柴油超深度加氢脱硫（RTS）技术研究

通过分析影响柴油超深度脱硫的主要因素,提出并开发了柴油超深度加氢脱硫（RTS）工艺, 进行了RTS技术生产超低硫柴油的工艺研究。结果表明,采用RTS技术,通过工艺流程和操作条件优化,对以高硫直馏柴油为主的原料,可在比常规加氢精制工艺高50%以上的空速下生产出硫含量小于50μg/g和10μg/g的超低硫柴油产品。RTS技术稳定性试验结果表明,RTS技术可以满足工业装置长周期运转的需要。     

直馏柴油络合萃取脱硫的实验研究

采用自制的脱硫络合萃取剂(TS-1),考察其对直馏柴油中硫化物的脱除效果。在萃取温度20℃、萃取时间5 min、相分离时间15 min、剂油体积比为2%的条件下,直馏柴油A的硫含量从711μg/g降到245μg/g,脱硫率为65.6%,柴油收率为99.6%,达到国Ⅲ车用柴油硫含量标准(350μg/g);继续增加剂油比到5%,柴油A的硫含量可降到42μg/g,脱硫率达94.1%,柴油收率为99.5%。在最佳操作条件下,对低硫柴油B(硫含量374μg/g)和高硫柴油C(硫含量1 737μg/g)进行络合萃取脱硫实验。结果表明,使用脱硫络合萃取剂TS-1后柴油B、柴油C都可达到较高的脱硫率。     

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.     

A Comparative Study of the HDS Kinetics of Straight Run and Coker Gas Oils Under Deep Desulfurization Conditions

Abstract

Deep desulfurization of diesel blending streams has gained considerable importance in the petroleum refining industry in recent years due to environmental regulations which limit the sulfur content of diesel fuel to very low levels. Among the various factors influencing deep desulfurization of diesel to lower and lower sulfur levels, the quality of the feedstock plays an important role. In the present work, the degree of desulfurization of two different feedstocks, namely, coker gas oil (CGO) and straight run gas oil (SRGO) and their blends was investigated under different operating severities. The distributions of different types of sulfur compounds in both feeds were examined by GC-SCD. Kinetics of desulfurization of both feeds under deep desulfurization conditions was also studied. The results revealed that SRGO, in spite of having a significantly larger amount of total sulfur, desulfurized more easily and produced diesel fuel with low sulfur levels in the desired range (< 350 ppm) at lower temperatures compared with CGO. More severe operating conditions (higher temperature, lower LHSV etc.) were found necessary to bring about deep desulfurization of CGO and its blends with SRGO to the same sulfur level. Kinetic experiments showed a reaction order of 1.5 for the overall HDS of both types of feeds, but the activation energy was higher for CGO (30 kcal/mole) than SRGO (24 kcal/mole). The results are explained on the basis of the differences in the concentrations of nitrogen and refractory sulfur compounds present in the two feeds.     

机动车燃油的脱硫技术及机理

介绍了世界燃油质量标准,简要报道了机动车用汽、柴油中硫化物的种类和含量,详细报道了燃油的加氢、生物、氧化和吸附脱硫机理及技术。噻吩类化合物占汽油总含硫量的83%,柴油中的硫主要以苯并噻吩及二苯并噻吩形式存在。吸附脱硫将会成为具有良好发展前景的燃油脱硫技术。插图6幅,数据表4张,参考文献37篇。     

常温液态丙烯精脱硫技术的工业应用

简述常温液态丙烯精脱硫原理及工艺流程,介绍T-907型COS水解剂和Tc-22型常温脱硫剂在丙烯腈装置丙烯原料净化过程中的工业应用情况。应用结果表明,脱后丙烯总硫含量可降到1μg/g以下,脱硫效果良好。     

高硫柴油加氢处理生产低硫,低芳烃柴油的研究

利用中型试验装置对中东原油生产的高硫直馏柴油进行加氢处理生产低硫、低芳烃柴油的工艺研究。考察了反应温度、氢分区、空速、氢油比等工艺参数以及原料油性质和循环氢中Ｈ２Ｓ浓度等操作条件对深度脱硫、脱芳烃效果的影响。研究结果表明：利用ＲＮ－１加氢处理催化剂，对含硫量（质量分数）１．３％左右的高硫直馏柴油的加氢脱硫（ＨＤＳ），可以在缓和的条件（ＰＨ＝３．２ＭＰａ，ＬＨＳＶ＝３．０ｈ－１）下生产出硫含量低于０．０５％的低硫柴油；在中等压力（ＰＨ＝６．４ＭＰａ）和降低空速的条件下生产出低硫、低芳烃（Ｓ＜０．０５％、芳烃（体积分数）＜２０％或１０％）柴油。     

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.     

Span-60乳化剂用于流化催化裂化柴油氧化脱硫

以Span-60为乳化剂、双氧水为氧化剂、固载磷钨酸的半焦为催化剂,对流化催化裂化(FCC)柴油进行氧化脱硫;考察了反应时间、反应温度、Span-60乳化剂用量和双氧水用量对脱硫率的影响。实验结果表明,FCC柴油氧化脱硫的优化反应条件为:反应时间60m in、反应温度60℃、Span-60乳化剂用量(基于FCC柴油的质量分数)0.6%、双氧水用量(基于FCC柴油的质量分数)2%、催化剂用量(基于FCC柴油的质量分数)1.2%。在此条件下对FCC柴油进行氧化脱硫,FCC柴油中的硫含量由1 400μg/g降至84μg/g,脱硫率达94%。气相色谱分析结果显示,氧化脱硫后FCC柴油中的苯并噻吩衍生物、二苯并噻吩及其衍生物基本上被脱除。     

高低温双反应区平台工艺RTS在炼油领域的应用

为了更好地实现深度脱硫、脱氮以及芳烃饱和等反应,开发了高低温双反应区平台工艺技术RTS。该平台工艺技术可以用于柴油质量升级、催化裂化柴油（LCO）加氢促进多环芳烃饱和、高氮含量或高终馏点喷气燃料低压加氢、重整预加氢掺炼二次加工石脑油等领域。工业装置运行数据表明：采用RTS技术处理掺炼质量比例25%左右的二次加工柴油馏分的原料时,得到的精制柴油硫质量分数小于10 μg/g,多环芳烃质量分数小于5%,满足国Ⅵ柴油质量标准,且装置运转周期可达到3年以上,实现了长周期稳定运行。     

柴油深度脱硫中砜类氧化产物的萃取分离

 用极性有机溶剂萃取分离柴油催化氧化脱硫反应中的砜类氧化产物,筛选出萃取效果最好的萃取剂N,N-二甲基甲酰胺（DMF）,并采用功率超声萃取和恒温振荡萃取增强萃取脱硫效果。考察了萃取剂用量即剂/油体积比及两种操作状况下各主要工艺参数对萃取脱硫效果的影响,从而确定最佳操作条件。结果表明,当柴油/萃取剂(DMF)体积比为1,在功率超声萃取条件下(功率500W,频率59kHz,时间20min),柴油硫含量可从1703μg/g降至74.8μg/g;在恒温振荡萃取条件下(转速180r/min,温度40℃,时间40min),柴油硫含量可从1703μg/g降至116.0μg/g。     

FH-UDS催化剂在FCC柴油深度加氢脱硫中的应用研究

采用FH-UDS催化剂对FCC柴油和富硫柴油进行脱硫,考察了脱硫反应条件对脱硫效果的影响。结果表明,以FCC柴油为原料,在反应温度为360℃,氢分压为6.0MPa,体积空速为1.5,1.0h-1,氢油体积比为350的条件下,柴油产品硫含量分别低于50,10μg/g,满足欧Ⅳ和欧Ⅴ标准。以富硫柴油为原料,在反应温度为345℃,氢分压为6.3MPa,体积空速为2.3h-1,氢油体积比为320的条件下,产品硫含量低于50μg/g,脱硫率可达99.6%。     

用于FCC柴油氧化萃取脱硫的负载型磷钨酸催化剂和复合萃取剂

采用浸渍法制备磷钨酸(HPW)质量分数不同的半焦负载型催化剂HPW/Sc,利用扫描电镜、紫外漫反射吸收光谱和 N₂吸附-脱附分析方法表征了所制备 HPW/Sc 催化剂的结构,并在FCC 柴油的氧化萃取脱硫过程中将其作为氧化催化剂,考察了HPW 的负载量和萃取剂种类对氧化萃取脱硫率的影响。结果表明,半焦是 HPW 的良好载体,HPW 负载到半焦后保持了原有的Keggin 结构;在最优氧化反应和萃取条件下,FCC 柴油中的硫质量分数由1100 μg/g 降至89.1 μg/g, 脱硫率达到91.9%;评选出了柴油氧化萃取脱硫的专用复合萃取剂,用氢键理论和位阻效应解释了复合萃取剂可以提高回收率的原因。     

LPG铜片腐蚀原因分析及解决方案研究

实验对温米采油厂提供的液化石油气（LPG）样品进行定性、定量检测,确定引起LPG铜片腐蚀不合格的原因是H。S含量超标,样品LPG的硫含量为2．55μg／g。采用干法加速评价法来脱除LPG中的H2S。从常用的脱硫剂中评选出CNDS-1为最优脱硫剂,其最佳脱硫操作条件为吸附温度20℃～40℃,空速0．8h－1～1．5h－1。在最佳条件下,可将LPG中的H2S含量从302．40μg／g降到0．30μg／g以下,LPG铜片腐蚀实验合格,CNDS--1对H2S的吸附硫容量为8．20％（w）。根据对CNDS-1脱硫效果的实验研究,提出了固定床干法脱硫的原则工艺流程。该脱硫工艺流程简单,投资和操作费用低,无新增能耗,可以满足LPG产品铜片腐蚀合格的要求。     

催化裂化柴油空气氧化脱硫工艺研究

实验以空气作氧化剂,甲酸作催化剂,甲醇作萃取剂,以催化氧化反应与溶剂萃取相结合法,对催化裂化柴油进行氧化萃取脱硫。经单因素实验考察了催化剂用量、催化氧化温度、时间、空气压力及萃取剂的用量等对催化裂化柴油硫含量的影响。适宜的脱硫条件为:反应温度80℃,反应时间60 min,空气压力0.6 MPa,催化剂用量10%(与柴油的体积比)。经催化氧化,柴油硫含量可由1 694.2μg/g降至347.3μg/g,脱硫率达79.5%。     

柴油逆流加氢超深度脱硫脱芳烃技术的研究和开发

介绍了柴油逆流加氢超深度脱硫脱芳烃技术（简称FCSH）。气液逆流操作可克服常规并流工艺的劣势，提高氢分压并降低液相中H2S浓度，可以获得更高的脱硫、脱芳烃程度。试验结果表明，无论是单级反应器还是二级反应器串联，都体现了逆流操作的优势，采用一级并流，二级逆流串联操作方式，可生产硫含量低于10μg／g的超低硫清洁柴油。所开发的催化剂具有三级孔道结构，可防止液泛，在逆流反应器的循环氢中H2S浓度很低的情况下仍能保持较高的活性和稳定性。[编者按]     

SLHT连续液相加氢技术的工业应用

中海油东方石化有限责任公司采用SLHT连续液相加氢技术,新建一套600 kt/a柴油加氢装置。该技术采用配套新型超深度柴油加氢脱硫RS-2000催化剂,上流式反应器,并将热高压分离器整合进反应器,取消循环氢系统,使得工艺流程简化,投资省、占地少,耗能低。装置以直馏柴油和少量催化裂解柴油为混合原料,生产硫质量分数不大于10 μg/g、氮质量分数不大于5 μg/g、十六烷值60左右的满足国Ⅴ排放标准要求的超低硫柴油产品,装置能耗相比滴流床工艺降低了25%,具有良好的经济效益。     

柴油超深度加氢脱硫RTS技术的工业应用

为了生产满足京V排放标准的超低硫柴油,中国石化北京燕山分公司新建了2.6 Mt/a柴油加氢装置,于2013年9月开工投产。该装置采用中国石化石油化工科学研究院开发的柴油超深度加氢脱硫RTS技术,使用RS-2000加氢催化剂及RG-1保护剂。工业应用结果表明：装置运行平稳,柴油产品硫质量分数不大于10 ?g/g,产品性质稳定;RS-2000催化剂活性稳定性良好,可以在较低压力条件下长周期稳定生产超低硫柴油;装置能耗综合能耗为344.17 MJ/t,比设计值（397.79 MJ/t）低53.62 MJ/t,达到了设计指标要求。     

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.     

An Improved Desulfurization Process Based on H2O2/Formic Acid Oxidation and Liquid-Liquid Extraction 2. FCC Diesel Oil Feedstocks

Abstract

Semi-empirical molecular orbital theory and parametric model 3 methods were used to calculate the quantum chemistry properties of dibenzothiophene (DBT) and its corresponding sulfone compounds to investigate the essential theory of a formic acid/H₂O₂ oxidation desulfurization system. To study oxidation kinetics of the oxidation desulfurization reaction, DBT was also employed as a model compound to obtain the oxidation kinetic parameters. Desulfurization of fluid catalytic cracking (FCC) diesel was also performed in this process, and the sulfur content was reduced from 7,200 μg·g^?1 to 598 μg·g^?1 after being extracted by polyethylene glycol 200.