂的异丙醇安生产工艺 |
| JP2021041330A (ja) * | 2019-09-10 | 2021-03-18 | 国立大学法人 大分大学 | メタンの脱水素芳香族化反応用触媒及び芳香族化合物の製造方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507517A (en) * | 1983-10-31 | 1985-03-26 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a boron compound containing catalyst |
| EP0228267A1 (en) * | 1985-12-23 | 1987-07-08 | The British Petroleum Company p.l.c. | Production of aromatics from hydrocarbon feedstock |
| US4975402A (en) * | 1989-02-21 | 1990-12-04 | Concordia University | Catalyst for aromatization of olefins and paraffins |
| CN1102359A (zh) * | 1993-11-04 | 1995-05-10 | 中科院大连化学物理研究所 | 甲烷直接合成芳烃的催化剂及其在合成反应中的应用 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507517A (en) * | 1983-10-31 | 1985-03-26 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a boron compound containing catalyst |
| EP0228267A1 (en) * | 1985-12-23 | 1987-07-08 | The British Petroleum Company p.l.c. | Production of aromatics from hydrocarbon feedstock |
| US4975402A (en) * | 1989-02-21 | 1990-12-04 | Concordia University | Catalyst for aromatization of olefins and paraffins |
| CN1102359A (zh) * | 1993-11-04 | 1995-05-10 | 中科院大连化学物理研究所 | 甲烷直接合成芳烃的催化剂及其在合成反应中的应用 |
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