Diesel desulfurization using a ultrasound-assisted oxidative process

In this study, the removal of sulfur compounds from diesel samples using ultrasound-assisted oxidative desulfurization (UAODS) process in presence of different types of oxidizing agents was studied. Experiments were performed to assess the effects of influential parameters on the performance of UAODS process including ultrasonic irradiation time, oxidant type, mass ratio of oxidant to diesel fuel (oxidant: diesel), and finally acetic acid as an oxidative promoter. The efficiency of sulfur compounds removal from the diesel fuel dramatically improved using appropriate oxidative process with the assistance of ultrasound irradiation. H₂O₂ was found to be the most promising oxidant component whose concentration in the media directly affected total sulfur removal and thiol group conversion efficiencies. Using 4 wt% of H₂O₂ followed by 15 min of ultrasonic irradiation leaded to sulfur removal efficiency of 76% and thiol group conversion of 79% at ambient temperature and atmospheric pressure. Using acid acetic as the promoter of H₂O₂ also leaded to further sulfur compounds removal.     

含氨脱硫干气制氢工艺技术探讨

阐述了某新建的制氢装置以加氢裂化干气和天然气为主要原料,为加氢裂化装置提供加氢原料的工艺技术。干气NH3含量超标,若直接进入加氢反应器,氨与有机硫存在竞争吸附,造成催化剂活性的减弱或丧失。选择了3种工艺改进方案进行对比,结果表明,更换催化剂与其它方案相比具有明显的技术优势。     

Prediction of dibenzothiophene conversion in the ultrasound assisted oxidative desulfurization process

In order to produce ultra-low sulfur diesel, ultrasound-assisted oxidation desulfurization of dibenzothiophene (DBT) was carried out with acetic acid and hydrogen peroxide. Due to its complexity, ultrasound-assisted oxidation process lacks a precise analytical solution. This paper explores the application of linear multiple regression and neural network for the prediction of dibenzothiophene conversion. Models were employed with respect to hydrogen peroxide dosage, temperature, reaction time, initial DBT concentration, and rate constant. The most accurate results were achieved by neural network model. Developed models facilitate future research in terms of better understanding the influence of process conditions of DBT conversion.     

焦化柴油中二苯并噻吩类含硫化合物的加氢脱硫反应动力学

采用20 mL高压连续反应装置,在压力5.0 MPa、体积空速0.7～3.0 h^-1、氢/油体积比400、温度330℃的条件下,考察了焦化柴油中难脱除的二苯并噻吩类含硫化合物（DBTs）在工业化负载型NiMo/γ-Al₂O₃催化剂上的加氢脱硫（HDS）反应活性。采用气相色谱 脉冲火焰光度检测器（GC-PFPD）对加氢前后焦化柴油中含硫化合物进行了定量分析,研究了它们在深度HDS过程中的脱除规律,建立了难脱除DBTs的HDS反应一级动力学模型。焦化柴油的深度HDS过程中,DBTs尤其是4位和6位取代的DBTs是最难脱除的含硫化合物,各含硫化合物的HDS反应速率常数大小顺序为DBT、 4-MDBT、4-EDBT、3,6-DMDBT、4-E,6-MDBT、2,4,6-TMDBT、4,6-DMDBT。     

硫化氢对胺法气体脱硫能耗的影响

利用PRO/Ⅱ软件对胺法气体脱硫工艺进行模拟分析,研究了贫胺液中H_2S含量与再生塔的冷凝器、再沸器热负荷的关系,指出了胺法气体脱硫优化操作的方向,为胺法气体脱硫工艺的生产调优提供理论依据,有效地降低了脱硫的能耗。     

废塑料裂化降解制汽油及柴油工艺过程研究

以废聚乙烯（PE）、聚丙烯（PP）和聚苯乙烯（PS）等为原料，研究了通过热裂化、催化裂化、催化改质反应制备车用汽油、柴油的工艺过程，得出了各反应过程优化的工艺条件：采用SH－1型催化剂在380℃下进行催化裂化反应，油品收率可达86.0%，辛烷值在80左右；采用JD－01型催化剂进行异构化反应，油品收率可达82.0％，辛烷值达93。     

Ultra-deep adsorptive desulfurization process over activated carbon and effects on quality of real diesel

Fuel cell applications require ultra-low-sulfur diesel (ULSD, total sulfur content ≤1?μg/g). With a breakthrough sulfur content of 1?μg/g, dynamic adsorptive desulfurization (ADS) and regeneration performance over activated carbon were investigated under ambient conditions for commercial diesel (total sulfur content of 34.83?μg/g). The quality of ULSD was in a rounded analysis. Results show that polyaromatic hydrocarbons (PAHs) have a negative impact on ultra-deep ADS. Cetane number, acidity, and content of PAHs in ULSD are superior to current standards of State V or Euro VI, which means that ultra-deep ADS has little effect on diesel quality.     

焦化柴油氧化脱硫脱氮工艺条件优化

研究了工艺条件对焦化柴油氧化萃取脱硫脱氮效果的影响。结果表明,氧化体系选用双氧水溶液(H2O2质量分数为30%)和甲酸,以磷钨酸为催化剂,以糠醛为萃取剂,在氧化温度为70℃,恒温回流搅拌时间为60 min,V(氧化体系)/V(焦化柴油)为0.4,V(甲酸)/V(双氧水溶液)为0.5,磷钨酸用量为0.20 g/L,采用二级萃取的优化工艺条件下,可将焦化柴油中硫的质量分数由817.563×10-6降至45.613×10-6,氮质量分数由734.577×10-6降至13.620×10-6。     

柴油加氢脱硫绝热反应动力学模型

研究了NiMo型催化剂在柴油加氢反应过程中的动力学规律,综合考虑硫化氢、氮化物和芳烃的抑制作用,建立了三集总加氢脱硫反应动力学模型。通过对反应过程中放热和温升的估算,建立了柴油绝热加氢脱硫反应动力学模型。根据模型计算了等温和绝热环境中物流性质沿反应器轴向的变化规律。结果显示,二者的变化规律存在明显差异,达到相同脱硫深度时,绝热条件中硫化物和氮化物前期脱除速率慢于等温条件。另外,通过模型详细描述了绝热条件各集总硫化物、氮化物和芳烃含量沿反应器轴向的变化规律,获得了各集总在反应器不同位置硫化物、氮化物和芳烃含量的定量数据,结果显示,硫化物、氮化物和芳烃含量各集总的变化趋势均不相同。     

Ultrasound assisted catalytic oxidative desulfurization of diesel oil using CdO nanoparticles

In this paper, sol-gel auto-combustion method is used to synthesize CdO nanoparticles. The synthesised sample is characterized for its size and structure using X-Ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. And some molecular groups containing in the nanoparticle are detected by Fourier transformer Infra Red (FT-IR). Then, the sample is used to remove the organic sulfur from hydrogenation desulfurated diesel under ultrasonic condition. The influence parameters including catalyst dosage, oxidant dosage, oxidation temperature, oxidation time and extracting times are been researched. The obtained result indicates that under the optimal condition, the desulfurization degree can be reached 72.7%.     

Efficient desulfurization of gasoline fuel using ionic liquid extraction as a complementary process to adsorptive desulfurization

The extractive desulfurization of a model gasoline containing several alky]thiols and aromatic thiophenic compounds was investigated using two imidazolium-based ionic liquids(ILs).1-butyl-3-methylimidazolium tetrachloroaluminate,and l-oetyl-3-methylimidazolium tetrafluoroborate.as extractants.A fractional factorial design of experiments was employed to evaluate the effects and possible interactions of several process variables.Analysis of variance tests indicated that the number of extraction steps and the IL/gasoline volume ratio were of statistically highly significant,but none of the interactions were significant.The results showed that the desulfurizalion efficiency of the model gasoline by the ILs could reach 95.2%under the optimal conditions.The optimized conditions were applied to study the extraction of thiophenic compounds in model gasoline and several real gasoline samples:the following order was observed in their separation:benzothiophene > thiophene > 3-methylthiophene > 2-melhylthiophene.with 96.1%removal efficiency for benzothiophene.The IL extraction was successfully applied as a complementary process to the adsorptive desulfurization with activated Raney nickel and acetonitrile solvent.The results indicated that the adsorptive process combined with IL extraction could provide high efficiency and selectivity,which can be regarded as a promising energy efficient desulfurization strategy for production of low-sulfur gasoline.     

柴油质量升级技术方案优化研究

国内某炼油厂柴油产品产率和密度均偏低,导致全厂仅能生产调合硫质量分数低于350μg/g的国Ⅲ标准车用柴油产品.根据柴油国Ⅴ质量升级的需要,对该厂现有0.80 Mt/a加氢改质和0.15 Mt/a柴油加氢精制装置进行加工方案优化,使其具备生产硫质量分数低于10 μg/g的国Ⅴ标准柴油产品的能力,增加-20号、0号柴油产品产量.采用FRIPP开发的加氢改质降凝工艺技术（FHIW）对两套加氢装置的原料进行优化调整,结果显示：生产-20号柴油方案时,使用两套加氢装置分别加工四组分混合油和直馏轻柴油的柴油产率为90.71％,较五组分混合油一起加工提高1.81％;生产0号柴油方案时,使用Ⅰ套加氢装置加工五组分混合油柴油产率为97.20％,较Ⅱ套加氢装置提高1.95％.     

柴油加氢改质过程烃类反应与十六烷值的关系

在固定床中型加氢实验装置上,以石家庄炼化分公司催化裂化柴油为原料,在氢分压10.0 MPa、体积空速1.14 h^-1、氢/油体积比1000、反应温度360℃的条件下,考察了加氢改质精制段各主要烃类的化学反应过程;在氢分压10.0 MPa、体积空速2.68 h^-1、氢/油体积比1000、精制段反应温度360℃的条件下,考察了加氢改质的改质段不同反应温度下的化学反应过程。结果表明,精制段中,芳烃的加氢饱和反应对十六烷值的正向贡献约为18.46个单位,长侧链烃类断裂为短侧链烃类的反应对十六烷值的负向贡献约为1.06个单位,正负向的综合作用使得十六烷值提高17.40个单位;改质段中,芳烃加氢饱和反应和环状烃开环裂化反应对十六烷值的正向贡献为3.93~6.60个单位,长侧链烃类断裂为短侧链烃类的反应对十六烷值的负向贡献为0.33~1.19个单位,综合作用的结果使得改质产品柴油与精制油相比十六烷值提高3.60~5.50个单位。     

劣质柴油非加氢精制技术

劣质柴油必须进行精制才能满足规格指标和环保要求 ,加氢精制是精制劣质柴油生产优质柴油馏分的理想工艺技术 ,但投资大和操作费用高 ,非加氢技术精制劣质柴油是提高柴油产品质量满足环保要求比较经济、可行的途径。介绍了化学精制、溶剂精制、吸附精制、氧化 /萃取脱硫、生物脱硫等柴油的非加氢精制技术的最新进展情况 ,认为吸附精制是提高我国柴油质量的有效途径     

330MW火电机组脱硫系统供浆量自动控制技术设计

本文通过具体工程概况分析出利用定量计算和PID闭环控制可以有效实现330MW火电机组脱硫系统供浆量自动控制,提高了脱硫工艺控制的可靠性,减少了人为因素导致的脱硫净烟气SO2超标事故。     

柴油非加氢脱硫技术进展

对各种柴油脱硫技术进行了综述，提出了离子液体脱硫技术是一项很有前途的技术，尽管其脱硫率不高，但它具有非常明显的优点，能够脱除所有的芳烃和硫化物。国内西南石油学院开发的催化氧化脱硫新技术用空气代替价格较高的过氧化氢氧化剂，属于环保绿色技术，应用前景很好。     

焦化柴油催化氧化吸附脱硫工艺条件优化

以磷钼酸季铵盐为催化剂,三氟乙酸为氧化剂,糠醛为萃取剂,采用催化氧化-萃取吸附组合工艺对焦化柴油进行脱硫处理。结果表明,在反应温度为60℃,氧化剂用量（V（氧化剂）/V（焦化柴油））为0.2,催化剂用量（m（催化剂）/V（焦化柴油））为8 g/L,反应时间为60 min,萃取剂用量（V（萃取剂）/V（焦化柴油））为1.0,萃取时间为30 m in的最佳工艺条件下,焦化柴油的硫质量分数可从1.05×10-3下降为42×10-6。     

抚顺页岩油柴油馏分加氢脱硫动力学

针对抚顺页岩油柴油馏分加氢脱硫(HDS)反应的特点,采用集总的方法建立了抚顺页岩油柴油馏分加氢脱硫三集总动力学模型,并对相应的动力学参数进行了计算。结果表明,利用该模型计算得到的产物硫剩余率与实测值吻合较好,误差较小。该模型能够预测抚顺页岩油柴油馏分 HDS 过程中的硫化物脱除情况,所求取的动力学参数可靠,且模型具有一定的外推性。     

脱硫过程对废胶粉改性沥青粘度的影响

通过对高温反应和存储时间的试验研究,验证了脱硫程度对废胶粉改性沥青性能有着重要的影响.并通过添加活化剂来加速脱硫反应的进行,从而使废胶粉改性沥青获得更好的应用性能.     

原料性质对柴油中压加氢改质反应的影响

在固定床加氢中试装置上,以不同性质的混合柴油为原料,在氢分压75 MPa、体积空速10 h-1、氢/油体积比 800、反应温度350~370℃的条件下,进行柴油中压加氢改质实验,考察了原料性质对柴油加氢改质反应中芳烃饱和率、多环环烷烃开环率和断链率的影响。结果表明,原料芳烃含量较低时,更有利于芳烃饱和反应以及多环环烷烃开环反应的进行;断链反应使得产物中柴油馏分的链烷烃量高于原料。对于同一种原料,随反应温度增加,芳烃饱和率的增幅较为缓和,而多环环烷烃开环率显著增加;原料中芳烃含量越低,多环环烷烃开环率随反应温度的变化越显著。