多组分吸附剂级配技术提高FCC汽油吸附脱硫性能

以催化裂化汽油为研究对象,采用静态和动态吸附脱硫技术将不同金属离子改性分子筛单组分床层与多种分子筛级配床层的吸附脱硫性能进行对比,探讨级配床层中吸附剂的组合顺序和比例对脱硫效果的影响。结果表明：对于单组分而言,Al-Ti-SBA-15分子筛的吸附脱硫性能优于改性Y分子筛,两者总脱硫率相差28百分点以上;双组分级配时,从穿透曲线的结果来看,CeY/NiY组合的穿透曲线出现了一个平台,可能是吸附剂对各种硫化物的吸附和脱除出现了动态平衡,穿透速率较慢,则其脱硫性能最佳,而Cu(I)Y/NiY组合的脱硫性能次之;对于三组分吸附剂级配,m（CeY）: m（NiY）: m（Al-Ti-SBA-15）=1:1:4时穿透速率最慢,是脱硫性能较好的组合。     

Ni/ZnO-HY吸附剂对模型汽油的反应吸附脱硫性能研究

The reactive adsorption desulfurization of model gasoline was carried out on Ni/ZnO-HY adsorbent. The Ni/ZnO-HY adsorbent was characterized by N2 adsorption-desorption test (BET), X-ray diffractometry ...     

膜法FCC汽油的脱硫

膜分离汽油脱硫技术在炼油和膜分离领域均是崭新的技术,利用实验室渗透汽化膜脱硫放大装置对膜法FCC汽油深度脱硫技术进行了系统研究,探讨了操作条件包括进料温度、操作压力以及进料流量对膜分离性能的影响,并通过色谱对试验得到的高硫汽油、低硫汽油产品进行了族组成和辛烷值分析。结果表明,经过膜脱硫处理,FCC汽油硫含量从750μg/g降至70μg/g左右,低硫产品的收率保持在70%以上;相对于原料汽油的辛烷值,低硫产品的辛烷值稍有增加,高硫产品的辛烷值稍有降低,总体变化不大。     

FCC汽油深度脱硫技术的进展

介绍了RSDS、S-Zorb、Prime-G+、SCANfiningⅡ代和CDHydro/CDHDS等FCC汽油深度脱硫技术,这些技术催化剂比较新颖且均具有脱硫率高、辛烷值损失少的优点。指出了目前FCC汽油脱硫技术存在的不足,并对今后脱硫技术的发展方向进行了展望。     

Ni/ZnO-Al_2O_3-SiO_2汽油脱硫吸附剂的再生

采用湿混法制备了Ni/Zn O-Al_2O_3-SiO_2汽油脱硫吸附剂,利用空气氧化燃烧法对失活吸附剂进行再生,考察了再生过程中再生条件对吸附剂再生性能的影响,并利用XRD、压汞、SEM、XPS等手段对新鲜吸附剂、失活吸附剂和再生吸附剂进行表征。表征结果显示,吸附剂失活的主要原因是ZnS和NiS_x的生成减少了活性中心的数量,并出现了一定程度的聚集,阻塞了吸附剂大孔道,使孔体积和孔径有所减小;再生吸附剂和新鲜吸附剂的晶体结构基本一样,但颗粒粒径有所增大,孔体积和比表面积减小。实验结果表明,在常压、温度480℃、再生气流量500 mL/min、再生气氧含量2%(φ)的再生条件下,再生后吸附剂的活性基本可以恢复至新鲜吸附剂水平。     

FCC汽油的膜分离法脱硫

 膜分离汽油脱硫技术在炼油和膜分离领域均是崭新的技术,利用实验室渗透汽化膜脱硫放大装置对膜法FCC汽油深度脱硫技术进行了系统研究,探讨了操作条件包括进料温度、操作压力以及进料流量对膜分离性能的影响,并通过色谱对试验得到的高硫汽油、低硫汽油产品进行了族组成和辛烷值分析。结果表明,经过膜脱硫处理,FCC汽油硫含量从750μg/g降至70μg/g左右,低硫产品的收率保持在70%以上;相对于原料汽油的辛烷值,低硫产品的辛烷值稍有增加,高硫产品的辛烷值稍有降低,总体变化不大。     

FCC汽油轻馏分非加氢脱硫脱氮的实验室研究

随着环保要求的日益苛刻和汽车工业的发展,汽油质量标准不断升级,降低汽油中的硫、烯烃、芳烃和苯含量并改进汽油辛烷值分布是未来汽油质量升级的发展趋势。国内催化裂化（FCC）汽油占汽油比重达80％,成品汽油中90％以上的硫含量来自于FCC汽油;同时FCC汽油中烯烃含量也高达40％以上。因此,FCC汽油的脱硫、降烯烃是我国汽油质量升级的主要任务。随着车用汽油标准的升级,对硫含量的限制尤其严格：2013年年底,我国将实施国家第1V阶段机动车排放标准（国lV排放标准）。满足国lV排放标准的汽油要求硫含量〈50mg／kg;     

WO_3-ZSM-5/MCM-41用于FCC汽油催化氧化脱硫工艺研究

利用钨酸对ZSM-5/MCM-41复合分子筛载体进行改性,制备WO3-ZSM-5/MCM-41(10%)催化剂。该催化剂具有明显的MCM-41介孔特征峰和适宜的孔容和孔径。以H2O2为氧化剂,甲醇为助剂,去离子水和甲醇为萃取剂,考察WO3-ZSM-5/MCM-41催化氧化FCC汽油脱硫的工艺条件。结果表明:FCC汽油20mL,三氧化钨负载量为10%,剂油质量比1∶50,反应温度60℃,反应时间120min,脱硫率可达67.35。     

催化裂化轻汽油深度脱硫吸附剂的研制及性能

采用等体积浸渍法制备了一系列Ni-Cu/ZnO-Al_2O_3脱硫吸附剂,考察了不同金属活性组分及其负载量、不同助剂及其负载量、焙烧温度等因素对催化裂化轻汽油中噻吩脱除性能的影响,并采用XRD、压汞技术对制备的吸附剂进行表征。表征结果显示,500℃下焙烧制得的Ni-Cu/ZnO-Al_2O_3吸附剂的比表面积最大,表现出较高的脱硫活性,其中,NiO为Ni-Cu/ZnO-Al_2O_3吸附剂脱除噻吩硫的主要活性组分。实验结果表明,在Ni负载量为6%(w)、Cu含量为5%(w)、焙烧温度为500℃、反应温度为350℃、压力为0.6 MPa、液态空速2 h~(-1)条件下,Ni-Cu/ZnO-Al_2O_3吸附剂的饱和硫容为1.70%。     

CDHydro/CDHDS FCC汽油选择性加氢脱硫工艺设计

介绍了国内引进的第一套美国CDTECH公司的选择性加氢脱硫CDHydro,CDHDS技术的工艺设计情况,该技术将加氢脱硫反应与蒸馏组合在一座塔器中进行,具有工艺路线成熟、高脱硫率、高汽油收率、低辛烷值损失和催化剂寿命长等特点。     

The Preparation of Ni/ZnO Adsorbent via a Low-Temperature Solid-State Method for Ultra-deep Desulfurization

Abstract

One novel synthetic approach has been proposed to prepare Ni/ZnO adsorbent via low-temperature solid-state reaction. Thermal analysis (thermogravimetry differential scanning calorimetry [TG-DSC]) revealed that the nickel–zinc oxalate precursor obtained is a single-phase composite oxalate. Transmission electron microscopy analysis (TEM) shows that the NiO/ZnO composite materials are composed of nanoparticles with good dispersivity, whereas the elements of Ni and Zn are well distributed. The activity evaluation indicates that the Ni/ZnO adsorbent has good ultra-deep desulfurization activity of removing organic sulfur compounds. The sulfur concentration in the treated gasoline is less than 1.0 μg/g, which meets the need of ultra-low-sulfur fuels for use in fuel cells.     

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。     

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。     

Desulfurization of FCC Gasoline Over Mordenite Modified with Al2O3

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.     

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.     

Catalytic Coprocessing of Delayed Coker Light Naphtha with Light Straight-run Naphtha/FCC Gasoline

Abstract

Upgrading of delayed coker light naphtha (DCLN) is difficult due to its high diolefin and silicon content. Mixtures of light straight-run naphtha (LSRN) and DCLN fractions were hydrotreated in two stages over NiMo/Al₂O₃ and CoMo/Al₂O₃ catalysts (diolefin saturation followed by hydrodesulphurization (HDS). Naphtha fractions free of diolefins, olefins, sulfur, and silicon were produced, which are excellent feeds for naphtha isomerization. One-stage selective HDS tests were also conducted with blends of DCLN (up to 5 vol%) and fluid catalytic cracked (FCC) gasoline over CoMo/Al₂O₃. Diolefin-free products of <10 mg/kg sulfur could be produced with a research octene number (RON) loss of max. 3.     

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.     

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.     

Study on Olefin Decrement Reformulation and Increasing Light Olefins of FCC Gasoline by Catalytic Cracking

Abstract

Catalytic upgrading of fluid catalytic cracked (FCC) gasoline obtained from Huabei Petrochemical Company, PetroChina (Renqiu, Hebei, China), was investigated using a microreactor and gas chromatograph integrated unit in order to decrease the content of olefins in gasoline and increase the light olefins (ethylene, propylene, and butylene) content. The experimental results showed that the olefin content in upgraded gasoline can be decreased from 42.6% in raw material to nearly 10%, meeting the requirements of the new gasoline standard, whereas iso-alkane and aromatics contents were markedly increased, from 28.4 and 18.2% to 47 and 36.1%, respectively, so the octane number of gasoline should not be reduced. In addition, higher yields of light olefins were obtained after FCC gasoline was reformulated under laboratory conditions. Higher reaction temperature, longer reaction time, higher weight ratio of catalyst to oil, and higher catalyst activity were beneficial to decrease the olefin content of FCC gasoline and increase the yields of light olefins.