CN1058909C - 非氧化条件下甲烷脱氢芳构化催化剂 - Google Patents
非氧化条件下甲烷脱氢芳构化催化剂 Download PDFInfo
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Abstract
非氧化条件下甲烷脱氢芳构化催化剂，涉及一种甲烷催化脱氢芳构化制芳烃负载型催化剂，通式为SO4 2--MoO4 2--Aox/HZSM-5，以HZSM-5分子筛为载体，AOx为Zn、Co、Ni、Cu等过渡金属氧化物，各组分含量(重量百分比)为AOx0.5～10%，SO4 2-0.5～8%，MoO4 2-1.5～12%，余量为HZSM-5。本发明提供的催化剂在对非氧化条件下甲烷催化脱氢芳构化中显示出高活性、高选择性。甲烷转化率高达21～22%，苯的选择性～92%，甲苯选择性～5%。因此具有相当好的工业应用前景。
Description
本发明涉及一种甲烷催化脱氢芳构化制芳烃负载型催化剂。
近几年来，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有所报道，但数量不多。有些学者把担载有Pd，Pt，Re，Mo等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，但芳烃收率较低。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，Aked，Nauks SSR，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％。我国大连化物所王林胜等(Catal.Lette.21(1993)35-41)报道了甲烷在MoHZSM-5催化剂上非氧化脱氢芳构化，反应在连续流动固定床反应器进行，催化剂用量为2g，粒度10～30目，反应压力为了200KPa，反应温度为973K，原料气甲烷空速144ml/g-h，甲烷转化率为7.2％，苯的选择性达100％。
本发明的目的旨在提供一种高活性、高选择性的非氧化条件下甲烷催化脱氢芳构化制芳烃的催化剂。
本发明所说的催化剂为SO4 2--MoO4 2--AOx/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，最好为18～38，AOx为金属氧化物，A为Zn、Co、Ni、Cu等过渡金属，催化剂中各组份的含量为(重量百分比)：AOx为0.5～10％，最好1～6％，SO4 2-为0.5～8％，最好1～5％，MoO4 2-以MoO3折合量计为1.5～12％，最好2～9％，余量为HZSM-5。
HZSM-5分子筛可直接使用市售品，也可通过NaZSM-5或NH4ZSM-5分子筛经由离子交换制备。
催化剂采用浸渍法制备：按催化剂中各组份的配比首先把HZSM-5分子筛载体于383K预处理2小时后，将MoO4 2-溶液浸渍于HZSM-5分子筛载体上，该物料在383K烘于2小时，673～1073K焙烧4～12小时，继将A的硫酸盐或硝酸盐溶液再浸渍于其上，于383K烘干2小时，673～1073K焙烧4～12小时，最后，以H2SO4或硫酸铵溶液浸渍，或以硫酸盐溶液浸渍烘干后，再以过量的14N NH4OH浸渍之，然后依次在383K烘干2小时，673K～1073K焙烧4～12小时，即得SO4 2--MoO4 2--AOx/HZSM-5负载型催化剂。
甲烷非氧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，每次试验催化剂用量为0.6g，原料气CH4纯度99.9％，空速1500ml/h-g，反应体系压力为120kPa，反应温度973K。甲烷转化率由色谱分析数据按工作曲线法计算达22％。在含碳产物中苯选择性为92％，甲苯选择性～5％。
本发明提供的催化剂，可以使甲烷通过非氧化脱氢芳构化转化为芳烃，这个过程具有一些独到的优点，如技术上较少复杂性，不存在象氧化过程用空气作氧化剂因而带来的反应产物受CO或N2稀释的问题，主要产物芳烃与来转化的CH4及副产物H2很容易分离，而副产物H2又可作为油品精制工业所需大量H2的来源。由于本发明所提供催化剂在甲烷非氧化转化制芳烃反应中，显示出高的甲烷转化率和芳烃选择性，具有很好的工业应用前景。
下面由实施例进一步说明本发明。
实施例1：
将经折算合0.18g MoO3的钼酸铵溶液浸渍于6g经383K预处理2小时的HZSM-5分子筛上，于383K烘干2小时，673K焙烧4小时，得到催化剂前驱物，置于干燥器中备用。
将经折算含0.04g ZnO的硫酸锌溶液，浸渍于3g经383K预处理的上述催化剂前驱物上，于383K烘干2小时，随后将过量的14N氨水浸渍于其上，于383K烘干2小时，673K焙烧4小时，即得到SO4 2--MoO4 2--ZnO/HZSM-5负载型催化剂。
甲烷非氧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，每次试验催化剂用量为0.6g，粒度40～60目，反应体系压力为120KPa，空速1500ml/h-g，在反应升温过程中，催化剂处于N2气氛保护之下，当温度达到973K时直接导入纯度99.9％的原料气CH4，反应物和产物由在线气相色谱仪(102GD型)热导检测器和氢焰检测器联合作现场分析；色谱柱填料为D.N.P.，柱长2米，以N2为色谱载气。实验数据取自反应开始45min体系达到稳态之后。甲烷转化率由色谱分析数据按工作曲线法计算，XCH4达21.5％。在含碳产物中苯选择性为93％，甲苯选择性～4％。
实施例2：
提高浸渍溶液中过渡金属含量，使钼酸铵溶液中经折算合有MoO3量为0.36g，硫酸锌溶液中经折算含有ZnO含量为0.05g，按照例1制备程序制得SO4 2--MoO4 2--ZnO/HZSM-5负载型催化剂。
甲烷非氧化脱氢芳构化制芳烃试验同例1，结果见表1。
表1反应时间(h) 1 2 3 4 5 6 7 8 9 10 11 12甲烷转化率(％) 20.8 22.4 22.5 22.2 21.1 20.0 19.8 20.2 19.3 18.2 18.4 18.0苯选择性(C％) 93 92 91 91 90 90 89 89 89 89 88 88甲苯选择性(C％) 4.1 4.9 5.4 5.9 7.2 7.2 8.0 8.0 8.2 8.6 8.6 9.0
实施例3：
按照例1制备催化剂含钼前驱物；将经折算含0.03g ZnO的硝酸锌溶液，浸渍于3g经383K预处理2小时的上述催化剂前驱物上，将浸渍后的物料于383K烘干2小时，673K焙烧4小时，后降温到383K，浸渍经折算含有0.04g SO4 2-的硫酸铵溶液，后于383K烘干2小时，673K焙烧4小时，得到SO4 2--MoO4 2--ZnO/HZSM-5负载型催化剂。
甲烷非氧化脱氢芳构化制芳烃试验同例1，甲烷转化率为12％，苯选择性为87％，甲苯选择性为10％。
实施例4：
按照例1制备催化剂含钼前驱物；将经折算含0.03g ZnO的硝酸锌溶液，浸渍于3g经383K预处理2小时的上述催化剂前驱物上，将浸渍后的物料于383K烘干2小时，673K焙烧4小时，后降温到383K，浸渍以经折算含有0.04g SO4 2-的2N H2SO4溶液，后于383K烘干2小时，得SO4 2--MoO4 2--ZnO/HZSM-5负载型催化剂。
甲烷非氧化脱氢芳构化制芳烃试验同例1，反应1小时，相应之甲烷转化率达22％，苯选择性为94％，甲苯选择性为～5％。反应2小时，相应之甲烷转化率降为16％，苯选择性89％，甲苯选择性10％。
实施例5～8：
催化剂制备方法同例1。
改变不同组成的AOx，考察相应制得的SO4 2--MoO4 2--Ni2O3/HZSM-5，SO4 2--MoO4 2--Co2O3/HZSM-5，SO4 2--MoO4 2--CuO/HZSM-5，SO4 2--MoO4 2--ZnO/HZSM-5等四种负载型催化剂上甲烷非氧化脱氢芳构化的反应活性。
甲烷非氧化脱氢芳构化制芳烃试验同例1，其结果列于表2。
表2
催化剂 甲烷转化率(％) 选择性(C％)实施例
苯 甲苯5 SO4 2--MoO4 2--Ni2O3/HZSM-5 5.2 ～99 痕量6 SO4 2--MoO4 2--Co2O3/HZSM-5 15.8 91 67 SO4 2--MoO4 2--CuO/HZSM-5 21.7 84 68 SO4 2--MoO4 2--ZnO/HZSM-5 22.3 93 4
Claims (3)
1.一种非氧化条件下甲烷脱氢芳构化催化剂，为SO4 2--MoO4 2--AOx/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，AOx为Zn、Co、Ni或Cu的过渡金属氧化物；催化剂中各组份的含量的重量百分比为：AOx为0.5％～10％，SO4 2-为0.5％～8％，MoO4 2-以MoO3折合量计为1.5％～10％，余量为HZSM-5。
2.如权利要求1所述的非氧化条件下甲烷脱氢芳构化催化剂，其特征在于HZSM-5分子筛中Si/Al比为18～38。
3.如权利要求1所述的非氧化条件下甲烷脱氢芳构化催化剂，其特征在于催化剂中AOx的含量重量比为1％～6％，SO4 2-为1％～5％，MoO4 2-以MoO3折合量计为2％～9％。
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| CN101767031B (zh) * | 2009-01-07 | 2012-03-14 | 中国石油化工股份有限公司 | 甲烷部分氧化制合成气的低温转化催化剂 |
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| WO2009140790A1 (en) * | 2008-05-21 | 2009-11-26 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Production of aromatics from methane |
| CN102099317B (zh) * | 2008-05-21 | 2013-11-13 | 巴斯夫欧洲公司 | 在单独的位置由c1-c4烷烃与氢气共配料获得苯、甲苯(和萘)的方法 |
| CN102921453B (zh) * | 2012-10-25 | 2014-10-29 | 浙江工业大学 | 一种低温制备甲烷无氧芳构化催化剂的方法 |
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| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767031B (zh) * | 2009-01-07 | 2012-03-14 | 中国石油化工股份有限公司 | 甲烷部分氧化制合成气的低温转化催化剂 |
| CN105832896B (zh) * | 2016-05-12 | 2019-06-21 | 江苏康缘药业股份有限公司 | 一种治疗宫颈炎的中药及其制备方法、应用 |
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