流化床催化裂化汽油加氢改质催化剂及工艺研究
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摘要
生产低硫、低烯烃和高辛烷值的清洁汽油是国家保持能源经济可持续发展的必然要求。我国将于2011年在全国范围内实施《轻型车污染物排放限值及测量方法(中国Ⅳ阶段)》标准,要求汽油中烯烃体积分数≯18%,芳烃体积分数≯35%,硫含量≯50μg／g。在我国成品汽油80%以上来自FCC装置,FCC汽油中的硫含量占汽油中硫含量的90%以上,FCC汽油具有较高的烯烃含量30-55vol.%,较高的硫含量为150-1500μg／g。
本课题要解决全馏份催化裂化汽油脱硫,是在保证辛烷值损失较小(RON≤1)的前提下实现。为此必须结合不同催化剂和原料油的特点对改质工艺优化组合,我们得到以下结论：
1采用两步法改质过程：
(1)Ni-Al2O3(DQG0905)脱硫催化剂用于催化裂化汽油加氢改质评价140 h。反应后,硫含量从288μg／g降低到71μg／g,加氢脱硫率75%；烯烃含量从33.2 vol.%降低到26.2vol.%,降烯烃率21%;辛烷值损失3.3个单位。La2O3-HZSM-5(DQG0904)芳构化催化剂用于催化裂化汽油加氢改质评价220 h。反应后,硫含量从288μg／g降低到184μg／g,加氢脱硫率为36%；烯烃含量从33.2 vol.%降低到19.9 vol.%,降烯烃率40%;芳烃含量从21.1 vol.%升高到26.1 vol.%；改质后辛烷值从92.9升高到93.3
(2)采用先芳构化(DQG0904)后脱硫(DQG0905)的组合顺序,用于催化裂化汽油加氢改质评价660 h。反应后,硫含量从242μg／g降低到73μg／g,加氢脱硫率70%；烯烃含量从36.8 vol.%降低到24.9 vol.%,降烯烃率34%；芳烃含量从18.9.vol.%升高到19.9 vol.%；改质后辛烷值从87.8升高到89.4
2 CoMo-MgOAl2O3作为脱硫催化剂用于催化裂化汽油的加氢改质,考察了不同条件下催化剂的催化性能。结果显示在反应温度为240-260℃、4.0-6.0h-1,2Mpa的条件下硫含量可降低到<50μg／g、RON损失<1.0,活性稳定性能优良。
3以钛酸四丁酯为钛源,采用浸渍法研制了一系列TiO2改性的Ni-Mo/HZSM-5催化剂,通过系统表征,并在连续微反固定床装置上评价了其全馏分催化裂化汽油加氢脱硫性能。结果表明,ZiO2改性可以弱化MoO3和HZSM-5之间的相互作用,抑制Al2(MoO4)3的形成,从而使催化剂脱硫活性大大提高。
Production of low sulfur, low olefin and high-octane number clean gasoline is energy economy to maintain its essential requirement for sustainable development. In China, "Limits and Measurement Methods for Emissions from Light-Duty vehicles (Phase IV)" standards will be executed on 2011, in which less than 18vol.%of olefin content,35 vol.%of aromatic content, and 50μg/g of sulfur content in gasoline are required to meet the No. IV emission standards. FCC gasoline constitutes approximate 80%of the total gasoline pool and sulfur content of FCC gasoline accounted for more than 90%of the total value. FCC gasoline consists of great value of olefin (30～55 vol.%) and sulfur (150-1500μg/g).
The key issue of this article will focuses on the realization of desulfurization of full-range FCC gasoline by means of the little loss of octane number(RON≤1). Thus, The article have to combine different characteristics of catalysts and feedstock composition on the upgrading process optimization. Conclusions from the experiments are summarized as follow:
1 Adopt to two-step hydro-upgrading process:
(1) NiS04-Al203 (DQG0905) desulfurization catalyst was prepared and used in the FCC gasoline hydro-upgrading for 140 h. After hydrotreatment, the sulfur decreases from 288 to 71μg/g, with a 75%conversion rate of hydrodesulfurization (HDS); Olefin decreased from 33.2vol.%to 26.2vol.%, with a 21%conversion rate of hydrodeolefinization (HDO); The RON of product lost 3.3 compared with feed. La2O3-HZSM-5(DQG0904) Aromatization catalyst was prepared and used in the FCC gasoline hydro-upgrading for 220 h. After hydrotreatment, the sulfur decreases from 288 to 184μg/g, with a 36%conversion rate of HDS; the olefin decreased from 33.2vol.%to 19.9vol.%, with a 40%conversion rate of HDO; the aromatic content increased from 21.1 vol.%to 26.1 vol.%; the RON of gasoline has only a slight change from 92.9 to 93.3 after the upgrading process.
(2) Applying the sequence that aromatization(DQG0904) followed by desulfurization(DQG0905), hydrotreatment was performed for hydro-upgrading of FCC gasoline for 660h. After hydrotreatment, the sulfur decreases from 242 to 73μg/g, with a 70% conversion rate of HDS; the olefin content decreased from 36.8vol.%to 24.9vol.%, with a 34%conversion rate of HDO; the aromatic increased from 18.9.1vol.%to 19.9vol.%; the RON of gasoline has change from 87.8 to 89.4 after the upgrading process.
2 CoMo-MgOAl2O3 as desulfurization catalyst is used to study different conditions on catalytic performance and evaluat hydro-upgrading of FCC gasoline. The results show that 240-260℃,4.0-6.0 h-1,2.0Mpa conditions can reduce the sulfur content to< 50μg/g, RON loss of< 1.0, excellent activity and stability.
3 A series of TiO2-modified Ni-Mo/HZSM-5 catalysts were prepared by impregnation method with tetrabutyl titanate as a titanium source, and characterized and evaluated by hydrodesulfurization (HDS) activity for full-range fluid catalytic cracking (FCC) gasoline in a continuous-flow fixed-bed micro-reactor. The results show that the coverage of TiO2 on HZSM-5 can weaken the interaction between MoO3 and HZSM-5 and inhibites the formation of Al2(MoO4)3, so that the catalyst desulfurization activity increases substantially.
本课题要解决全馏份催化裂化汽油脱硫,是在保证辛烷值损失较小(RON≤1)的前提下实现。为此必须结合不同催化剂和原料油的特点对改质工艺优化组合,我们得到以下结论：
1采用两步法改质过程：
(1)Ni-Al2O3(DQG0905)脱硫催化剂用于催化裂化汽油加氢改质评价140 h。反应后,硫含量从288μg／g降低到71μg／g,加氢脱硫率75%；烯烃含量从33.2 vol.%降低到26.2vol.%,降烯烃率21%;辛烷值损失3.3个单位。La2O3-HZSM-5(DQG0904)芳构化催化剂用于催化裂化汽油加氢改质评价220 h。反应后,硫含量从288μg／g降低到184μg／g,加氢脱硫率为36%；烯烃含量从33.2 vol.%降低到19.9 vol.%,降烯烃率40%;芳烃含量从21.1 vol.%升高到26.1 vol.%；改质后辛烷值从92.9升高到93.3
(2)采用先芳构化(DQG0904)后脱硫(DQG0905)的组合顺序,用于催化裂化汽油加氢改质评价660 h。反应后,硫含量从242μg／g降低到73μg／g,加氢脱硫率70%；烯烃含量从36.8 vol.%降低到24.9 vol.%,降烯烃率34%；芳烃含量从18.9.vol.%升高到19.9 vol.%；改质后辛烷值从87.8升高到89.4
2 CoMo-MgOAl2O3作为脱硫催化剂用于催化裂化汽油的加氢改质,考察了不同条件下催化剂的催化性能。结果显示在反应温度为240-260℃、4.0-6.0h-1,2Mpa的条件下硫含量可降低到<50μg／g、RON损失<1.0,活性稳定性能优良。
3以钛酸四丁酯为钛源,采用浸渍法研制了一系列TiO2改性的Ni-Mo/HZSM-5催化剂,通过系统表征,并在连续微反固定床装置上评价了其全馏分催化裂化汽油加氢脱硫性能。结果表明,ZiO2改性可以弱化MoO3和HZSM-5之间的相互作用,抑制Al2(MoO4)3的形成,从而使催化剂脱硫活性大大提高。
Production of low sulfur, low olefin and high-octane number clean gasoline is energy economy to maintain its essential requirement for sustainable development. In China, "Limits and Measurement Methods for Emissions from Light-Duty vehicles (Phase IV)" standards will be executed on 2011, in which less than 18vol.%of olefin content,35 vol.%of aromatic content, and 50μg/g of sulfur content in gasoline are required to meet the No. IV emission standards. FCC gasoline constitutes approximate 80%of the total gasoline pool and sulfur content of FCC gasoline accounted for more than 90%of the total value. FCC gasoline consists of great value of olefin (30～55 vol.%) and sulfur (150-1500μg/g).
The key issue of this article will focuses on the realization of desulfurization of full-range FCC gasoline by means of the little loss of octane number(RON≤1). Thus, The article have to combine different characteristics of catalysts and feedstock composition on the upgrading process optimization. Conclusions from the experiments are summarized as follow:
1 Adopt to two-step hydro-upgrading process:
(1) NiS04-Al203 (DQG0905) desulfurization catalyst was prepared and used in the FCC gasoline hydro-upgrading for 140 h. After hydrotreatment, the sulfur decreases from 288 to 71μg/g, with a 75%conversion rate of hydrodesulfurization (HDS); Olefin decreased from 33.2vol.%to 26.2vol.%, with a 21%conversion rate of hydrodeolefinization (HDO); The RON of product lost 3.3 compared with feed. La2O3-HZSM-5(DQG0904) Aromatization catalyst was prepared and used in the FCC gasoline hydro-upgrading for 220 h. After hydrotreatment, the sulfur decreases from 288 to 184μg/g, with a 36%conversion rate of HDS; the olefin decreased from 33.2vol.%to 19.9vol.%, with a 40%conversion rate of HDO; the aromatic content increased from 21.1 vol.%to 26.1 vol.%; the RON of gasoline has only a slight change from 92.9 to 93.3 after the upgrading process.
(2) Applying the sequence that aromatization(DQG0904) followed by desulfurization(DQG0905), hydrotreatment was performed for hydro-upgrading of FCC gasoline for 660h. After hydrotreatment, the sulfur decreases from 242 to 73μg/g, with a 70% conversion rate of HDS; the olefin content decreased from 36.8vol.%to 24.9vol.%, with a 34%conversion rate of HDO; the aromatic increased from 18.9.1vol.%to 19.9vol.%; the RON of gasoline has change from 87.8 to 89.4 after the upgrading process.
2 CoMo-MgOAl2O3 as desulfurization catalyst is used to study different conditions on catalytic performance and evaluat hydro-upgrading of FCC gasoline. The results show that 240-260℃,4.0-6.0 h-1,2.0Mpa conditions can reduce the sulfur content to< 50μg/g, RON loss of< 1.0, excellent activity and stability.
3 A series of TiO2-modified Ni-Mo/HZSM-5 catalysts were prepared by impregnation method with tetrabutyl titanate as a titanium source, and characterized and evaluated by hydrodesulfurization (HDS) activity for full-range fluid catalytic cracking (FCC) gasoline in a continuous-flow fixed-bed micro-reactor. The results show that the coverage of TiO2 on HZSM-5 can weaken the interaction between MoO3 and HZSM-5 and inhibites the formation of Al2(MoO4)3, so that the catalyst desulfurization activity increases substantially.
引文
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