Oxidative Desulfurization of Fuel Oil: Modeling Based on Artificial Neural Network

Abstract

Oxidative desulfurization of fuel oil was investigated using a process consisting of oxidation and distillation steps. In the oxidation step, various organic carboxylic acid/H₂ O₂ systems, especially acetic acid/H₂ O₂, were used as oxidant. They oxidize both easy and refractory sulfur compounds and convert them into oxidized sulfur compounds. The oxidized sulfur compounds are finally removed from fuel oil by distillation in the presence of water. The sulfur content of fuel oil was decreased to levels as low as 20 ppm (up to 90%) in a short contact time, ambient temperature, and atmospheric pressure. The results showed that applying this process did not have any deleterious influence on the distillation characteristic, composition, and content of fuel oil that was examined. An artificial neural network, using back propagation (BP), was also utilized for modeling oxidative desulfuration process of fuel oil. The comparison between the output of ANN modeling and the experimental data showed satisfactory agreement.     

C6H11NO/2TsOH型低共熔溶剂的制备及其催化氧化脱硫性能

通过加热溶解己内酰胺和对甲苯磺酸的混合物制备CC₆H₁₁NO/2TsOH型低共熔溶剂(DESs),并对 C₆H₁₁NO/2TsOH进行红外和氢谱分析。以C₆H₁₁NO/2TsOH为萃取剂和催化剂,H₂O₂为氧化剂,催化氧化脱除模拟油中的硫化物。考察了反应温度、n(H₂O₂)/n(S)、C₆H₁₁NO/2TsOH用量和不同硫化物类型对脱硫效果的影响。结果表明：在低共熔溶剂加入量为1.0 g、温度为60 ℃、n(H₂O₂)/n(S)=4、模拟油体积为5 mL的反应条件下,C₆H₁₁NO/2TsOH对二苯并噻吩(DBT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)和苯并噻吩(BT)的脱除率分别为97.32%、86.60%、77.80%;C₆H₁₁NO/2TsOH循环使用5次,催化活性无明显下降;动力学分析表明,作用下的氧化脱硫过程符合一级反应动力学。     

氢氧直接合成的过氧化氢原位氧化反应研究进展

过氧化氢（H₂O₂）的活性氧含量高且降解时副产物只有水,可作为工业常用氧化剂的替代物。H₂和O₂直接合成H₂O₂是一种高原子利用效率的绿色合成新技术,有望替代当前传统的工业生产方式,实现H₂O₂清洁生产与原位选择性氧化的一步集成。综述了H₂和O₂直接合成H₂O₂与丙烯环氧化、Fenton废水处理、甲烷氧化等反应的集成,介绍现已取得的成果及面临的挑战,拓宽H2、O2和有机物的原位氧化反应体系,为未来化学品的绿色合成提供新思路。     

多孔双功能钛硅新材料的合成与表征

利用H₂和O₂直接生产H₂O₂的工艺与其下游制备高附加值含氧有机化学品的工艺相耦合的一步法工艺,是新一代极具竞争力的烃类选择性氧化工艺,其核心为多孔双功能钛硅催化剂。设计并合成出了用于一步法工艺且性能优异的多孔双功能钛硅新材料RN-1,并对所合成的样品进行了物化性质和结构的分析表征以及催化性能评价。结果表明,RN-1的晶粒为多孔结构,同时具有微孔和介孔甚至大孔;含有一定量的Pd金属组分且高度分散,含有的Ti绝大部分以骨架Ti的形式存在;RN-1的催化氧化性能优异,在催化以丙烯与H₂和O₂直接环氧化反应中,目标产物环氧丙烷的选择性达到94.5%。     

煤直接液化重油胶质和沥青质中杂原子化合物的分子表征

采用傅里叶变换离子回旋共振质谱(FT-ICR MS)研究沸点大于360℃的煤直接液化重油中胶质、沥青质的组成,通过在分子水平上对杂原子化合物进行表征分析胶质、沥青质中杂原子类型、碳数分布和等效双键(DBE)。结果表明,煤直接液化重油中胶质及沥青质中杂原子化合物的分子组成十分复杂,采用正离子电喷雾结合高分辨傅里叶变换离子回旋共振质谱鉴定出了N₁、N₁O₁、N₂、N₂O₂、N₂S₁ 5类不同分子组成的碱性氮化物和S₁、S₂ 2种含硫化合物;采用负离子电喷雾鉴定出了N₁、N₁O₁、N₁O₂、N₂、N₂O₁、N₂O₂ 6类非碱性氮化物和O₁、O₂、O₃、O₄、O₅、O₆、O₁S₁、O₂S₁、O₃S₁、O₄S₁ 10类含氧化合物,其中碱性氮化物相对丰度较高的是N₁类化合物,含硫化合物相对丰度较高的是S₁类化合物,非碱性氮化物相对丰度最高的是N₁O₂类化合物,含氧化合物相对丰度最高的是O₂类化合物。根据各类化合物的DBE和碳数分布,获得了煤直接液化重油中胶质、沥青质分子组成的重要信息。碱性N₁类化合物主要母核结构是吡啶和喹啉为中心官能团的化合物,非碱性N₁类化合物主要母核结构是苯并咔唑,S₁类化合物主要以高缩合、长侧链的稠环含硫芳烃为主,O₂类化合物主要母核结构是菲二酚及蒽二酚。     

钨酸铋的制备及其催化氧化脱硫性能

催化氧化脱硫法因反应条件温和、可高效深度脱除燃料油中二苯并噻吩(DBT)类硫化物,是一种有潜力的非加氢脱硫方法。以钨酸钠和五水合硝酸铋为原料,采用直接沉淀法和水热法制备钨酸铋(Bi₂WO₆)。采用傅里叶变换红外光谱(FT-IR)、X-射线衍射(XRD)、电子扫描显微图像(SEM)、能量色散X射线光谱(EDS)和N₂等温吸附-脱附等分析方法对其结构、组成、表面形貌和比表面积进行表征。分别以DBT、苯并噻吩(BT)、4-甲基-二苯并噻吩(4-MDBT)和4,6-二甲二苯并塞吩(4,6-DMDBT)为代表性硫化物,以正癸烷为溶剂、十四烷为内标物配制含硫模拟油,以制备的Bi₂WO₆为催化剂、过氧化氢(H₂O₂)为氧化剂、乙腈(CH₃CN)为萃取剂构建催化氧化脱硫体系,系统地考察了其催化氧化脱硫性能。结果表明,水热法制备的Bi₂WO₆(BWO-2)表现出较优的脱硫性能。在反应温度...     

CO-PROCESSING OF ALBERTA SUBBITUMINOUS COAL WITH OIL SAND BITUMEN

Co-processing of six Alberta subbituminous coals and Suncor bitumen (Athabasca deposit) by using H₂ (Fe₂ O₃ catalyst) and CO/steam (K₂CO₃ catalyst) as reducing atmospheres have been studied. Results show that CO/steam gives significantly higher overall conversion compared to H₂ with certain coals. However, the quality of products (as determined by distillation and subsequent extraction) are better when H₂ was used in the co-processing of coal with bitumen. A second stage catalytic hydrogenation is required to upgrade heavy hydrocarbons (extracts) which form almost 50% of the product.     

COMPARISON BETWEEN THE PERFORMANCE OF CONVENTIONAL AND HIGH-METAL Co-Mo AND Ni-Mo CATALYSTS IN DEEP DESULFURIZATION OF KUWAIT ATMOSPHERIC GAS OIL

Due to environmental constraints, sulfur content of diesel fuel has been restricted to very low levels (500 ppm maximum) in many countries. As a result, a greater emphasis has been placed in recent years on the development of catalysts and processes for deep desulfurization of diesel blending streams to produce low sulfur diesel fuel. In the present work we have compared the performance of a conventional Co-Mo catalyst with that of high metal loading Co-Mo and Ni-Mo catalysts in deep desulfurization of Kuwait atmospheric gas oil. The tests were carried out in a fixed bed reactor unit using 75 ml of catalyst under the conditions: P=32 bar; LHSV = 4h^-1; H₂/oil ratio = 100 ml/ml; temperature range = 330 - 390°C. HDS activity of the high molybdenum Co-Mo catalyst was superior to that of the conventional Co-Mo hydrotreating catalyst. High metal loading Co-Mo/Al₂O₃ catalyst also showed a substantially higher HDS activity than the Ni-Mo/Al₂O₃ catalyst containing a similar high metal loading. The unreacted sulfur compounds remaining in the product after high severity hydrotreating were identified as dibenzothiophenes with alkyl substituents next to the sulfur atom. The desulfiirization of such low reactive alkyl dibenzothiophenes was found to occur at a substantially lower temperature over the high metal loading Co-Mo catalyst compared with the conventional Co-Mo catalyst. The results have been explained on the basis of the stacking and dispersion of MoS₂ slabs as well as in terms of the nature of the sulfur vacancies in the MoS₂ layers in these catalyst systems.     

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

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.     

复合催化氧化直馏柴油脱硫的研究

在高压反应釜中,采用均相催化氧化脱硫催化剂和纯Oz对直馏柴油进行催化氧化脱硫,可达到很好的脱硫效果,但此法得到的氧化柴油酸值较大,加入助剂可以抑制烃类化合物的氧化,降低了氧化柴油的酸值,提高了氧化油收率,且硫含量也可达到欧洲Ⅱ类柴油标准(总硫<300μg/g)。结果表明,复合催化氧化脱硫使柴油中硫的质量分数降到271μg/g,酸值下降89.2%,氧化油收率提高1.4%。     

OXIDATION CHEMISTRY IN ASPHALT

A possible mechanism of asphalt oxidation with O₂ or photo-excited O₂ is presented herein. The oxidation reaction will occur via an allowed reaction pathway -charge-transfer (CT) complexes. Oxidation reactions transform the sulfur-containing compounds from electron donors to electron acceptors - sulfoxides. These new electron acceptors form CT complexes with electron donors, particularly nitrogen-containing compounds and aromatic compounds. An increase in the average molecular weight after oxidation of asphalt may be due to the formation of CT complex. Treatment with H₂SO₄ or p-chloranil increases the electron acceptor concentration in asphalt. The resulting products show extremely large increases in viscosity. ESR studies show decreases in the signal intensity ratio of vanadyl porphyrins to free radicals in asphalt after oxidation. The decrease in this ratio may be due to the formation of CT complexes. The introduction of deactivating groups such as nitro or fluoro functional groups, or hydroquinone in asphalt will increase the elastic recovery of original asphalt and thin film oven test residues. These results suggest that the rheological properties of asphalt can be strongly affected by controlling the formation of CT complexes.     

生产低硫汽油的新型催化裂化工艺研究

通过调变催化剂中V的价态,借助X射线光电子能谱（XPS）分析、小型固定床和中型提升管装置实验,开发了以自制催化剂c为基础、再生斜管部分增加H₂还原预处理器的催化裂化（FCC）新工艺。催化剂经H₂还原预处理后,其所含V由5价态降为4价、3价,甚至更低价态,在催化反应中可与氧化态硫接触反应,从而降低FCC汽油硫含量。经H₂还原预处理的自制催化剂c（V质量分数0.6%）的催化脱硫效果显著,适宜的H₂预还原温度为550℃,预还原时间为20 min。采用自制催化剂c,在H₂预还原温度650℃、还原时间20 min、H₂流量40 L/h、反应温度500℃、再生温度690℃、剂/油质量比6的条件下,新工艺的FCC汽油S质量浓度由880 μg/mL降至515 μg/mL。     

辽河油田杜84块H2S成因探讨

辽河油田杜84块超稠油由蒸汽吞吐转为蒸汽辅助重力泄油（SAGD）开发后,产生了较高浓度的H₂S,导致脱硫设施投入和油气处理成本增加。通过原油、伴生气、地层水和储层矿物地球化学测试分析,H₂S产量与原油含硫量、地层水SO₄2-浓度无明显相关性,而与储层中黄铁矿含量一致性强,黄铁矿中的硫属于生物来源,同位素范围与原油基本一致,起源于原油稠化阶段,大量形成于稠油热采阶段。高温高压热模拟实验表明,注蒸汽热力采油过程中,除含硫有机质热裂解（TDS）和硫酸盐热化学还原反应（TSR）外,黄铁矿氧化分解也是H₂S形成途径之一,当注入低矿化度蒸汽对地层水稀释后,SO₄2-浓度下降,黄铁矿分解是H₂S的主要生成途径,H₂S的生成和分布受控于油藏地质条件、开发方式、开发时间和受热温度。      

催化氧化法在液化气深度脱硫中的应用研究

针对精制液化气(LPG)的硫含量经常不能满足下游用户要求的情况,开展了在特定催化剂作用下以H2 O2作为氧化剂的LPG高选择性超深度脱硫研究.以精制LPG中最常见的残余硫化物配制模型油,考察反应条件的影响,然后在最佳条件下对炼油厂精制C4进行脱硫试验.结果表明:模拟油脱硫的最佳条件为采用C催化剂、反应温度35℃、n(H...     

加拿大油砂沥青中极性化合物的电喷雾—高分辨质谱研究

目前,生物降解作用对饱和烃生物标志物、芳香烃生物标志物参数以及小分子含氮化合物参数影响的研究较多,而对大分子极性化合物组成影响的研究较少。采用负离子电喷雾—傅立叶变换离子回旋共振质谱(ESI FT-ICR MS)分析不同降解级别的加拿大油砂沥青中酸性及非碱性氮化合物分子组成,结果表明,加拿大油砂沥青中杂原子化合物组成非常复杂,共鉴定出10种不同杂原子类型(N1、N1O1、N1O2、N1S1、O1、O1S1、O2、O2S1、O3、O4)的化合物,其中以O2类化合物为主。随着生物降解程度的加深,N1、N1O1及O1类化合物的相对丰度逐渐降低,而O2及O2S1类化合物的相对丰度显现出逐渐增加的趋势;高分辨质谱分析在石油大分子杂原子化合物研究方面所独有的优势,为石油地球化学研究提供了新的思路。     

催化裂化催化剂积炭的杂原子组成及其再生转化机理

以不同工艺条件下的催化裂化待生、再生催化剂及催化剂再生烟气为研究对象,分析催化剂积炭的杂原子组成。依据密度泛函理论,利用Gaussian 09软件在B3LYP/def2-TZVP水平下对积炭中典型的含氮、含硫化合物进行几何优化,得到其最稳定构型;以Laplacian键级为判据,研究积炭中杂原子的转化机理。结果表明：催化剂积炭中的含氮化合物主要是吡啶类、吡咯类和季胺类化合物,含硫化合物主要是噻吩类化合物;催化剂再生初期,含氮化合物以∶NH和·CN的形式逸出,主要转化成NH₃和HCN;含硫化合物以·HS和∶S等形式逸出,主要转化为H₂S、COS;随着再生过程的进行,NH₃、HCN和H₂S、COS最终分别转化为NO_x和SO_x。模拟结果与不同再生工艺条件下再生烟气组成一致。     

EFFECTS OF OXYGEN ON THE FT SYNTHESIS OVER Fe-Cu-K CATALYST

The poisoning of commercial coprecipilated Fe-Cu-K catalyst by oxygen in the Fischer-Tropsch synthesis was investigated, since synthesis gas obtained by the gasification of coal contains O₂. The pretreated catalysts were oxidized in a oxygen-containing syngas.The effects of poisoning methods, reaction temperature, and oxygen fed to catalyst on the catalytic behavior of reduced Fe-Cu-K catalyst in a fixed bed were studied for synthesis tests with the ratio H₂/CO of 2.3 containing O₂ 5.16×10^-3 under 2.62 MPa and 524.2 K. The relative activity of catalyst exceeded 1 for the first few hours of poisoning by oxygen both in prepoisoning and poisoning in situ process, then decreased linearly with the increasing of oxygen fed to catalyst, and finally increased to the relative activity of 0.6-0.7. The activity decreased less rapidly poisoning in situ than that of prepoisoning. The gaseous hydrocarbons average molecular weight increased greatly when poisoned by oxygen. The wax weight percentage in products and the ratio of olefin to paraffin decreased as poisoned by oxygen. Oxygen also affects the composition of oils and the contents of oxygenated compounds formed in water phase.     

低浓度H2S酸气硫回收工艺技术的优化

针对靖边气田某天然气净化厂硫磺回收装置尾气SO₂排放不达标等问题,以提高H₂S转化率、降低SO₂排放量为目标,在传统Clinsulf-DO工艺的基础上,从工艺流程和催化剂方面进行优化设计,形成了双反应器选择性氧化硫回收工艺及尾气碱洗技术,并采用国产催化剂HS-35和HS-38进行催化反应。工业标定结果表明,改造后装置总硫转化率由原工艺的80.27%提升到94%以上,尾气中SO₂的质量浓度降低到100 mg/m³以下,达到了新环保法规《石油炼制工业污染物排放标准（GB31570—2015）》的规定。较好的工业应用结果可为同行业低含H₂S酸性气硫回收和尾气排放达标提供一定的参考。     

酸气回注技术发展现状及其在中国的应用前景

零排放的酸气回注技术是一种替代硫磺回收工艺的经济可行的酸气处理方法,同时也是一个减少温室气体排放的环保方法。为此,总结了酸气回注技术的发展和应用现状,结合实例对酸气回注和硫磺回收进行了经济技术和环保对比分析,结果表明：酸气回注方案的硫处理费用为1 270美元/t;而硫磺回收的硫处理费用为1 400美元/t,若进一步考虑CO₂排放、硫磺销售等因素,其综合处理费用将超过1 779美元/t。同时,分析了酸气回注在中国的应用需求及条件,展望了该技术在中国的应用前景,指出在下述几种情况下,为了取得最好的经济和环保效益,酸气回注会是一个不错的选择：①老气田气质变化后,硫磺回收装置已不适应生产需要而需改造;②新开发气田太偏远或H₂S含量太低,硫磺回收不经济或工艺技术不好解决;③部分新开发气田的天然气组成不稳定,进行硫磺回收投资大、风险高;④部分碳酸盐岩开发油田伴生气含H₂S,但含量变化大,进行硫磺回收工艺选择难度大;⑤火驱开发油田和采用蒸汽辅助重力泄油开发的稠油油田,其伴生气中H₂S含量大,但气量小,回收不经济;⑥低渗透油田用CO₂提高采收率等。     

准噶尔盆地南缘井筒堵塞物中沥青质分子组成研究

采用傅里叶变换离子回旋共振质谱分析技术,分析了准噶尔盆地南缘高探1井原油及井筒堵塞物抽提物中沥青质化学组成及差异,探讨了沥青质的组成及结构与沥青质沉积关系,对于沥青质聚集理论研究具有重要意义.研究结果显示,高探1井原油及井筒堵塞物抽提物中沥青质分子主要为N1、N1 O1、O1、O2、O3和O4类化合物,但堵塞物抽提物中...