Desulfurization of FCC Gasoline Over Mordenite Modified with Al2O3

Abstract

Mordenite modified with Al₂O₃ (Al₂O₃/mordenite) was synthesized and used for the desulfurization of FCC gasoline. The influences of operating parameters on the results were studied for the model solution composed of dibenzothiophene (DBT) and isooctane. Al₂O₃/mordenite exhibits higher sulfur capacity than other kinds of chemisorbents. The suitable composition of the chemisorbent is 30 wt% Al₂O₃ to 70 wt% mordenite. The optimal operating parameters are: temperature 160°C; velocity 3 h^?1 (WHSV). Under the stated conditions, desulfurization was carried out for the FCC gasoline with sulfur content of 220.4 μg/g. The chemisorbent can maintain the sulfur content under 50 μg/g for 40 h and has good regeneration ability after desorption using benzene.     

FCC汽油反应吸附脱硫催化剂NiZnO/SiO2-Al2O3的还原过程

采用中压固定床加氢实验装置研究了NiZnO/SiO2-Al2O3反应吸附脱硫剂在H2气氛下的还原反应规律,采用XRD、XPS等多种手段分析了还原工艺条件对NiZnO/SiO2-Al2O3催化剂基本性质和晶相结构的影响。结果表明,NiZnO/SiO2-Al2O3催化剂在不同还原工况下具有四种晶相结构;高还原温度和长还原时间会导致NiZn合金的生成,从而显著降低吸附的脱硫能力。催化汽油反应吸附脱硫评价表明,优化的还原工艺条件是保证催化剂的NiO完全还原,同时防止NiZn合金的生成。     

改性半焦脱除FCC汽油中含硫化合物的研究

以扎赉诺尔半焦为原料，采用硝酸活化、水热活化和浸渍活性组分等改性方法，制备了改性半焦脱硫剂，并用于脱除FCC汽油中的各种硫化物。通过正交试验法考察了工艺参数对改性半焦脱硫效果的影响，探讨了最佳工艺条件下制备的脱硫剂对FCC汽油单次脱硫的效果。实验结果表明，半焦经水热和硝酸活化，负载0．5％的氧化铜，于700℃下焙烧制备的脱硫剂对FCC汽油脱硫效率可达38．85％；硝酸活化半焦过程中要采用较高的水浴温度和较低的固定床焙烧温度。     

FCC汽油选择性加氢脱硫CoMo/Al2O3催化剂的CO吸附原位红外光谱表征

 采用CO吸附原位红外光谱对系列硫化态CoMo/Al₂O₃催化剂进行表征,获得了加氢脱硫催化剂活性相的信息,并将表征结果与微反加氢脱硫活性和选择性评价结果进行关联分析。结果表明,CoMoS和MoS₂活性中心上吸附的CO数目的比值与HDS选择性具有良好的相关性;催化剂表面CoMoS相相对含量的增多有利于提高HDS的活性和选择性;CoMoS活性中心的强缺电子特性是CoMoS相有助于提高HDS活性和选择性的重要原因。     

催化裂化汽油重馏分在MoCo/Al2O3催化剂上的加氢脱硫性能

以FCC汽油为原料,在中型试验装置上考察了230～400 ℃范围内硫化温度对MoCo/Al2O3催化剂加氢脱硫率及烯烃加氢饱和率、辛烷值损失性能的影响。结果表明在260 ℃反应温度下,随着硫化温度的提高,加氢脱硫率由84.4%逐步提高到91.1%;在280 ℃反应温度下,随着硫化温度的提高,加氢脱硫率维持在96.0%以上基本不变。在上述两种情况下,250 ℃硫化催化剂烯烃加氢饱和率最低,辛烷值损失最小。表明250 ℃硫化催化剂加氢脱硫选择性最好。250 ℃下硫化充分且碳含量较少是FCC汽油加氢脱硫选择性最好的原因。     

催化裂化汽油烷基化脱硫技术研究及进展

介绍了催化裂化汽油烷基化脱硫的特点及原理,综述了近年来国内外烷基化脱硫的工艺现状及脱硫催化剂的研究发展情况。认为烷基化脱硫具备了脱硫效率高、可降低油品烯烃含量且辛烷值损失小、操作费用低、投资设备少等优点,适合大力开展研究。     

Modeling of the FCC Gasoline Desulfurization Process by Liquid Extraction with Sulfolane

Abstract

Extractive desulfurization of fluid catalytic cracking (FCC) gasoline with sulfolane was studied in a batch apparatus. The influence of three inlet parameters (temperature, inlet sulfur content, and solvent ratio) on the process response, that is, desulfurization efficiency, was investigated with the use of a Box-Behnken experimental design by response surface methodology. A mathematical model that can be used for predicting sulfur content in raffinate after extractive batch processing with sulfolane was statistically developed and proven with analysis of variance. Statistical analysis showed that the largest influence on desulfurization efficiency was solvent ratio, the second most significant influence was inlet sulfur content, followed by temperature, and last the interaction between solvent ratio and inlet sulfur content. The obtained second-order polynomial model shows that maximum desulfurization efficiency of 65.34% can be achieved at temperature of 50°C and higher values of inlet sulfur content and solver ratio in the researched range of inlet parameter values.     

The Oxidation-Extraction Desulfurization of FCC Gasoline

Abstract

With increasing environmental concern and stricter regulations, sulfur content is restricted in a low range. So there are many studies on the desulfurization methods to light oils. The oxidation-extraction desulfurization method for light oils provided a prospective way to reduce the sulfur content. The effects of the oxidation-extraction system were studied in this article. The results showed that the best oxidation time is 25 min, the best proportion of oil, catalyst, and oxidant is 50:5:1, temperature nearly has no effect on the oxidation desulfurization. This research provided a good prospect for the industrial application of the oxidation-extraction desulfurization.     

Aromatization of FCC Gasoline Over Modified HZSM-5 Catalyst

Zinc and phosphorus incorporated HZSM-5 catalyst was prepared by adopting incipient wet co-impregnation (Zn-P/HZSM-5). Zn-P/HZSM-5 catalyst exhibited the lowest acidity but the highest aromatization activity with stable performance in the studied period of 16 hr. The process conditions on aromatization reaction and the coke deactivation mechanism of Zn-P/HZSM-5 catalyst were studied on a small-scale, fixed bed reactor using FCC naphtha (75-120°C). The weight contents of ZnO and P₂O₅ were 2% and 4%, respectively. Results showed that Zn-P/HZSM-5 catalyst under a temperature of 450°C, liquid hourly space velocity of 1.0 h^-1, and pressure of 0.1 MPa, the conversions of olefins and alkanes are 96.77% and 88.94%, respectively, the contents of olefins, aromatics in liquid product are 6.79% and 74.57%, respectively. Carbon deposition was the major reason for catalyst deactivation due to the catalyst's good performance as a fresh catalyst after regeneration. All of the blending products fitted the standards of Chinese gasoline.     

Aromatization of FCC Gasoline Over Modified HZSM-5 Catalyst

Abstract

Zinc and phosphorus incorporated HZSM-5 catalyst was prepared by adopting incipient wet co-impregnation (Zn-P/HZSM-5). Zn-P/HZSM-5 catalyst exhibited the lowest acidity but the highest aromatization activity with stable performance in the studied period of 16 hr. The process conditions on aromatization reaction and the coke deactivation mechanism of Zn-P/HZSM-5 catalyst were studied on a small-scale, fixed bed reactor using FCC naphtha (75–120°C). The weight contents of ZnO and P₂O₅ were 2% and 4%, respectively. Results showed that Zn-P/HZSM-5 catalyst under a temperature of 450°C, liquid hourly space velocity of 1.0 h^?1, and pressure of 0.1 MPa, the conversions of olefins and alkanes are 96.77% and 88.94%, respectively, the contents of olefins, aromatics in liquid product are 6.79% and 74.57%, respectively. Carbon deposition was the major reason for catalyst deactivation due to the catalyst's good performance as a fresh catalyst after regeneration. All of the blending products fitted the standards of Chinese gasoline.     

Ti掺杂对Ni/ZnO-TiO2吸附剂用于FCC轻汽油脱硫性能的影响

采用混捏法制备了不同Ti含量的ZnO-TiO₂载体,采用等体积浸渍法制备了NiO/ZnO-TiO₂汽油脱硫吸附剂前驱体,并采用X射线衍射(XRD)、压汞、NH₃程序升温脱附(NH₃-TPD)、H₂程序升温还原(H₂-TPR)和H₂程序升温脱附(H₂-TPD)等手段对其进行了表征。以催化裂化轻汽油为原料,于氢气氛围下对NiO/ZnO-TiO₂前驱体还原得到Ni/ZnO-TiO₂吸附剂,在固定床上考察了Ti掺杂对该吸附剂脱硫性能的影响。结果表明：Ti的掺杂提高了Ni/ZnO吸附剂中活性组分Ni的分散度,增加了Ni活性位点,增强了吸附剂中强酸酸性及酸强度,Ti掺杂的吸附剂脱硫性能显著提高;Ti的掺杂能够减少游离Ni,有效抑制烯烃饱和;吸附剂脱硫性能随着Ti掺杂量的增加呈现先增强后减弱的趋势,当Ti掺杂质量分数为5%时,吸附剂具有最优脱硫性能,能够将FCC轻汽油中硫质量分数由300 μg/g降低至5 μg/g以下,穿透硫容为6.711%(每克吸附剂吸附硫67.11 mg),烯烃质量分数增加0.6百分点,降低了汽油辛烷值损失。     

Mo-Ni/Al2 O3催化剂对FCC汽油硫醚化反应的催化性能

针对当前FCC汽油选择性加氢脱硫技术中的硫醚化反应催化剂的研究,利用FCC汽油评价了Mo Ni/Al2O3催化剂的硫醚化反应催化性能,并进行了工艺条件优化和催化剂寿命评价。结果表明,Mo Ni/Al2O3催化FCC汽油硫醚化反应的优化条件为反应压力25 MPa、空速4 h-1、H2/油体积比3、反应温度130℃,在该条件下Mo Ni/Al2O3催化FCC汽油硫醚化反应运转600 h,硫醇转化率维持在95%以上,二烯选择性加氢率在100%,烯烃未发生加氢现象,辛烷值保持恒定。     

Oxidative Desulfurization of Model Gasoline Over Modified Titanium Silicalite

The oxidative desulfurization of model gasoline consisting of thiophene dissolved in n-octane was investigated with a series of modified titanium silicalite (TS) catalysts in presence of hydrogen peroxide and formic acid systems, and the reaction mechanism of the oxidative desulfurization of thiophene was preliminarily researched. The results showed that the copper modified TS was an active catalyst for thiophene oxidation while the other metal modified TSs were less active catalysts. When Cu-TS at a Cu/Si molar ratio of 0.015 was used as a catalyst for oxidation of model gasoline, the conversion of thiophene was 94.1% at 120 min. The conversion of thiophene was easily enhanced by increasing reaction time or reaction temperature, and reduced with addition of xylene and cyclohexene.     

催化裂化汽油脱硫技术研究及进展

对国内外开发或正在开发的各种汽油脱硫技术的特点及汽油中硫类型含量分布状况进行了综述。针对我国产品汽油组成和硫含量普遍偏高的特点，提出我国催化汽油脱硫技术开发的方向。     

Ce4+与H2O2对FCC汽油氧化脱硫比较研究

This article describes two kinds of model oil samples made of a benzothiophene/octane mixture and a 2-me- thylthiophene/octane mixture. Furthermore, this paper investigates the oxidative desulfurization selectivity and reaction efficiency when Ce4+ compound and H2O2 having identical electron equivalent weight were used as oxidants. The test re- sults showed that the two kinds of oxidants were more effective to remove benzothiophene in the model oil samples. For oxidative desulfurization of 2-methylthiophene, Ce4+ compound was obviously superior than H2O2. This paper by means of quantum chemistry analyses elaborates the complex formed between Ce4+ species and 2-methylthiophene and FT-IR spec- trograms of model oil samples before and after oxidation by Ce4+ compound and H2O2, respectively. The results demonstrat- ed that Ce4+ compound could remove sulfur compounds not only through oxidation reaction but also through complexation reaction.     

添加组分对Cu/ZnO/Al_2O_3催化剂顺酐加氢合成γ-丁内酯活性的影响

在常压固定床反应装置上研究了不同添加组分对顺酐加氢催化剂催化性能的影响 ,在反应温度 2 70℃ ,氢气与顺酐摩尔比 5 5 ,顺酐空速 0 16h- 1 的条件下 ,考察了添加碱金属、碱土金属、ⅥB族、ⅦB族和Ⅷ族金属元素对顺酐加氢催化剂活性的影响 ,并探讨了引起活性变化的原因。结果表明 ,在所有添加组分中 ,Cr是唯一既不影响催化剂活性又能提高γ -丁内酯选择性的助剂 ,但其添加量应不超过 5 % (摩尔分数 ) ;碱金属元素和Mo、Mg对催化剂有毒害作用 ;Ba对催化剂加氢活性影响不大 ;添加其它金属元素时催化剂的加氢活性虽下降不大 ,但γ -丁内酯的选择性却大幅度降低     

Al2O3改善FCC催化剂抗镍性的机理研究

研究了不同比表面积和孔径分布的Al2O3作为基质添加组分对FCC催化剂 性能的影响，结果表明，基质中添加活性Al2O3有利于改善FCC催化剂的重油转化能力、焦炭选择性以及抗Ni性能；借助XRD、TPR等手段研究了NiO在Al2O3表面上的分散度和还原性，结果表明：NiO在大孔径（4－60nm),低比表面积（46m^2/g)Al2O3上分散度较低，不易被还原，因而其脱氢活性低，致使FCC催化剂的抗镍性能较好。添加10％该Al2O3的催化剂与空白对比剂相比，重油转化率增加了3．6个百分点，焦炭选择性降低了0．36个百分点。     

喹啉对在Co-Mo/Al2O3及Ni-Mo/Al2O3催化剂上二苯并噻吩加氢脱硫活性的影响

在工业催化剂FHUDS-5(Co-Mo/Al2O3)和FHUDS-6(Ni-Mo/Al2O3)上,模拟工业柴油加氢工艺,考察了喹啉对二苯并噻吩(DBT)加氢脱硫(HDS)活性的影响,还讨论了喹啉抑制DBT加氢脱硫反应的机理。结果表明,喹啉对DBT的HDS反应有强烈抑制作用,对加氢路径(HYD)的抑制作用大于对氢解路径(DDS)的抑制作用;反应温度高于300℃时,在同一温度下,喹啉对在Co-Mo/Al2O3及Ni-Mo/Al2O3催化剂上DBT加氢脱硫反应活性的影响不同;当氢分压大于4.8 MPa时,在同一氢分压下,喹啉对在Co-Mo/Al2O3及Ni-Mo/Al2O3催化剂上DBT加氢脱硫反应活性的影响不同。     

Influence of ZnO and P2O5 Content on Modified HZSM-5 on Aromatization of FCC Gasoline

Catalytic properties of different content of ZnO and P₂O₅ supported on HZSM-5 zeolites were studied in the conversion of FCC gasoline (75°C-120°C) into aromatic hydrocarbons with a temperature of 430°C, a liquid hourly space velocity of 1.0 hr^-1, and a pressure of 0.1 MPa. In the reaction, when the contents of ZnO and P₂O₅ are 2% and 4%, respectively, Zn-P/HZSM-5 showed the highest selectivity and activity to aromatic hydrocarbons and conversion of olefins. The content of aromatics in the liquid product and the yield of aromatics reached as high as 94.53%, 68.87%, and 51.74%, respectively.     

Influence of ZnO and P2O5 Content on Modified HZSM-5 on Aromatization of FCC Gasoline

Abstract

Catalytic properties of different content of ZnO and P₂O₅ supported on HZSM-5 zeolites were studied in the conversion of FCC gasoline (75°C–120°C) into aromatic hydrocarbons with a temperature of 430°C, a liquid hourly space velocity of 1.0 hr^?1, and a pressure of 0.1 MPa. In the reaction, when the contents of ZnO and P₂O₅ are 2% and 4%, respectively, Zn-P/HZSM-5 showed the highest selectivity and activity to aromatic hydrocarbons and conversion of olefins. The content of aromatics in the liquid product and the yield of aromatics reached as high as 94.53%, 68.87%, and 51.74%, respectively.