回顾中国石油炼制工业的技术进步和技术创新

半个世纪以来,中国石油炼制取得令人瞩目的进展,不仅炼油能力已跃居世界第二位,而且炼油技术也基本达到世界先进水平。在炼油技术持续进步的过程中,自主技术创新占有重要位置。系统回顾了20世纪60年代以来重要炼油技术(催化裂化、加氢裂化与加氢处理、催化重整、延迟焦化、常减压蒸馏等)的发展历程,总结了所取得的有益经验和基本体会。     

Fenton氧化法处理炼化企业二级出水的研究

通过检测·OH间接生成率与COD去除率考察了Fenton氧化法深度处理炼化企业二级出水的效果及影响因素。结果表明,采用Fenton氧化法处理炼化企业二级出水,处理后的出水各项指标均达到《城市污水再生利用工业用水水质》(GB/T 19923—2005)的要求。最佳反应参数为:H2O2投加量为4 mmol/L,FeSO4·7H2O投加量为0.5mmol/L,废水pH=4,反应时间为2 h,反应温度为50℃。     

Use of zeolites in petroleum refining and petrochemical processes: recent advances

Zeolites and molecular sieves have revolutionized oil refining and petrochemical processes with a step change in product selectivity and operation parameters. However, stringent emission norms and depleting refinery gross margins in view of volatile crude oil price and its quality has demanded search for novel zeolytic materials. Such developments are envisaged to improve existing zeolite based processes or to develop new and energy efficient processes to enhance the product yields and quality in oil refining and petrochemical processes, respectively. As a result, focused and sustained efforts have led to discovery of novel molecular sieves such as ITQ-n, EMM-n in recent time. The present paper illustrates a brief overview of such developments and is aimed to understand the applicative potential of novel molecular sieves in terms of their novel zeolite chemistry and structural-property aspects.     

石化企业挥发性有机物无组织排放监测技术进展

无组织排放占石化企业挥发性有机物（VOCs）排放的主导地位,排放点多、面广、量大、分散、无规则,总体表现为大型面源或体积源,监测难度很大。本文评述了点、线和面(通量)等VOCs无组织排放监测技术及应用进展,总结了石化企业VOCs无组织排放监测存在的主要问题与难点,提出了石化企业VOCs无组织排放监测体系及适用监测技术。总体上,石化企业VOCs无组织排放监控存在排放清单质量不高、源头监测及溯源困难、排放烟羽及其迁移扩散途径无定形、厂界等开放空间难以封闭监测、常规监测的时间和空间覆盖有限等问题或技术难点,可复合应用点、线、面及通量监测技术,结合常规离线、实时在线、排放通量、移动快速响应等监测设计,构建覆盖排放与环境影响的多元化、网络化、立体化监控体系。未来石化企业VOCs无组织排放监控将向多层级、智能化和大数据应用发展。     

Competitive reactions catalyzed by NiMo-containing zeolites

The rates of benzene hydrogenation and of n-heptane hydroconversion were measured simultaneously over a series of bifunctional catalysts. The catalysts were Y zeolites containing a Ni or Mo sulfide. At 280 °C, and for the more acidic catalysts, both rates appeared linearly correlated, suggesting that the hydrogenation function was limiting.     

Hydrogenation of aromatics under mild conditions on transition metal complexes in zeolites. A cooperative effect of molecular sieves

The hydrogenation of aromatics, i.e. benzene, toluene, -methylstyrene, anisole, and ethyl benzoate, can be carried out under a very low (1/12000) catalyst to substrate ratio, and mild reaction conditions (80°C, 6 atm of H₂O), on Rh and Ni organometallic complexes anchored on USY zeolites. A strong cooperative effect between the faujasite surface and the transition metal surface complex is thought to be responsible for the simultaneous enhancement of concentrations of arene and H₂ in the neighborhood of the catalytic centers, and for the observed electronic effects.     

Supported alkali catalysts for steam gasification of carbonaceous residues from petroleum

Steam reforming of petroleum residues was investigated at 1173 K and atmospheric pressure in a fluidized-bed flow system using a series of alumina-supported catalysts of alkali metal compounds. The catalytic activity increased with decreasing ionization potential of the catalytic alkali metals: Cs >; K >Na >Li. Catalysis was elucidated in terms of an oxygen transfer mechanism proposed for the catalysis by alkali metal compounds in graphite-or char-steam reaction.     

美国炼油业的发展动向对我国的启示

美国是世界第一大炼油国，本文分析了当前美国炼油业发展现状，指出美国炼油能力主要集中在五大区域，其中PADD3区的墨西哥湾不仅是美国也是世界最大炼油中心。2013年以来，美国炼油厂开工率一直维持在90%左右，毛利始终保持世界第一。伴随原油质量的变化和油品质量的不断升级，催化裂化、催化重整占比有所下降，加氢能力显著提高，装置结构持续优化。同时，文章总结最新发展动向，主要表现：一是得益于页岩油气革命的成功，美国原油产量、油品产量及出口量持续增长，2017年原油对外依存度降至42.07%，油品净出口量43.8万桶/日。二是为了提高行业及企业的竞争力，进一步加快落后产能淘汰及兼并重组步伐，持续推进国际化；三是更加注重整体区域化和基地化发展，特别是拥有资源、物流、市场优势的PADD3区和PADD2区；四是不断创新与升级催化裂化、加氢裂化与处理、烷基化等传统炼油技术，加大分子炼油、原油直接生产化工品、智能化炼油厂等前沿性技术的研发。本文分析认为，鉴于美国炼油业的地位和发展新态势，今后我国炼油业要实现高质量发展，应在保障国家石油安全的基础上，在国家政策的积极引导下，持续推进供给侧结构性改革，促进基地化、区域化、一体化发展，推进国际化进程，高度重视安全环保与质量升级，不断加强科技创新、苦练内功，实现炼油强国的“中国梦”。     

Physical refining of edible oils

Crude oils obtained by oilseed processing have to be refined before the consumption in order to remove undesirable accompanying substances. The traditional alkali refining is often replaced by physical refining in which the use of chemicals is reduced. The most widely used method is steam refining. The crude oil quality is very important in order to obtain high quality refined oil. Furthermore, the oil should be efficiently degummed to remove phospholipids as well as heavy metals and bleached to remove pigments. The most important step consists of the application of superheated steam under low pressure and at temperatures higher than 220 °C. Both free fatty acids and objectionable volatiles, formed by cleavage of lipid oxidation products, are removed. A disadvantage is the partial loss of tocopherols. Side reactions, particularly isomerization of polyunsaturated fatty acids, should be minimized. The quality of physically refined oil is close to that of alkali refined oils, but losses of neutral oil are lower and the environment is less polluted. Among other methods of physical refining the application of selective membranes is promising.     

元素分析仪测定石油炼制催化剂积炭含量的研究和应用

采用元素分析仪建立了一种石油炼制催化剂中积炭含量的测定方法,通过高温燃烧将催化剂中的积炭完全氧化为二氧化碳,排除干扰气体后,送入热导检测器定量检测。通过选择合适的标准物质绘制标准曲线,使得该方法适用于几乎所有的石油炼制催化剂。通过调整仪器参数,确定了最佳工作条件,得出试样量为2～20mg、通氧时间为80～140s,且针对不同积炭含量选取合适条件时效果最佳。选取不同类型的催化剂样品进行了方法对比实验,通过T检验得出两者不存在显著性差异,通过加标回收试验考察了方法的准确性。实验结果表明,本方法操作简便,测定结果准确可靠,广泛适用于各种类型的石油炼制催化剂。     

炼油与化工一体化 有效利用原油资源--从多种化学反应剖析多产石化产品途径

介绍了炼油过程中多产石油化工原料的有关工艺技术,从化学结构转化角度阐明了理论依据.由于原油特别是重油中丰富的烷基碳、环烷碳和芳碳资源均能通过一定途径转化为低碳烯碳以及芳碳,其潜在资源超过单纯依靠石脑油所能提供的数量,因而在经济合理和技术可行的原则下尽量提高其转化率成为当前炼油-化工一体化的研究热点.     

Flexibility in zeolites:29Si NMR studies of ZSM-5 frame transitions

Zeolites are most often perceived as rigid solids. Recent evidence has demonstrated that the temperature or the adsorption of molecules whose dimensions approach the pore dimensions induce changes in the solid structure, i.e., a flexing of the solid lattice. For pentacil zeolites, as ZSM-5, a transition between monoclinic and orthorhombic forms of the crystalline structure is found with a change in temperature or the adsorption of ring containing molecules. We find that the temperature at which this transition occurs depends on the Si/Al ratio within ZSM-5 and the discrete, reversible transition can be measured by²⁹Si NMR, confirming prior X-ray studies. A similar dependence is found for ZSM-11. Phosphorous modification of the ZSM-5 does not change the transition temperature; however, steam treating of the zeolite does. The implications of these measurements to the flexibility and to the potential for transport is discussed. An analogy between transport and flexibility in one-dimensional polymers and that in the three-dimensional, open, solid network of zeolites is suggested.We wish to thank Union Carbide, Mobil, Haldor Topsøe, Johannes Lercher, peter Jacobs and Mark Davis for generously providing samples for this study.     

Aldol condensation of butanal over alkali metal zeolites

Alkali metal zeolites and metal oxides were used for the aldol condensation of n-butanal to 2-ethyl-2-hexenal. The order of activity at 150 °C and 1 atm. was: CsNaY > NaY > LiNaY > MgO >Al₂O₃. Selectivity to 2-ethyl-2-hexenal was 100% for both pure and mixed isomer feed. Infrared spectroscopic studies showed that stable catalysts were produced by propene pretreatments which blocked Lewis acid sites. Adsorption of ammonia and carbon dioxide on CsNaY during aldol condensation of n-butanal causes a decrease in rate. This result, along with the order of activity, suggests that the presence of both acid and basic sites produce higher activity than strongly basic MgO.Work performed at San Jose State University.     

Toward rational design of hierarchical beta zeolites: An overview and beyond

The ever-growing need to increase the efficiency of crude oil refining raises the prospects for utilizing advanced catalytic materials to supply increasing global demands for fine chemicals and petrochemicals. Zeolites have been used as indispensable catalysts in many commercial refining processes. Among them, zeolite beta is one of the most widely produced zeolite materials with industrial significance due to its large micropores and three-dimensional pore structures. This article discusses recent progress on hierarchical beta zeolites from various synthetic strategies. Using zeolite beta as a representative case, we provide an overview on key aspects that are applicable to different zeolites via a variety of topics, such as selection of different template materials, tailoring of mesopore sizes by base leaching, organotemplate-free synthesis of hierarchical zeolites, and selective desilication. This article concludes with a perspective on the design of scalable hierarchical zeolites that are more relevant as industrial catalysts in commercial processes.     

Mesoporous zeolite single crystal catalysts: Diffusion and catalysis in hierarchical zeolites

During the last years, several new routes to produce zeolites with controlled mesoporosity have appeared. Moreover, an improved catalytic performance of the resulting mesoporous zeolites over conventional zeolites has been demonstrated in several reactions. In most cases, the mesoporous zeolites exhibit higher catalytic activity, but in some cases also improved selectivity and longer catalyst lifetime has been reported. The beneficial effects of introducing mesopores into the zeolites has in most instances been attributed to improved mass transport to and from the active sites located in the zeolite micropores. Here, we briefly discuss the most important ways of introducing mesopores into zeolites and, for the first time, we show experimentally that the presence of mesopores dramatically increases the rate of diffusion in zeolite catalysts. This is done by studying the elution of iso-butane from packed beds of conventional and mesoporous zeolite catalysts. Moreover, we discuss in detail the recent observation of improved activity and selectivity in the alkylation of benzene with ethene using mesoporous zeolite single crystal catalysts. For this reaction, we show by calculation of the Thiele modulus that this improved performance can be mainly attributed to a diffusional limitation of ethylbenzene in the zeolite pores. This is verified in new ethylbenzene dealkylation experiments where mesoporous zeolite catalysts show significantly improved activity over conventional zeolite catalysts.     

Selective isomerization of isophorone oxide over zeolites

Ring-contracted main product formed by isomerization of isophorone oxide (1) is 2-formyl-2,4,4-trimethylcyclopentanone (2); a high yield of (2) could be achieved by use of zeolites as heterogeneous catalysts. The reaction could be carried out in a discontinuous liquid-phase batch reactor as well as in a continuous vapor-phase fixed-bed reactor. The formation of (2) by decarbonylation of (2) could be reduced by increasing the catalyst loading or by carrying out the reaction under short contact time in gas phase conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

润滑油白土补充精制吸附过程

采用正交试验设计方法测定了润滑油经白土吸附后润滑油的色度与浊度,通过对正交试验结果的极差分析,得到了白土类型、用量、吸附方法、温度、吸附时间等对润滑油吸附效果影响的主次关系.正交试验结果表明白土用量和白土类型分别是影响白土吸附后润滑油的色度和浊度的主要因素.在此基础上通过单因素试验进一步研究了各参数对润滑油质量的影响规律.研究结果为白土吸附的工业生产提供了试验依据.     

Pyrolysis of petroleum asphaltene in tetralin

The pyrolysis of a petroleum asphaltene in tetralin donor solvent at 450 °C has been examined, and the products characterized by elemental, molecular weight, n.m.r. and g.c.-m.s. analysis. Degradation to mainly lower molecular weight products takes place, the residual asphaltene having a smaller average cluster size, higher aromaticity and a heteroatom content resistant to further reaction. β-bond scission is important in the early stages of reaction.     

国外石油炼制催化剂的技术进展

以国外炼油催化剂生产具有代表性的大公司推荐的新产品为例,综述了催化裂化、加氢精制、加氢处理、加氢裂化和催化重整五类石油炼制催化剂的技术发展近况,并列举了部分应用实例。同时介绍了石油炼制催化新材料研制的进展情况,并分析了其应用前景。