凹凸棒黏土脱硫剂脱除3-甲基噻吩的实验研究

选用经分散剂六偏磷酸钠提纯、硝酸处理的凹凸棒黏土为载体,采用浸渍法负载Fe系和Ag系化合物,制备凹凸棒黏土脱硫剂,用于含3-甲基噻吩的模拟汽油的脱硫。通过正交实验进行脱硫剂制备条件的优化。结果表明,在Fe系化合物质量分数5%、Ag系化合物质量分数0.5%、400℃焙烧4.5 h的条件下制备的凹凸棒黏土脱硫剂,在常温常压条件下,使模拟汽油硫质量分数从500 μg/g降至约191 μg/g,脱硫率达到61.8%。     

微反产物中汽油馏分段硫化物类型分布的测定

采用气相色谱-原子发射光谱,结合多维色谱中的反吹技术,建立了以减压馏分油为原料的微反产物中汽油馏分段中各种硫化物类型分布的分析方法。考察了色谱条件对汽油馏分段各种硫化物分离的影响,定性分析了微反产物中汽油馏分段中的37种硫化物,计算了恒压模式程序升温下汽油馏分段中各种硫化物的保留指数,为不同实验室的定性分析提供了依据。微反产物中各主要组分峰面积重现性的相对标准偏差小于5％。该方法已被应用于微反催化剂评价硫化物的类型分布研究,并可推广到固定床、流化床工艺脱硫条件的选择。     

改性凹凸棒粘土脱硫剂在汽油脱硫中的应用

Attapulgite clay is a kind of special silicate mineral with high adsorption capacity thanks to its loose structure andporous surface. In this paper, the attapulgite clay was treated effectively with acid under microwave thermal activation andultrasonic vibration, respectively, and characterized by XRD, N2 adsorption, FT-IR and SEM. The desulfurization performanceof the modified attapulgite clay was then evaluated by using simulated gasoline as the feed. The test results showedthat the thiophene removal rate increased with an increasing dosage of hydrochloric acid during microwave modificationof attapulgite clay. When the concentration of hydrochloric acid reached 15%, the increase of desulfurization rate becameslower, and the desulfurization rate was about 69%.     

柴油加氢与微生物脱硫过程中硫化物类型变化规律研究

采用气相色谱-原子发射光谱联用(GC-AED)技术,研究了柴油馏分加氢前后各种硫化物的变化。在加氢脱硫过程中,二苯并噻吩类化合物中的硫最难脱除,催化剂的类型及各操作参数的选择应以柴油中二苯并噻吩类化合物含量来确定。研究了某加氢柴油进行微生物脱硫处理后各种硫化物的变化,并研究了硫含量不同的柴油馏分进行微生物脱硫处理后各种硫化物的分布。可选取在加氢脱硫过程中将柴油中的硫含量降到多大时,再进行生物脱硫技术处理的最佳方案。     

改性凹凸棒用于FCC汽油的吸附脱硫

采用改性凹凸棒黏土为载体,混合法制备了TiO2-凹凸棒黏土复合型脱硫剂(TiO2-GATB),用于FCC汽油吸附脱硫,考察了脱硫剂活性组分种类、活性组分含量、活化温度、活化时间,脱硫剂用量、脱硫温度、脱硫时间对脱硫率的影响;并利用红外光谱(FT-IR)、光电子能谱(XPS)等手段进行表征和分析。结果表明,采用600℃活化4h制备的负载5%(质量分数)TiO2的凹凸棒黏土脱硫剂(5%TiO2-GATB),在脱硫温度40℃、脱硫时间1h的条件下,40 mL FCC汽油加5 g脱硫剂的脱硫效果最佳;经二次脱硫,FCC汽油中的硫质量分数由1100 μg/g降至141 μg/g,脱硫率达87.18 %。在该复合材料中,TiO2 颗粒间不发生团聚,与凹凸棒黏土结合牢固。     

汽油馏分的硫化物形态分布研究

采用气相色谱和硫化学发光检测器（GC-SCD）技术，经过对色谱条件的优化，建立了汽油馏分硫化物形态分布的测定方法。用标准物质的保留时间辅以化学法脱除硫醇、硫醚的方法对107个硫化物进行了定性；标准硫化物保留时间重复测定结果的RSD≤0．25％。用内标法对主要的硫化物和总硫进行了定量，方法的加标回收率在96％-115％范围；同一样品重复测定5次，含硫大于7mg／kg的硫化物组分重复测定结果的RSD≤8．9％。将所建立的方法用于不同装置的汽油馏分的硫化物形态分布规律的研究。     

用CGC—AED法分析汽油中的硫化物

用ＣＧＣ－ＡＥＤ联用技术建立了汽油中硫化物含是分析方法，探索了优化分析条件并考查了烃类对硫化物定量的影响，对汽油中大部分硫化物作了定性以及定量精密度研究。     

催化裂化汽油中硫化物的吸附脱除研究

采用气相色谱-硫化学发光检测器（GC-SCD）分析研究催化裂化汽油中硫化物在S Zorb吸附剂上的吸附脱除情况。结果表明,催化裂化汽油中硫化物在S Zorb吸附剂上的脱除从难到易的顺序为：C3-和C4-噻吩相似文献   

气相色谱—脉冲火焰光度法测定催化裂化汽油中的硫化物

采用气相色谱-脉冲火焰光度检测器(GC-PFPD),对几种催化裂化汽油中的硫化物进行了定性和定量研究。在此基础上,考察了PFPD检测器硫响应与信号输出方式以及硫化物结构的关系。同时,确定了在开平方模式下,PFPD检测器与硫化物的硫浓度的线性方程。     

气相色谱法测定热裂解汽油C6～C8馏分中硫化物

根据火焰光度检测器(FPD)的特性，考察了氢气与空气流量比、芳烃干扰等因素对响应的影响情况，在一定程度上提高了FPD(S)的灵敏度和选择性，在此基础上，采用工作曲线法对热裂解汽油C6～C8馏分中的噻吩、2-甲基噻吩、2，5-二甲基噻吩等反应特征硫化物进行了定量检测，取得了较为满意的结果。     

Imidazolium-based Alkylsulfate Ionic Liquids and Removal of Sulfur Content From Model of Gasoline

Two ionic liquids, butyl-methyl-imidazolium octylsulfate, [BMIM][OCSO₄], and ethyl-methyl-imidazolium ethylsulfate, [EMIM][EtSO₄], were demonstrated to be effective for the removal of aromatic sulfur compounds such as benzothiophene and thiophene from model of gasoline. Organic compounds with higher aromatic π-electron density were favorably adsorbed by using ionic liquids. It was shown that the extractive ability of the alkylsulfate IL_s was dominated by the structure and size of cation and anion. The cation and anion structure and size of ionic liquids are important factors affecting the absorption capacity for aromatic compounds. It is found that [BMIM][OCSO₄] has the best effect on the selective removal of sulfur compounds from gasoline. Sulfur extractive selectivity for specified IL followed the order BT>T>3-MT>2-MT.     

几种汽油脱硫工艺中含硫化合物类型变化规律

采用气相色谱-原子发射光谱联用(GC—AED)技术,研究了几种不同的脱硫工艺(加氢脱硫、吸附脱硫和抽提脱硫)中各种含硫化合物的变化。加氢脱硫工艺中含硫化合物的脱除效果最好,硫脱除率可达98％以上,硫醇、硫醚最易脱除,仅有少量的烷基取代噻吩不易被脱除,加氢脱硫条件的选择应以汽油中噻吩类化合物的含量而定;吸附脱硫工艺中,硫醇、硫醚、四氢噻吩类化合物最易脱除,受空间位阻的影响,取代噻吩比噻吩难脱除;在抽提脱硫工艺中,因苯并噻吩与所用抽提剂结构相近,最易被脱除,而空间位阻较大的三甲基噻吩和四甲基噻吩不能被脱除。采用GC—AED技术,可根据汽油馏分中含硫化合物的分布来选择合适的脱硫工艺。     

Preparation of the Modified Y Zeolite for Removal of Organic Sulfur Compounds from FCC Gasoline

Abstract

Ce(IV)-loaded modified NaY (NH₄Y) zeolite was prepared for selective adsorptive desulfurization from fluid catalytic cracked (FCC) gasoline. Ce(β)Y was obtained from NH₄Y using a liquid-phase ion-exchange method. Ce(IV)Y was obtained from calcining Ce(β)Y at 550°C. The structures of the Ce(IV)Y and NaY samples, selective adsorption of organic sulfur compounds on Ce(IV)Y and NaY zeolite, sulfur content of FCC gasoline, and mechanism for adsorption of thiophene on Ce(IV)Y and NaY zeolite were investigated using X-ray diffraction (XRD), gas chromatography–sulfur chemiluminescence detection (GC-SCD), sulfur analysis, Fourier transform infrared (FTIR), frequency response (FR), and intelligent gravimetric analysis (IGA). The selective adsorption desulfurization from FCC gasoline containing organic sulfur compounds (S = 135 μg/g) was investigated with Ce(IV)Y adsorbent for removal.

The sulfur content was reduced to 20.14 μg/g. The thiophene adsorption mechanism showed that Ce(IV)Y can adsorb thiophene via π electronic interaction directly, and thiophene and Ce(IV) can form a stable sulfur–metal bond (S-M bond) that enhances the adsorption capacity of Ce(IV)Y for thiophene. This method for the modification of NaY zeolite provides a promising selective desulfurization process to prepare clean fuels.     

Ionic Liquid-based Extraction of Sulfur Compounds From Gasoline as a Complementary Process to Oxidative Desulfurization

The extractive desulfurization of a model and several real gasoline samples was investigated using imidazolium-based ionic liquids (ILs). Factorial design of experiments indicated that, among several process variables, the number of extraction steps and the IL/gasoline volume ratio were statistically highly significant. The results showed a desulfurization efficiency of 95.2% under the optimal conditions. The following order was observed for the extraction of thiophenic compounds: benzothiophene>thiophene>3-methylthiophene>2-methylthiophene, with 96.1% removal efficiency for the first one. The IL extraction was applied as a complementary process for the oxidative desulfurization by hydrogen peroxide and formic acid, which provided high efficiency and selectivity for desulfurization of gasoline.     

活性炭基脱硫剂吸附脱除汽油中含硫化合物的研究

以活性炭为载体,采用等体积浸渍负载非贵金属制备了汽油吸附脱硫剂,利用固定床动态吸附法对脱硫剂的吸附性能进行了评价。分别考察了脱硫剂制备条件及固定床动态实验条件对活性炭基脱硫剂吸附脱硫性能的影响。结果表明,活性金属含量为3．0％,焙烧温度为350℃,焙烧时间为1．0～2．0h,吸附温度为120℃,吸附空速为3．0h^-1时,脱硫剂的脱硫率最高,可达55．60％。活性炭载体经硝酸处理后,负载活性组分脱硫剂的脱硫性能得到了较大改善,该脱硫剂更有利于FCC汽油中苯并噻吩类化合物的脱除。     

Experiments of Mercaptans Removal from FCC Gasoline by NaOH Aqueous in Membrane Contactor

Abstract

The process of mercaptans removal from fluid catalytic cracked (FCC) gasoline by NaOH aqueous in a hollow fiber contactor was studied. The results showed that fractional removal of mercaptans was greater in a hydrophobic membrane than that in a hydrophilic membrane at the same condition. The mass transfer coefficient of mercaptans increased significantly while the gasoline flow rate increased because the predominant resistance lies in the gasoline boundary layer. HA-18 modified the solubility of mercaptans in caustic solution and enhanced mercaptans extraction from gasoline. The membrane module should be cleaned by a prolonged operation to recover the membrane property due to membrane fouling.     

1.2 Mt/a S Zorb装置生产超低硫清洁汽油运行概况

介绍了中国石化北京燕山分公司S Zorb装置生产满足京Ⅴ标准的汽油的运行情况。通过对装置加工负荷、原料硫含量进行控制,对吸附剂的反应-再生循环参数进行优化,可以连续稳定地生产硫质量分数低于8 μg/g的满足京Ⅴ排放标准要求的汽油调合组分。同时也对影响装置稳定生产的主要因素进行了分析,提出了相应的对策。