Preparation of HZSM-5 zeolite assisted by glycerin and its catalytic performance for methane aromatization
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摘要: 以正硅酸乙酯（TEOS）为硅源，甘油为辅助剂，在水热条件下合成HZSM-5分子筛。考察甘油添加量、晶化时间对HZSM-5分子筛的晶粒尺寸、相对结晶度和酸性等性质及其甲烷无氧芳构化催化性能的影响。利用X射线衍射（XRD）、扫描电镜（SEM）、氨程序升温脱附（NH3-TPD）等分析手段对不同条件合成的HZSM-5分子筛样品进行表征。结果表明，在添加一定量的甘油辅助剂的条件下，通过调控晶化时间，可以提升HZSM-5分子筛的相对结晶度，在一定程度上抑制无定型SiO2的产生，增加其酸量。在甲烷无氧芳构化反应中，甘油辅助合成的HZSM-5分子筛催化剂表现出优良的催化性能，与未添加甘油合成的HZSM-5分子筛催化剂相比，甲烷转化率、苯选择性和芳烃选择性均有较大提高，且具有较强的稳定性与容炭能力。Abstract: HZSM-5 zeolite was synthesized under hydrothermal condition with TEOS as silicon source and glycerin as auxiliary agent. The effects of glycerol addition and crystallization time on the grain size, relative crystallinity and acidity of HZSM-5 molecular sieves and their catalytic performance for anaerobic aromatization of methane were investigated. XRD, SEM, NH3-TPD and other analytical methods were used to characterize the HZSM-5 molecular sieve samples synthesized under different conditions. The results show that the relative crystallinity of HZSM-5 molecular sieve can be increased through adding certain amount of glycerol adjuvant and adjusting the crystallization time, meanwhile, the formation of amorphous SiO2 can be suppressed and the acid content can be increased. The HZSM-5 prepared with glycerol assistance shows excellent catalytic performance in methane anaerobic aromatization. Compared with the HZSM-5 catalyst synthesized without the addition of glycerin, the methane conversion rate, benzene selectivity and aromatic selectivity are all greatly improved, and it has better stability and resistance to carbon deposition.
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Key words:
- glycerin /
- HZSM-5 /
- methane /
- anaerobic aromatization /
- aromatics
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图 2 反应装置示意图
Figure 2 Diagram of reaction device
1-one way valve; 2-mass flow controller; 3-four way valve; 4-distribution board; 5-U-shaped quartz tube reactor; 6-reaction heating furnace; 7-pipeline with temperature control; 8-ten way valve; 9-on line chromatography
图 3 不同甘油添加量合成的HZSM-5分子筛的SEM照片
Figure 3 SEM images of the HZSM-5 zeolite synthesized with different amount of glycerol addition
(a): HZSM-5x=0; (b): HZSM-5x=1; (c): HZSM-5x=2; (d): HZSM-5x=3
图 4 不同甘油添加量合成的HZSM-5分子筛的XRD谱图
Figure 4 XRD patterns of the HZSM-5 zeolite synthesized with different amount of glycerol addtion
图 5 不同甘油添加量合成的HZSM-5分子筛的N2吸附-脱附等温线
Figure 5 N2 adsorption and desorption isotherms of the HZSM-5 synthesized with different amount of glycerin addition
图 6 不同甘油添加量合成HZSM-5分子筛的孔径分布
Figure 6 Pore size distribution of the HZSM-5 molecular sieves synthesized with different amount of glycerol addition
图 7 不同水热晶化时间和合成的HZSM-5分子筛的SEM照片
Figure 7 SEM images of the HZSM-5 zeolite synthesized with different hydrothermal crystallization time
(a): HZSM-5t=24; (b): HZSM-5t=48; (c): HZSM-5t=72; (d): HZSM-5t=96
图 8 不同水热晶化时间合成的HZSM-5分子筛的XRD谱图
Figure 8 XRD patters of the HZSM-5 zeolite synthesized by different hydrothermal crystallization time
图 9 不同水热晶化时间合成的HZSM-5分子筛的N2吸附-脱附等温线
Figure 9 N2 adsorption desorption isotherms of the HZSM-5 synthesized by different hydrothermal times
图 10 不同晶化时间合成HZSM-5分子筛的孔径分布
Figure 10 Pore size distribution of the HZSM-5 synthesized with different crystallization time
(a): HZSM-5t=24; (b): HZSM-5t=48; (c): HZSM-5t=72; (d): HZSM-5t=96
图 11 不同水热晶化时间合成的HZSM-5分子筛的NH3-TPD谱图
Figure 11 NH3-TPD profiles of the HZSM-5 synthesized with different hydrothermal crystallization time
图 12 市售6%Mo/HZSM-5甲烷无氧芳构化催化反应性能
Figure 12 Catalytic performance of the commercial 6% Mo/HZSM-5 for MDA
图 13 不同甘油添加量合成的催化剂甲烷无氧芳构化催化反应性能
Figure 13 Catalytic performance of the MDA catalysts synthesized with different glycerol content
图 14 不同水热晶化时间合成的催化剂甲烷无氧芳构化催化反应性能
Figure 14 Catalytic performance of the MDA catalysts synthesized with different hydrothermal time
表 1 不同甘油添加量合成的HZSM-5分子筛的比表面积和孔容
Table 1 Specific surface area and pore volume of the HZSM-5 synthesized with different amount of glycerol content
Sample Specific surface area A/(m2·g-1) Pore volume v/(cm3·g-1) mesopore micropore total mesopore micropore total HZSM-5x=0 113.9 142.0 255.9 0.066 0.059 0.125 HZSM-5x=1 136.5 207.8 344.3 0.091 0.084 0.175 HZSM-5x=2 186.7 215.1 401.8 0.098 0.090 0.188 HZSM-5x=3 166.3 215.7 382.0 0.090 0.089 0.179 
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表 2 分子筛的比表面积和孔容
Table 2 Specific surface area and pore volume of molecular sieve
Sample Specific surface area A/(m2·g-1) Pore volume v/(cm3·g-1) mesopore micropore total mesopore micropore total HZSM-5t=24 186.7 215.1 401.8 0.098 0.090 0.188 HZSM-5t=48 185.4 189.3 374.7 0.108 0.080 0.188 HZSM-5t=72 146.0 183.7 329.7 0.094 0.076 0.170 HZSM-5t=96 156.4 172.5 328.9 0.092 0.071 0.163 6%Mo/HZSM-5t=24 101.0 217.5 318.5 0.065 0.086 0.151
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表 3 不同晶化时间合成HZSM-5分子筛的酸量
Table 3 Acid content of the HZSM-5 zeolite synthesized with different crystallization time
Sample HZSM-5 6%Mo/HZSM-5 t=24h t=48h t=72h t=96h t=24h t=48h t=72h t=96h Acid amount
/(mmol·g-1)weak 0.5799 0.5308 0.5242 0.5716 0.4453 0.4377 0.4147 0.4336 mediate 0.1629 0.1451 0.1552 0.1584 0.1723 0.1721 0.169 0.1716 strong 0.3232 0.2842 0.2776 0.3330 0.1474 0.1421 0.1725 0.1419 total 1.0660 0.9600 0.9570 1.0630 0.7650 0.7520 0.7490 0.7470
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表 4 失活催化剂的失重率
Table 4 Weight loss rate of the deactivated MDA catalysts
Deactivated catalyst HZSM-5t=24 HZSM-5t=48 HZSM-5t=72 HZSM-5t=96 Weight loss rate /% 5.19 5.35 4.63 4.69
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