A novel ultra-stable zeolite, NSZ, rich in secondary pores was developed through the combination of gas-phase andmild hydrothermal methods. This zeolite was successfully tested in an industrial setting for the first t...A novel ultra-stable zeolite, NSZ, rich in secondary pores was developed through the combination of gas-phase andmild hydrothermal methods. This zeolite was successfully tested in an industrial setting for the first time in the world. The porestructure characteristics of the NSZ zeolite prepared for industrial use were analyzed and characterized using BET. The resultsindicate a significant increase in the secondary pore volume of NSZ zeolite compared to the existing ultra-stable zeolite HSZ-5, which is produced through a conventional gas-phase method. The average secondary pore volume to total pore volume ratioin NSZ zeolite was found to be 58.96% higher. The catalytic cracking performance of NSZ zeolite was evaluated. The resultsshowed that the NSC-LTA catalyst, with NSZ as the active component, outperformed the HSC-LTA catalyst with HSZ-5 zeolitein terms of obtaining more high-value products (gasoline and liquefied petroleum gas) during the hydrogenated light cycle oilprocessing. Additionally, the NSC-LTA catalyst showed a significant improvement in coke selectivity.展开更多
The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total ...The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature （excluding 800 ℃）. The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature. The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5 zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking.展开更多
A new type of zeolite La-USL （ultra stable zeolite L （zeolite USL） modified by La）, which has superior activity, stability and selectivity in catalytic cracking of hydrocarbons and thus can be used as an active ca...A new type of zeolite La-USL （ultra stable zeolite L （zeolite USL） modified by La）, which has superior activity, stability and selectivity in catalytic cracking of hydrocarbons and thus can be used as an active catalyst component, is reported in this paper. The zeolite L with relative crystallinity of above 90% was synthesized by the hydrothermal crystallization method under optimum conditions and characterized by means of XRD, NH3-TPD and isotherm adsorption techniques. The in-situ synthesized zeolite L with a SiO2/Al2O3 mole ratio of 5-6 was modified by cation ion exchange, hydrothermal dealumination and chemical modifications with La in order to prepare La-containing USL with a higher framework SiO2/Al2O3 mole ratio of 15-30. The modified zeolite La-USL was used as an active additive component of fluid catalytic cracking （FCC） catalyst and the resulting catalysts were evaluated by microactivity test （MAT） and fixed-fluidized bed （FFB） experiments using heavy oil as feedstock. The influence of La content in La- USL on cracking product distribution, gasoline group composition and research octane number （RON） was investigated. The results showed that when La content in La-USL was 0.8 wt%, the addition of the corresponding La-USL could result in a FCC catalyst that produced significant improvement in product distribution and gasoline quality.展开更多
This article investigated the deactivation caused by hydrothermal treatment and metal contamination of two cracking catalysts containing the Y and ZRP- 1 zeolites aimed at maximization of light olefin yield.Test resul...This article investigated the deactivation caused by hydrothermal treatment and metal contamination of two cracking catalysts containing the Y and ZRP- 1 zeolites aimed at maximization of light olefin yield.Test results had shown that the hydrothermal stability and resistance to metal contamination of the ZRP-1zeolite were apparently better than those of the Y zeolite. Hydrothermal treatment and metal contamination had not only changed the catalytic cracking performance of respective zeolites, but at the same time had also modified to a definite degree of the relative proportions of effective components in these two zeolites and affected the synergistic effects between them, resulting in a relative enhancement of secondary cracking ability of the catalyst and increased olefin selectivity in the FCC products. In the course of application of catalyst for maximization of light olefins yield appropriate adjustment of the relative proportion of two active components can help to alleviate the products distribution and selectivity changes caused by deactivationof FCC catalysts.展开更多
研究发现,四氯化硅气相法制备高硅Y型沸石与稀土离子交换相结合,能使高硅Y型沸石中RE_2O_3含量达到6％～9％,在晶胞常数相近的情况下,与水热法制备USY相比,RE_2O_3含量提高近3倍,有效地提高了高硅Y型沸石的裂化活性和氢转移活性。用XBD...研究发现,四氯化硅气相法制备高硅Y型沸石与稀土离子交换相结合,能使高硅Y型沸石中RE_2O_3含量达到6％～9％,在晶胞常数相近的情况下,与水热法制备USY相比,RE_2O_3含量提高近3倍,有效地提高了高硅Y型沸石的裂化活性和氢转移活性。用XBD、FT-IB,^(27)Al MAS NMB及BET-N_2吸附方法进行表征,从反应机理和制备工艺上探讨了两种制备方法提高稀土含量的差异,提出及时清理硅铝碎片,保持孔道畅通,是有效提高高硅Y型沸石中稀土含量的关键。展开更多
基金the National Key R&D Program of China(2022YFA1504404)the SINOPEC Research Program(121036-5).
文摘A novel ultra-stable zeolite, NSZ, rich in secondary pores was developed through the combination of gas-phase andmild hydrothermal methods. This zeolite was successfully tested in an industrial setting for the first time in the world. The porestructure characteristics of the NSZ zeolite prepared for industrial use were analyzed and characterized using BET. The resultsindicate a significant increase in the secondary pore volume of NSZ zeolite compared to the existing ultra-stable zeolite HSZ-5, which is produced through a conventional gas-phase method. The average secondary pore volume to total pore volume ratioin NSZ zeolite was found to be 58.96% higher. The catalytic cracking performance of NSZ zeolite was evaluated. The resultsshowed that the NSC-LTA catalyst, with NSZ as the active component, outperformed the HSC-LTA catalyst with HSZ-5 zeolitein terms of obtaining more high-value products (gasoline and liquefied petroleum gas) during the hydrogenated light cycle oilprocessing. Additionally, the NSC-LTA catalyst showed a significant improvement in coke selectivity.
基金The authors would like to thank the financial support from the National Basic Research Program of China fgrant No．2004CB 217806)the National Natural Science Foundation of China (Grant No．20373043) the Scientific Research Key Foundation for the Returned Overseas Chinese Scholars of State Education Ministry．
文摘The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature （excluding 800 ℃）. The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature. The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5 zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking.
文摘A new type of zeolite La-USL （ultra stable zeolite L （zeolite USL） modified by La）, which has superior activity, stability and selectivity in catalytic cracking of hydrocarbons and thus can be used as an active catalyst component, is reported in this paper. The zeolite L with relative crystallinity of above 90% was synthesized by the hydrothermal crystallization method under optimum conditions and characterized by means of XRD, NH3-TPD and isotherm adsorption techniques. The in-situ synthesized zeolite L with a SiO2/Al2O3 mole ratio of 5-6 was modified by cation ion exchange, hydrothermal dealumination and chemical modifications with La in order to prepare La-containing USL with a higher framework SiO2/Al2O3 mole ratio of 15-30. The modified zeolite La-USL was used as an active additive component of fluid catalytic cracking （FCC） catalyst and the resulting catalysts were evaluated by microactivity test （MAT） and fixed-fluidized bed （FFB） experiments using heavy oil as feedstock. The influence of La content in La- USL on cracking product distribution, gasoline group composition and research octane number （RON） was investigated. The results showed that when La content in La-USL was 0.8 wt%, the addition of the corresponding La-USL could result in a FCC catalyst that produced significant improvement in product distribution and gasoline quality.
文摘This article investigated the deactivation caused by hydrothermal treatment and metal contamination of two cracking catalysts containing the Y and ZRP- 1 zeolites aimed at maximization of light olefin yield.Test results had shown that the hydrothermal stability and resistance to metal contamination of the ZRP-1zeolite were apparently better than those of the Y zeolite. Hydrothermal treatment and metal contamination had not only changed the catalytic cracking performance of respective zeolites, but at the same time had also modified to a definite degree of the relative proportions of effective components in these two zeolites and affected the synergistic effects between them, resulting in a relative enhancement of secondary cracking ability of the catalyst and increased olefin selectivity in the FCC products. In the course of application of catalyst for maximization of light olefins yield appropriate adjustment of the relative proportion of two active components can help to alleviate the products distribution and selectivity changes caused by deactivationof FCC catalysts.
文摘研究发现,四氯化硅气相法制备高硅Y型沸石与稀土离子交换相结合,能使高硅Y型沸石中RE_2O_3含量达到6％～9％,在晶胞常数相近的情况下,与水热法制备USY相比,RE_2O_3含量提高近3倍,有效地提高了高硅Y型沸石的裂化活性和氢转移活性。用XBD、FT-IB,^(27)Al MAS NMB及BET-N_2吸附方法进行表征,从反应机理和制备工艺上探讨了两种制备方法提高稀土含量的差异,提出及时清理硅铝碎片,保持孔道畅通,是有效提高高硅Y型沸石中稀土含量的关键。
