FCC汽油加氢改质催化剂及改质工艺

研究开发出了适于FCC汽油加氢改质的选择性加氢脱硫催化剂和辛烷值恢复催化剂,并在300 mL绝热装置上,分别以全馏分FCC汽油或切割后的重馏分FCC汽油为原料,进行了FCC汽油加氢改质工艺的系统研究,结果表明：单独采用辛烷值恢复工艺或辛烷值恢复-选择性加氢脱硫组合工艺不能完全满足FCC汽油加氢改质的要求;而单独采用选择性加氢脱硫工艺或选择性加氢脱硫-辛烷值恢复组合工艺可以满足全馏分FCC汽油或切割后重馏分FCC汽油加氢改质的要求。将全馏分FCC汽油切割后进行加氢改质可以得到硫含量更低的改质产品或直接生产符合国Ⅳ标准的清洁汽油。     

FCC汽油脱硫技术新进展

综述了FCC汽油不同脱硫技术现状和发展趋势,着重介绍了FCC汽油选择性加氢脱硫和加氢处理／辛烷值恢复技术。对选择性加氢技术与加氢处理／辛烷值恢复技术的差异、应用条件和工艺以及其他脱硫技术等也进行了讨论。     

催化裂化汽油加氢脱硫技术研究

介绍了国内外典型的选择性加氢脱硫技术和具有辛烷值恢复功能的非选择性加氢脱硫技术的研究进展和工艺特点,并概述了目前工业上常用的FCC汽油加氢脱硫催化剂的基本情况。对FCC汽油加氢脱硫技术的发展趋势进行了预测。     

循环氢脱H2S对催化汽油加氢脱硫效果的影响

中国石油大学(北京)与中国石油石化研究院联合开发了催化裂化(FCC)汽油选择性加氢脱硫-辛烷值恢复工艺(GARDES工艺),于2010年在中国石油大连石化公司20万t/a全馏分FCC汽油加氢装置进行了工业试验,重点比较分析了增加循环氢脱H2S措施对产品汽油脱硫率的影响:在保持产品汽油辛烷值损失不大于1个单位的前提下,脱...     

FCC汽油加氢脱硫工艺研究进展

为了应对日趋严峻的环境问题,对汽油硫含量的要求越来越严格,而加氢脱硫技术是目前降低汽油硫含量最切实可行和最为有效的手段.综述了国内外有关FCC汽油加氢脱硫工艺的研究进展.现有的FCC汽油加氢脱硫工艺主要有两条技术路线:一是深度加氢脱硫后再恢复辛烷值(如Oct-Gain和Isal);二是选择性加氢脱硫(如Prime-C+...     

催化裂化汽油加氢精制技术研究

加氢脱硫降烯烃技术在FCC汽油加氢脱硫及烯烃饱和的同时,很好地减少汽油辛烷值损失问题。介绍了采用HDDO-01催化剂与HDDO-02催化剂组合工艺,对催化裂化汽油进行加氢处理,w（硫）〈50μg/g,汽油辛烷值损失〈2。     

全馏分催化汽油加氢脱硫降烯烃技术研究

加氢脱硫降烯烃技术在FCC汽油加氢脱硫及烯烃饱和的同时,很好地减少汽油辛烷值损失问题。介绍了采用HDDO-01催化剂与HDDO-02催化剂组合工艺,对催化裂化氢油进行加氢处理,硫质量分数达到50μg·g-1以下,汽油辛烷值损失<2。     

载体对FCC汽油加氢脱硫催化剂性能的影响

主要介绍了载体的种类及性能对FCC汽油加氢脱硫效果的影响。指出在制备FCC汽油加氢脱硫催化剂时,应选择具有适当酸碱度的物质作为载体,保证催化剂具有较高的加氢脱硫／加氢选择性,从而使脱硫后的FCC汽油满足低硫含量高辛烷值的要求。     

催化裂化汽油加氢及反应吸附脱硫进展

介绍了具有代表性的选择性和结合辛烷值恢复的催化裂化（FCC）汽油精制脱硫加氢工艺。而加氢工艺中的结合辛烷值恢复的加氢工艺更适合我国国情,并提出以辛烷值恢复技术中的异构化和芳构化为主线．研制脱硫能力强和辛烷值保持能力高的脱硫催化剂．适度增强催化剂的酸位疏通孔道,提高其芳构化活性及稳定性。针对反应吸附脱硫工艺,通过寻找硫容量高、吸附性能强的新材料、深度研究脱硫反应机理、简化工艺流程来开展脱硫效果更好、汽油辛烷值维持高的反应吸附脱硫工艺。     

OCT-M FCC汽油选择性加氢脱硫技术的开发和工业应用

开发了OCT-M FCC汽油选择性加氢脱硫技术,在压力1.6～3.0 MPa、温度260～280 ℃、空速2.0～6.0 h^－1、氢油体积比300～500的条件下,对国内外FCC汽油进行选择性加氢处理, 加氢脱硫率为85％～90％,烯烃体积分数降低7.0～13.0个百分点,研究法辛烷值RON损失小于2.0个单位,RON和MON 平均损失小于1.5个单位,汽油收率大于98.0%。     

Science and technology of novel processes for deep desulfurization of oil refinery streams: a review

Oil refinery related catalysis, particularly hydrodesulfurization (HDS) processes, is viewed as a mature technology and it is often stated that break-throughs are not to be expected. Although this could be a justified compliment to those who developed this area, at the same time it could also stifle potential new ideas.The applicability and perspectives of various desulfurization technologies are evaluated taking into account the requirements of the produced fuels. The progress achieved during recent years in catalysis-based HDS technologies (synthesis of improved catalysts, advanced reactor design, combination of distillation and HDS) and in ‘non-HDS’ processes of sulfur removal (alkylation, extraction, precipitation, oxidation, and adsorption) is illustrated through a number of examples.The discussed technologies of sulfur removal from the refinery streams lead to a wealth of research topics. Only an integrated approach (catalyst selection, reactor design, process configuration) will lead to novel, efficient desulfurization processes producing fuels with zero sulfur emissions.     

Control of hydrodesulfurization and hydrodearomatization properties over bimetallic Pd-Pt catalysts supported on Yb-modifed USY zeolite

Increasingly stringent regulations on the removal of aromatic and sulfur compounds in diesel fuel require the development of new catalysts and processes. Here, control of hydrodesulfurization (HDS) and hydrodearomatization (HDA) properties was studied by preparing bimetallic Pd-Pt catalysts supported on ytterbium-modified ultrastable Y (USY) zeolite by impregnation and subsequent calcination under different temperatures. Catalytic performances of the prepared catalysts, such as HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT) and HDA of tetralin, were investigated in a high-pressure continuous-flow reactor. With changing calcination temperature, the HDS activity is only slightly affected, although the maximum HDS conversion was obtained at 300°C. In contrast, the HDA activity decreased significantly, with hydrogenation selectivity remaining relatively constant as confirmed by the weak variation of the trans-decalin to cis-decalin ratio. A low calcination temperature of 200°C simultaneously favored both deep HDS and deep HDA, whereas a high calcination temperature of 500°C favored selective HDS reactions with minimal HDA reactions (i.e. saving of expensive hydrogen). These results clearly indicate that the selectivity of HDS to HDA can be controlled by simply changing the calcination temperature of Pd-Pt/Yb/USY zeolite catalysts.     

The chemical nature of asphaltenes from some coal liquefaction processes

Average chemical structures of asphaltenes from three coal liquefaction processes, namely hydroliquefaction (SRC-II), hydrogen-donor solvent extraction (HDS) and supercritical gas extraction (SCG), have been deduced using a structural analysis scheme in which data from ¹H and ¹³C NMR are combined with those from elemental, molecular weight and functional group analyses. Compared with SRC-II and HDS asphaltenes, SCG asphaltenes contain less-condensed aromatic nuclei which can be largely represented by 1- and 2-ring structures. They also contain more oxygen groups and slightly larger aliphatic substituents. CH₃ accounts for between 30 and 40% of the aliphatic carbon in all the asphaltenes investigated. Small amounts of long alkyl chains are present in the SCG asphaltenes but not in the SRC-II and HDS asphaltenes. SCG extraction is chemically less severe than the SRC process and HDS extraction since neither hydrogen nor HDS are employed and, as a result, SCG extracts are considered to be much more representative of the organic matter in the parent coals.     

炼油厂产品深度脱硫工艺的研究进展

综述了国内外开发和应用的脱硫技术,通过一系列实例阐述了近年来催化加氢脱硫及非加氢脱硫的工艺进展。该技术主要有催化加氢脱硫（改进催化剂的合成、先进的反应器设计、蒸馏与加氢脱硫组合等）及非加氢脱硫技术（烷基化脱硫、溶剂萃取脱硫、沉淀脱硫、吸附脱硫、氧化脱硫和膜分离脱硫等）;评述了催化加氢脱硫、烷基化脱硫、吸附脱硫和氧化脱硫等脱硫技术的特点和研究应用前景。     

焦炉气加氢催化剂及净化工艺的开发

介绍了适合于焦炉气加氢催化剂及净化工艺的研究实验结果,实验表明,JT-1及JT-8型加氢催化剂均可适用于含高浓度CO和CO2气氛下原料气的加氢净化,且净化度高,副反应小,并满足以焦炉气为原料的甲醇厂的原料净化要求,可将原料气中硫化物脱除至总硫体积分数<0.1×10-6。     

放射性35S同位素示踪技术在加氢脱硫反应研究中的应用

过渡金属硫化物催化剂广泛应用于石油炼制催化加氢过程。催化剂活性相的结构与加氢脱硫性能的关系一直是催化研究的热点。放射性³⁵S同位素示踪技术由于能够在线分析硫化态催化剂上硫的性能而备受关注。综述了放射性³⁵S示踪技术在辅助研究加氢脱硫催化剂预硫化过程、加氢脱硫反应机理及催化剂上硫的性能中的应用。     

On the hydrodesulfurization of FCC gasoline: a review

The possible origins of sulfur impurities in FCC gasoline are reviewed and discussed. Their mechanism of formation during the FCC process as well as their mechanism of transformation on hydrotreating catalysts are also examined.The article focuses on the desulfurization of FCC gasoline by means of catalytic processes considering the fact that deep desulfurization must be achieved (in accordance with new regulations) while preserving octane rating of the fraction. The various parameters (presence of a promoter, nature and modification of the support, additives and poisons) which may influence the selectivity in hydrodesulfurization (HDS) versus olefin hydrogenation are also discussed. Existing and potential processes for the HDS of FCC gasoline with octane preservation are described.     

CO2 sequestration using principles of shell formation

Biomimetic sequestration of carbon dioxide (CO₂) is one of the methods proposed to reduce the CO₂ released into the atmosphere. In this study, we compared soluble protein of hemocyte from diseased shell (HDS) and extrapallial fluid (EPF) extracted from Crassostrea gigas with bovine carbonic anhydrase II in terms of their ability to promote CO₂ hydration and the production of calcium precipitates. On the basis of the experiments of CO₂ hydration, the key role of HDS was identified. Moreover, mass‐spectroscopic analysis (MALDI‐TOF) and circular dichroism (CD) analysis were used for understanding molecular weight and secondary protein structure. From the amino acid sequence and secondary protein structure, the different processes of CO₂ hydration by bovine carbonic anhydrase II and HDS could be assessed.     

A unique way to make ultra low sulfur diesel

SK Corporation has developed a new process, SK HDS Pretreatment process that enables the refiners to produce economically ultra-low-sulfur-diesel of below 10 ppm. This technology is based on the adsorptive removal of nitrogen containing compounds (NCC) from the feedstock to conventional hydrodesulfurization (HDS) units. The NCC is known to interfere with the activity of HDS catalysts. In the SK HDS Pretreatment Process, the feedstock to the HDS unit is pretreated, and 90% or more of NCC in the feedstock is removed, resulting in higher desulfurization in a conventional HDS unit. It was found that the degree of improvement in HDS is proportional to the degree of NCC removal. SK HDS Pretreatment Process is a cost-effective method for refineries to choose for 10 ppm ULSD production. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.