改性内蒙高岭土在FCC脱硫催化剂中的应用研究
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摘要
随着环保法规的日益严格,降低汽油的硫含量势在必行。在目前众多的脱硫方法中,最具吸引力的是在催化裂化反应过程中将有机硫化合物原位裂解脱除,降低催化裂化汽油中的硫含量。本课题通过对FCC催化剂的基质(高岭土)进行改性处理,使其成为具有裂化和脱硫活性的助剂,在裂化反应的同时完成脱硫过程。主要研究了处理方法对内蒙高岭土的结构、表面酸性和裂化及脱硫性能的影响。
在酸碱处理过程中,重点对比分析了酸、碱处理土结构和性能的变化趋势,并制备了不同n(SiO_2)/n(Al_2O_3)碱处理土。利用吡啶-TPD分别对其进行了酸性表征,利用红外光谱仪测定不同n(SiO_2)/n(Al_2O_3)碱处理土的酸类型,并进行裂化脱硫活性测试。实验表明:酸处理土的酸性位数量和强度均高于碱处理土,但碱处理土的裂化脱硫性能优于酸处理土。随着n(SiO_2)/n(Al_2O_3)的减小,碱处理土的B酸、L酸含量以及表面酸性分布和裂化脱硫活性均呈现规律性变化。
为了进一步增强催化剂的氢转移能力,在碱处理土上负载具有氢转移功能的金属。考察了浸渍、离子交换、固相混合和添加尖晶石助剂等不同的负载方法,且对于不同的金属其裂化脱硫性能不同。结果表明:在碱处理土上以合适的方法负载适宜的金属能够有效提高催化剂的氢转移能力,增加催化剂表面中等强度酸性位的比例,从而使其裂化脱硫性能增强。
With environmental protection law and regulation gradually strict, the sulfur content of gasoline reducing is imperative. In actual numerous desulfuration methods, it is the most attractive that organic sulphur compound cracks and extricates at original place in catalytic cracking reaction process to reduce sulfur content of catalytic gasoline. Base material of FCC catalyst (kaolin) was treated to be the assistant having cracking and desulfuration activity, which could accomplish desulfuration during the cracking process. The effect which treatment method had on the structure, characteristic and cracking desulphurization performance of acid and alkali treated kaolin of Inner Mongolia was studied in this paper.
During the acid and alkali treatment, the change trend of the structure and performance of acid and alkali treated kaolin were given stress analysis.The alkali- treated kaolin with different molar ratio of n(SiO_2)/n(Al_2O_3) had been prepared. The effect of the ratio of n(SiO_2)/n(Al_2O_3) on the kaolin performance, including surface acidity, acid type, amount of acid sites and cracking desulphurization capability, were examined by pyridine-TPD, IR and the test of cracking activity. The results showed that the amount and the intensity of acid site of acid-treated kaolin were all higher than alkali-treated kaolin. The results of cracking desulphurization performance were conversed. The results also indicated that surface acidity and cracking activity of the alkali-treated kaolins had an obviously disciplinary change with the decrease of the ratio of n(SiO_2)/n(Al_2O_3), and the contents of B and L acid were changed through the adjustment of different molar ratio of n(SiO_2)/n(Al_2O_3).
For the sake of increasing the hydrogen transfer capability, the metal with the hydrogen transfer capability was loaded on the alkali-treated kaolin. Different methods of loading metal including dipping, ion-exchange, mix and spinel were examined.The cracking desulphurization performances of the catalysts loading different metal were different. The results showed that loading appropriate metal on the alkali-treated kaolin with appropriate method could improve the hydrogen transfer capability and increase the percent of medium intensity acid site, so the cracking desulphurization performances of the catalysts were enhanced.
在酸碱处理过程中,重点对比分析了酸、碱处理土结构和性能的变化趋势,并制备了不同n(SiO_2)/n(Al_2O_3)碱处理土。利用吡啶-TPD分别对其进行了酸性表征,利用红外光谱仪测定不同n(SiO_2)/n(Al_2O_3)碱处理土的酸类型,并进行裂化脱硫活性测试。实验表明:酸处理土的酸性位数量和强度均高于碱处理土,但碱处理土的裂化脱硫性能优于酸处理土。随着n(SiO_2)/n(Al_2O_3)的减小,碱处理土的B酸、L酸含量以及表面酸性分布和裂化脱硫活性均呈现规律性变化。
为了进一步增强催化剂的氢转移能力,在碱处理土上负载具有氢转移功能的金属。考察了浸渍、离子交换、固相混合和添加尖晶石助剂等不同的负载方法,且对于不同的金属其裂化脱硫性能不同。结果表明:在碱处理土上以合适的方法负载适宜的金属能够有效提高催化剂的氢转移能力,增加催化剂表面中等强度酸性位的比例,从而使其裂化脱硫性能增强。
With environmental protection law and regulation gradually strict, the sulfur content of gasoline reducing is imperative. In actual numerous desulfuration methods, it is the most attractive that organic sulphur compound cracks and extricates at original place in catalytic cracking reaction process to reduce sulfur content of catalytic gasoline. Base material of FCC catalyst (kaolin) was treated to be the assistant having cracking and desulfuration activity, which could accomplish desulfuration during the cracking process. The effect which treatment method had on the structure, characteristic and cracking desulphurization performance of acid and alkali treated kaolin of Inner Mongolia was studied in this paper.
During the acid and alkali treatment, the change trend of the structure and performance of acid and alkali treated kaolin were given stress analysis.The alkali- treated kaolin with different molar ratio of n(SiO_2)/n(Al_2O_3) had been prepared. The effect of the ratio of n(SiO_2)/n(Al_2O_3) on the kaolin performance, including surface acidity, acid type, amount of acid sites and cracking desulphurization capability, were examined by pyridine-TPD, IR and the test of cracking activity. The results showed that the amount and the intensity of acid site of acid-treated kaolin were all higher than alkali-treated kaolin. The results of cracking desulphurization performance were conversed. The results also indicated that surface acidity and cracking activity of the alkali-treated kaolins had an obviously disciplinary change with the decrease of the ratio of n(SiO_2)/n(Al_2O_3), and the contents of B and L acid were changed through the adjustment of different molar ratio of n(SiO_2)/n(Al_2O_3).
For the sake of increasing the hydrogen transfer capability, the metal with the hydrogen transfer capability was loaded on the alkali-treated kaolin. Different methods of loading metal including dipping, ion-exchange, mix and spinel were examined.The cracking desulphurization performances of the catalysts loading different metal were different. The results showed that loading appropriate metal on the alkali-treated kaolin with appropriate method could improve the hydrogen transfer capability and increase the percent of medium intensity acid site, so the cracking desulphurization performances of the catalysts were enhanced.
引文
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[8] 卜欣立,闫永辉,王玉环,FCC 汽油脱硫新技术.石家庄职业技术学院学报,2002,14(4):8～10
[9] 陈焕章,李永丹 ,赵地顺,催化裂化汽油脱硫技术进展,化工科技,2004,12(3):46～51
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[16] Zinnen H A. Removal of Organic Sulfur Compounds from FCC Gasoline Feed Stock.US:5935422,1999-06-05
[17] Gil J.Greenwood,Dennis Kidd,Next generation sulfur removal technology,2000 NPRA Annual Meeting,2000
[18] Forte P.Removal 0f sulfur from a FCC gasoline fraction,US:5582714,1996
[19] Bartek,Removal of sulfur from a hydrocarbon stream by low severity adsorption,US:5919354,1999
[20] Lesieur,System and method for desulfurizing gasoline or diesel fuel to produce a low sulfur content fuel for use in an internal combustion engine,US:6129835,2000
[21] Byron G.Johnson,Dennis Kidd,et a1 .Application of Phillips’Szorb process to distillates:meeting the challenge,2001 NPRA Annual Meeting,2001
[22] Rellillo G E. Desulfur Catalyst and Additive for FCC.Euro Chem News,2000,72(1901):23～27
[23] 汤海涛,凌珑,王龙延,含硫原油加工过程的硫转化规律,“面向 21 世纪石油炼制技术交流会论文集,南京:中国石油化工情报学台炼制会,1999,223～233
[24] 庞新梅,李春义,山红红等,硫化物在 FCC 催化剂上的裂化脱硫研究, 石油大学学报(自然科学版),2003,27(1):95～98
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