汽油深度脱硫的技术进展

介绍了加氢脱硫和非加氢脱硫2种汽油脱硫技术。综述了近年来汽油深度脱硫机理方面的研究和技术进展。     

炼油碱渣处理技术研究与应用进展

炼油碱渣是石油炼制过程中油品碱洗精制时产生的一种含有大量硫化物、酚类和石油类等污染物的碱性废液。介绍了国内外炼油碱渣主要处理技术与研究进展,指出了湿式空气氧化法是一种成熟的炼油碱渣处理方法,目前在国内外已获得广泛的工业应用,而生物处理法由于其反应条件温和、安全、成本低,有广阔的应用前景。     

超稠油炼制污水物化处理工程设计

辽河石化公司超稠油炼制污水具有组成复杂、含油量高、乳化严重、污染负荷高、生物毒性强等特点,常规炼油污水处理工艺难以实现其达标排放。为此,设计了"沉降除油-破乳隔油-一级DAF气浮-二级DAF气浮"组合物化处理工程,并结合破乳剂、絮凝剂的投加,实现了污染物(尤其是非溶解性污染物)的去除和石油类资源的最大化回收,保障了后续生化处理单元的稳定运行。     

炼油厂价值链分析与优化

运用价值链分析方法对炼油厂内、外部的价值活动进行了分析,将炼油厂内部价值链划分为主生产作业链、辅助生产作业链和辅助价值链三部分,通过分析指出产品结构不合理、炼油成本较高是影响炼油业务价值的主要原因,针对企业实际情况,提出价值链优化调整策略:提高炼油技术水平,优化装置结构和产品结构,增产高附加值产品,不断提高企业经济效益。     

The impacts of a GTL plant on Brazil's oil products supply and refinery expansion

This paper assesses the impacts of a GTL plant on the expansion of Brazil's oil refining segment. The GTL plant (50,000 bpd) was sized to start up operations in 2015, producing diesel and naphtha through the indirect route (FT-synthesis). This plant will consume the non-associated natural gas production from the recent discoveries at the Santos Basin (around 419 Bm³), and the associated gas production from the Campos Basin. Both basins are located in the Southeast of Brazil, the most populated, rich and industrialized region of the country. Two different criteria for refinery expansion were simulated in order to meet oil product demand scenarios. Findings show that depending on the refinery expansion criteria considered GTL will play a fundamental hole to meet the oil product demand forecast to Brazil in the next 10 years.     

煤焦油加工腐蚀机理及防腐技术探讨

通过对煤焦油加工过程中腐蚀机理的探讨,分析了生产中应重点关注的腐蚀部分,从原料预处理、工艺技术改进和提高设备等级等方面提出了在煤焦油加工过程中有效的防腐方法。     

Development of new catalysts for deep hydrodesulfurization of gas oil

TiO₂–Al₂O₃ composite supports have been prepared by chemical vapor deposition (CVD) over γ-Al₂O₃ substrate, using TiCl₄ as the precursor. High dispersion of TiO₂ overlayer on the surface of Al₂O₃ has been obtained, and no cluster formation has been detected. The catalytic behavior of Mo supported on Al₂O₃, TiO₂ and TiO₂–Al₂O₃ composite has been investigated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and methyl-substituted DBT derivatives. The conversion over the Mo catalysts supported on TiO₂–Al₂O₃ composite, in particular for the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT) is much higher than that of conversion obtained over Mo catalyst supported on Al₂O₃. The ratio of the corresponding cyclohexylbenzenes/biphenyls is increased over Mo catalyst supported on TiO₂–Al₂O₃ composite support. This means that the reaction rate of prehydrogenation of an aromatic ring rather than the rate of hydrogenolysis of C–S bond cleavage is accelerated for the HDS of DBT derivatives. The Mo/TiO₂–Al₂O₃ catalyst leads to higher catalytic performance for deep HDS of gas oil.     

Assessment of limitations and potentials for improvement in deep desulfurization through detailed kinetic analysis of mechanistic pathways

Utilizing an improved method for the assignment of the rate constants to the complicated network of reaction pathways in the hydrodesulfurization (HDS) of polyaromatic sulfur compounds (PASCs), new understanding has been obtained concerning the intrinsic limitations to achieving the new distillate fuels standards. Establishing the relative rates for hydrogenation of the parent sulfur compound and its desulfurized products, and considering thermodynamic limitations on hydrogenated intermediates are critical to these improved kinetics. With this new approach, it has been possible to more accurately assess the differences in performance of different catalysts such as Co–MoS_x/Al₂O₃, Ni–MoS_x/Al₂O₃ and analogous catalysts supported on carbons, the basic causes of selectivity change with temperature, and the mechanistic consequences of inhibitors on the HDS product distributions. Ni promoted catalysts were found to possess much higher hydrogenation activities than comparable Co promoted catalysts. Carbon supported catalysts appear to have potential for HDS at high temperatures. Inhibition by H₂S affects both hydrogenation and direct sulfur extraction HDS routes, but, secondary hydrogenation of desulfurized aromatic products was found to be the most sensitive to inhibition. Naphthalene inhibits all hydrogenation reactions but has little effect on direct HDS.     

生物炼制与石油炼制一体化——促进我国生物质能源发展的有效对策之一

生物炼制是与石油炼制互补的新型工业生产模式,对我国生物质能源发展有重要作用。我国生物炼制产业发展目前处于起步阶段,面临着原料、技术等问题。针对我国国情,提出了在条件适当地区,生物炼制企业建设采取生物炼制与石油炼制一体化建设的设想。以燃料乙醇项目建设为例,通过对单独建设和一体化建设两种方案的比较,从成本、未来发展和原料供应等方面分析了一体化建设的优势。研究表明生物炼制与石油炼制一体化模式将对我国能源、化工等行业的可持续性发展起到促进作用。     

Microbial desulfurization of coal and oil

Biotreatment of fossil fuels may be regarded as suitable technology for the desulfurization of oil and coal before combustion, especially for small-scale combustion plants where flue gas cleaning is too expensive.

Although several patents, especially on the field of biodesulfurization of oil, already exist, successful application in a large scale could not be demonstrated until now. “Organic sulfur” is characterized by covalent C-S bonds and can be regarded as an element which is integrated in the macromolecular matrix of coal and in organic sulfur compounds present in oil. As for the results of more semi-empirical approaches no reproducibility and transferability to other oil qualities could be demonstrated when model compounds representing the organic sulfur species were used.

This research strategy resulted in a number of promising biochemical pathways for the degradation and/or desulfurization of such compounds. However, up to now the use of microorganisms able to degrade model compounds in a biotechnological process for coal or oil desulfurization does not meet the expectations.

Thus, it has to be concluded that additional research is needed which should be focussed on the development of biocatalysts with a broad substrate specificity and on methods to improve the availability of the organically bound sulfur in the molecular structure of oil and coal.     

Effective supports to moderate H2S inhibition on cobalt and nickel molybdenum sulfide catalysts in deep desulfurization of gas oil

Deep desulfurization of gas oil was attempted in the presence of H₂S over commercially available catalysts. Hydrotreated gas oil containing 340 ppm of sulfur (ppmS) was successfully desulfurized to less than 10 ppmS under the presence of 1.67% H₂S over CoMoS and NiMoS supported on acidic supports. Such supports are believed to enhance the sulfur release from active sites and the hydrogenation of refractory sulfur species to accelerate their deep desulfurization.     

MTBE深度脱硫技术的应用

为生产满足京Ⅴ汽油含硫标准的甲基叔丁基醚(MTBE)产品,探讨了MTBE深度脱硫原理,利用MTBE脱硫体系的热力学基础数据,采用化工流程模拟与分析的方法,对MTBE脱硫过程进行了全面系统的模拟研究。通过对工艺条件的综合分析,明确了单塔、双塔两种脱硫工艺的利弊,提出了适于不同工况的可行的MTBE深度脱硫技术方案。在MTBE装置改造中取得了良好的应用效果,MTBE产品的硫含量不高于3 mg/kg。     

炼厂气回收过程中分离技术的能效分析

针对炼厂气多目标回收工艺设计时缺乏理论指导的问题,本文系统阐述了分离过程能效比的概念,将气体分离过程中压力和温度变化导致系统与外界交换的能量统一用电功表示,得到了分离过程能耗与产品回收量间关系的定量表示方法;以某厂炼厂气回收过程为例,比较了不同分离技术和不同分离过程的能效比。当产品氢纯度要求不高（≥97%）时,采用变压吸附（PSA）工艺的能效比较高（0.86）,与膜分离工艺相比,提高了28%;当产品氢纯度要求较高（≥99.9%）时,采用膜分离-PSA工艺可以获得更高的能效比（0.54）,与PSA-膜分离工艺相比,能效比提高了40%。研究结果表明：分离过程的能效比可以用于评价不同分离技术或不同分离过程的能量效率,可用于指导不同分离技术的适用范围和多技术耦合工艺过程的设计,能够为炼厂气回收工艺设计提供一定的理论指导。     

Laboratory simulated slipstream testing of novel sulfur removal processes for gasification application

The Wabash River Integrated Methanol and Power Production from Clean Coal Technologies (IMPPCCT) project is investigating an Early Entrance Coproduction Plant (EECP) concept to evaluate integrated electrical power generation and methanol production from coal and other carbonaceous feedstocks. Research, development and testing (RD&T) that is currently being conducted under the project is evaluating cost effective process systems for removing contaminants, particularly sulfur species, from the generated gas which contains mainly synthesis gas (syngas), CO₂ and steam at concentrations acceptable for the methanol synthesis catalyst. The RD&T includes laboratory testing followed by bench-scale and field testing at the SG Solutions Gasification Plant located in West Terre Haute, Indiana. Actual synthesis gas produced by the plant was utilized at system pressure and temperature for bench-scale field testing.     

炼油装置塔设备选型及现有塔设备的改造前景

在某大型燃料润滑油化工型炼油厂现有装置塔设备选型汇总基础上，探讨了塔设备的改造前景。     

Electrochemical pretreatment of heavy oil refinery wastewater using a three-dimensional electrode reactor

The pretreatment of heavy oil refinery wastewater (HORW) was experimentally investigated using a three-dimensional electrode reactor (TDER) with granular activated carbon (GAC) and porous ceramsite particle (PCP) as the combination particle electrode and DSA^® type anodes as the anode. The results showed that higher chemical oxygen demand (COD) removal was obtained in TDER comparing with the two-dimensional electrode reactor (without particle electrodes packed), and combination particle electrode was favorable to improve the COD removal efficiency and reduce the energy consumption. The treated HORW under the optimal experimental condition (GAC percentage = 75%, current density = 30 mA/cm², pH not adjusted and treatment time = 100 min) presented that the removal efficiencies of COD, total organic carbon and toxicity units were 45.5%, 43.3% and 67.2%, respectively, and the ratio of 5-day biochemical oxygen demand to COD was increased from 0.10 to 0.29, which is beneficial for further biological treatment. Furthermore, the application of electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to characterize polar compounds in HORW and their oxidation products was well demonstrated to reveal the composition variation.     

超稠油炼制污水生化处理工程设计

针对辽河石化稠油与超稠油加工污水高含油、高乳化、高CODCr、高NH3-N及高悬浮物的特点,设计了以一级水解酸化、CAST、二级水解酸化、曝气生物滤池(BAF)为核心的生化处理工艺,出水达到《辽宁省污水综合排放标准》(DB 21/1627—2008)中第二类污染物新扩改一级标准。     

Sensitivity analysis of a light gas oil deep hydrodesulfurization process via catalytic distillation

In this work, a sensitivity analysis of a light gas oil deep hydrodesulfurization catalytic distillation column is presented. The aim is to evaluate the effects of various parameters and operating conditions on the organic sulfur compound elimination by using a realistic light gas oil fraction. The hydrocarbons are modeled using pseudocompounds, while the organic sulfur compounds are modeled using model compounds, i.e., dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). These are among the most refractive sulfur compounds present in the oil fractions. A sensitivity analysis is discussed for the reflux ratio, bottom flow rate, condenser temperature, hydrogen and gas oil feed stages, catalyst loading, the reactive, stripping, and rectifying stages, feed disturbances, and multiple feeds. The results give insight into the qualitative effect of some of the operating variables and disturbances on organic sulfur elimination. In addition, they show that special attention must be given to the bottom flow rate and LGO feed rate control.     

深度脱硫吸附剂制备技术的研究进展

从不同的脱硫思路介绍了深度脱硫吸附剂的制备技术,主要包括离子交换法、单层分散法、溶胶-凝胶法、水热合成法、液-固相同晶取代法、气凝胶法、反相聚合法、酸改性法。比较了各技术制备的吸附剂的脱硫效果,为开发新的制备技术提供参考。     

炼油厂循环水塔的防腐与涂装

分析了炼油厂循环水塔的腐蚀原因,分别选择PF-01防腐涂料、聚酰胺环氧涂料和环氧玻璃钢,作为砼结构循环水塔长期受水喷淋的砼结构和钢结构以及长期浸水的砼结构的防腐涂层.讨论了循环水塔的防腐施工工艺和质量保证措施,按此方案施工的循环水塔,经过7年的使用后,防腐效果良好.