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.     

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.     

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.     

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.     

顺酐精制技术应用新趋势

介绍了顺酐精制技术中新塔盘的工艺应用,并进行了性能评价.结果表明:CTST塔盘具有高效、节能、工艺简单、经济效益明显等优点,对顺酐恒沸脱水生产具有较大优势,并对顺酐精制技术新趋势进行简单说明.     

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.     

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.     

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.     

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.     

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。     

ZSM-5分子筛在炼油工业中的应用

介绍了ZSM-5分子筛在炼油工业中的应用,包括柴油加氢降凝、润滑油加氢脱蜡、汽油恢复辛烷值和催化裂化（FCC）汽油降烯烃。     

糠醛抽出油族组分磺酸盐的结构与性能研究

通过柱层析法将糠醛抽出油分离为极性不同的4个族组分a,b,c和d.以各个族组分为原料,发烟硫酸为磺化剂,制备各个族组分磺酸盐.用电喷雾质谱法(ESMS)表征各个族组分磺酸盐的分子质量分布,用IR,1HNMR和元素分析法表征磺酸盐的分子结构,并测定了它们的表面活性、亲水亲油平衡(HLB)值、润湿力、乳化力.结果表明,族组分b,c和d磺酸盐具有较宽的相对分子质量分布,其平均相对分子质量分别为321,339和407;族组分b和c磺酸盐分子含有1～2个芳香环,烷基侧链含有6～7个C原子,每条烷基侧链平均有2～3条支链,族组分d磺酸盐平均含有2个芳香环,烷基侧链含有12～14个C原子,每条烷基侧链平均有6～7条支链;族组分b,c和d磺酸盐均具有较好的乳化性能,族组分d磺酸盐的cmc和γcmc均较低,润湿性能较差.     

谈如何提高二次精制盐水质量

介绍了锦化化工(集团)有限责任公司提高二次精制盐水质量的成功经验,讨论了过滤系统中碳素烧结管间距、一次盐水的质量及其游离氯含量、人为操作失误和助体给料量等五大因素对二次精制盐水质量的影响,并采取了相应的措施,如调整合适的碳素烧结管间距、改走砂滤器、更换过滤器碳素管等。介绍了二次精制盐水精制系统树脂塔精制盐水的操作要素,诸如控制盐水流量最高为68m3/h、温度在(60±5)℃、pH值在9左右,控制树脂塔的压差、树脂填充量、树脂性能、仪表阀的检查情况等,从而生产出高质量的二次精制盐水,保证了离子膜电解槽的平稳、高效运行。