FCC轻汽油在纳米ZSM-5沸石上的芳构化
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摘要
为了满足生产低硫汽油以及超低硫汽油的要求,对轻汽油进行脱硫处理的重要性日益突出。将轻汽油中的高含量烯烃通过芳构化反应转化为高辛烷值的芳烃和异构烷烃,有可能为轻汽油加氢脱硫技术提供有利条件。
本文采用纳米ZSM-5沸石催化剂对轻汽油中的烯烃芳构化进行了研究,得到以下主要结果:
(1)以FCC轻汽油(≤85℃)为原料,考察了芳构化反应条件及原料中二烯烃杂质对纳米ZSM-5催化剂反应性能的影响。结果表明,纳米ZSM-5催化剂具有较好的芳构化性能,但轻汽油芳构化反应的液收低,原料中的二烯烃能加速催化剂失活,这些问题使轻汽油芳构化反应技术的开发工作面临较大挑战。
(2)在FCC轻汽油(≤85℃)中掺入C4 LPG,可以弥补轻汽油在芳构化反应过程中的液收损失。C4 LPG的加入,对催化剂的芳构化及稳定性均有利。
(3)以FCC轻汽油(≤85℃)为原料,考察了纳米ZSM-5催化剂与一种Al_2O_3加氢脱硫催化剂(DLS-1)联合使用的效果。结果表明,将此两种催化剂以适当方式结合使用,有利于防止烯烃加氢饱和,使加氢脱硫催化剂DLS-1表现出更好的加氢脱硫稳定性和选择性。在280℃,1.6 MPa,V(H_2)=13 ml/min,WHSV=1.5h~(-1),催化剂混合为m(ZSM-5):m(DLS-1)=2:1,上端装填纳米ZSM-5催化剂,下端装填加氢脱硫催化剂DLS-1的情况下,组合催化剂的脱硫率为60%左右,烯烃饱和率为20%左右,与单独使用DLS-1催化剂时脱硫率为80%左右及烯烃饱和率为60%左右相比,其加氢脱硫的选择性提高。问题是,在如此低的反应温度下没有发现FCC轻汽油的芳构化产物。
In order to fulfill the standard of low sulfur and ultra-low sulfur gasoline,the hydrodesulfurization of FCC light gasoline is more and more important.The hydrodesulfurization selectivity of FCC light gasoline may be remarkably favored by pre-aromatization of the high level olefms in the light range gasoline.
Thus,the aromatization of FCC light gasoline was studied herein with a nano-sized HZSM-5 zeolitic catalyst.The following main results are obtained:
(1) The influence of reaction conditions and impurities in feedstock on the aromatization of FCC light gasoline(≤85℃) over nano-sized ZSM-5 catalyst is investigated.Results show that,nano-sized ZSM-5 catalyst exhibits wonderful performance of aromatization.But the gasoline yield of the reaction is quite low,and the deactivation of catalyst is very serious due primarily to the thermal oligomerization of diene in FCC light gasoline feedstock.These problems make the aromatization of FCC light gasoline highly challengeable in the course of commercialization.
(2) The co-feed of C4 liquefied petroleum gas(C4 LPG) with the FCC light gasoline (≤85℃) seems to be a good method to compensate the gasoline yield of the aromatization of FCC light gasoline.
(3) The combinational use of Nano-sized ZSM-5 catalyst with a Al_2O_3 supported hydrodesulfurization catalyst(DLS-1) at low temperature is another clue to FCC light gasoline(≤85℃) processing.Under the conditions of 280℃,1.6 MPa,V(H_2) = 13 ml/min, WHSV=1.5 h~(-1),the weight proportion of nano-sized HZSM-5 catalyst to hydrodesulfurization catalyst DLS-1 = 2,the loading of nano-sized HZSM-5 catalyst over the hydrodesulfurization catalyst DLS-1 gives 60%desulfurization rate and 20%olefm saturation rate.This hydrodesulfurization selectivity of the combined catalysts is better than the DLS-1 alone which results in 60%olefin loss at the desulfurization rate of about 80%.The only problem is that under such a low temperature the aromatization of FCC light gasoline over the zeolitic catalyst was not seen.
本文采用纳米ZSM-5沸石催化剂对轻汽油中的烯烃芳构化进行了研究,得到以下主要结果:
(1)以FCC轻汽油(≤85℃)为原料,考察了芳构化反应条件及原料中二烯烃杂质对纳米ZSM-5催化剂反应性能的影响。结果表明,纳米ZSM-5催化剂具有较好的芳构化性能,但轻汽油芳构化反应的液收低,原料中的二烯烃能加速催化剂失活,这些问题使轻汽油芳构化反应技术的开发工作面临较大挑战。
(2)在FCC轻汽油(≤85℃)中掺入C4 LPG,可以弥补轻汽油在芳构化反应过程中的液收损失。C4 LPG的加入,对催化剂的芳构化及稳定性均有利。
(3)以FCC轻汽油(≤85℃)为原料,考察了纳米ZSM-5催化剂与一种Al_2O_3加氢脱硫催化剂(DLS-1)联合使用的效果。结果表明,将此两种催化剂以适当方式结合使用,有利于防止烯烃加氢饱和,使加氢脱硫催化剂DLS-1表现出更好的加氢脱硫稳定性和选择性。在280℃,1.6 MPa,V(H_2)=13 ml/min,WHSV=1.5h~(-1),催化剂混合为m(ZSM-5):m(DLS-1)=2:1,上端装填纳米ZSM-5催化剂,下端装填加氢脱硫催化剂DLS-1的情况下,组合催化剂的脱硫率为60%左右,烯烃饱和率为20%左右,与单独使用DLS-1催化剂时脱硫率为80%左右及烯烃饱和率为60%左右相比,其加氢脱硫的选择性提高。问题是,在如此低的反应温度下没有发现FCC轻汽油的芳构化产物。
In order to fulfill the standard of low sulfur and ultra-low sulfur gasoline,the hydrodesulfurization of FCC light gasoline is more and more important.The hydrodesulfurization selectivity of FCC light gasoline may be remarkably favored by pre-aromatization of the high level olefms in the light range gasoline.
Thus,the aromatization of FCC light gasoline was studied herein with a nano-sized HZSM-5 zeolitic catalyst.The following main results are obtained:
(1) The influence of reaction conditions and impurities in feedstock on the aromatization of FCC light gasoline(≤85℃) over nano-sized ZSM-5 catalyst is investigated.Results show that,nano-sized ZSM-5 catalyst exhibits wonderful performance of aromatization.But the gasoline yield of the reaction is quite low,and the deactivation of catalyst is very serious due primarily to the thermal oligomerization of diene in FCC light gasoline feedstock.These problems make the aromatization of FCC light gasoline highly challengeable in the course of commercialization.
(2) The co-feed of C4 liquefied petroleum gas(C4 LPG) with the FCC light gasoline (≤85℃) seems to be a good method to compensate the gasoline yield of the aromatization of FCC light gasoline.
(3) The combinational use of Nano-sized ZSM-5 catalyst with a Al_2O_3 supported hydrodesulfurization catalyst(DLS-1) at low temperature is another clue to FCC light gasoline(≤85℃) processing.Under the conditions of 280℃,1.6 MPa,V(H_2) = 13 ml/min, WHSV=1.5 h~(-1),the weight proportion of nano-sized HZSM-5 catalyst to hydrodesulfurization catalyst DLS-1 = 2,the loading of nano-sized HZSM-5 catalyst over the hydrodesulfurization catalyst DLS-1 gives 60%desulfurization rate and 20%olefm saturation rate.This hydrodesulfurization selectivity of the combined catalysts is better than the DLS-1 alone which results in 60%olefin loss at the desulfurization rate of about 80%.The only problem is that under such a low temperature the aromatization of FCC light gasoline over the zeolitic catalyst was not seen.
引文
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