介-微孔复合分子筛的优化合成及应用

采用多次水解合并晶化结合母液循环使用的方法合成介-微孔复合分子筛AlSBA-15/HY,与常规合成方法相比,该法合成效率提高1倍,原料成本降低,减少了废酸水排放。采用浸渍法将Ni-W活性组分担载在AlSBA-15/HY载体上,制备复合分子筛加氢裂化催化剂NiW/AlSBA-15/HY。以大庆减压蜡油为原料,在200 mL一段串联加氢装置上,考察该催化剂的裂化性能。结果表明,在反应温度385 ℃、氢分压12.5 MPa、氢油体积比1 000、体积空速1.4 h-1的条件下,柴油馏分收率为52.84%,中间馏分油选择性为79.4％,重石脑油芳烃潜含量为43.5％,尾油BMCI值5.0,说明所制得的催化剂加氢裂化活性和中间馏分油选择性高,目标产品质量优。     

复合分子筛催化剂上重油加氢裂化反应研究

分别以介孔-微孔复合分子筛MCM-41/Beta和AlSBA-15/HY为载体,Ni-W为活性组分,制得两种负载型催化剂,以减压蜡油为原料考察了两种催化剂的加氢裂化性能。结果表明,NiW/MCM-41/Beta和NiW/AlSBA-15/HY都具有很高的加氢裂化活性,此外,NiW/AlSBA-15/HY还具有中间馏分油选择性高及目的产品质量优的特点,能够满足加氢裂化装置最大量生产中间馏分油的要求。     

Propane Dehydrogenation on PtSnNa/AlSBA-15 Catalyst:Influence of Tin as a Promoter

PtSnNa/AlSBA-15 catalysts with different amounts of Sn were prepared for propane dehydrogenation.The catalysts were characterized by XRF,BET,H2 chemisorption,NH3-TPD,H2-TPR,and TPO techniques.Test results indicated that the presence of tin not only modified the acid function and the interfacial character between metal and support,but also reduced the coke deposition effectively.Among these catalysts investigated thereby,the PtSn(0.7%)Na/AlSBA-15 catalyst had the best catalytic performance in terms of propane conversion and stability.With the continuous addition of Sn,more amounts of Sn0 species appeared,which was unfavorable to the reaction.The PtSn(0.7%)Na/AlSBA-15 catalyst was parametrically characterized in order to obtain necessary information to integrate the process operating conditions.A weight hourly space velocity of 3 h-1,a reaction temperature of 610 ℃ and a H2/C3H8 molar ratio of 0.25 were found to be optimum conditions for achieving a higher dehydrogenation activity of the catalyst.     

UPGRADING OF PETROLEUM RESIDUES BY VACUUM PYROLYSIS

ABSTRACT

Vacuum pyrolysis of petroleum residues which are classified as hazardous materials was performed in a batch reactor and enabled us to separate an upgraded oil from water and residual solids. Conversion of petroleum wastes to reusable oils reached 85% on an organic basis.

The pyrolysis oils and solid products were analysed for maltene, asphaltene and sulfur content. We found a significant increase in the pyrolysis oil maltene content. Much less sulfur was detected in the pyrolysis oil compared with the original organic waste material. The resin content of the pyrolysis oil decreased and the aliphatic, alicyclic and monoaromatic hydrocarbon content increased. The heavy portion of the pyrolysis oil contained approximately 5% of undesirable n-alkenes ranging from n-C₁₄ to n-C₃₈. Only trace amounts of organic and inorganic contamination was found in the solid phase leachate. The aqueous phase contained a small quantity of soluble organics which will be easily removed in a standard refinery water treatment plant. Results showed the merits of vacuum pyrolysis for upgrading petroleum residues.     

Characterization and catalytic activity of NiO/mesoporous aluminosilicate AlSBA-15 in conversion of some hydrocarbons

Mesoporous aluminosilicate AlSBA-15 was synthesized and adopted as a support for NiO with 3, 6 and 9 wt.% loadings. Characterization of various samples was performed through XRD, FTIR, DSC-TGA, TPR, SEM and TEM techniques. Textural and morphological characteristics were examined using N₂ adsorption–desorption isotherms. Catalytic activities were measured in cumene cracking for parent AlSBA-15 and in n-hexane and toluene cracking and cyclohexane dehydrogenation for supported NiO samples. Uniformity of the ordered 2D-hexagonal structure of AlSBA-15 was evident even after loading with NiO. NiO and NiOOH phases could be detected particularly in the sample containing 9 wt.% NiO. TPR profile of solid loaded with 3 wt.% NiO sample showed negative peaks at 400 and 600 °C, related to hydrogen spillover on reduced sample. Selectivity towards n-hexane and toluene cracking increased with both temperature and metal oxide loading, achieving 100% at 350 °C. In cyclohexane dehydrogenation, the sample loaded with 3 wt.% NiO was the most active and selective one towards benzene formation.     

Heavy oil upgrading: Unlocking the future fuel supply

Currently, more than half of the oil reserves (53.3%) in the world are in the form of restorable oils such as heavy oil, extra heavy oil, oil sand, tar sands, oil shale, and bitumen. Heavy oil is one of the petroleum oil varieties that contain long chain hydrocarbons. All types of heavy oils contain asphaltenes and thus are considered very dense substances. The asphaltenes are one of the most complex and heavy organic compounds present in the heavy oil. The heavy oil is defined as one having an American Petroleum Institute scale index equal or smaller than 20°. In conventional refining procedures, heavy oil poses many challenges. Recycling and re-refining are applied techniques for the processing of petroleum based heavy oils into reusable light oils such as gasoline and diesel fuel. In this regard, catalytic pyrolysis and thermal cracking are promising technologies for light oil production. The authors review the heavy oil upgrading processes and their associated challenges with ambition to find cost-effective ways to ensure a constant future fuel supply.     

STRUCTURAL CHARACTERIZATION OF PETROLEUM BASED FEEDSTOCKS FOR CARBON BLACK PRODUCTION

Some selected petroleum based feedstocks have been characterized by ¹H and ¹³C NMR spectroscopy for their possible use as carbon black feedstock (CBFS). Feedstocks studied are pyrolysis tars, clarified oils, aromatic extracts and vacuum residue. Analysis of average structural NMR parameters show that pyrolysis tars because of their being highly aromatic in character (high BMCI) are the most suitable feedstock for carbon black. Aromatic extracts rank the next. Clarified oils of Indian refinery origin needs further processing due to middle distillate mode refining severity.     

A kinetic model for pyrolysis of petroleum residue under nonisothermal conditions

Kinetic study on pyrolysis of petroleum residue was carried out by an accurate Arrhenius type equation at heating rate of 0.5–30.0°C/min under nonisothermal conditions. The influence of some critical parameters including temperature, heating rate and activation energy on mass conversion was evaluated. The apparent activation energies for during the pyrolysis process were in the range of 198–361 kJ/mol at various mass conversions of 5–94%. The reaction temperature was introduced as the most important parameter for the improvement of mass conversion, compared to that of other parameters. The pyrolysis of petroleum residue was occurred in a broad temperature range, from 150–650°C, yielding 33 wt% unpyrolyzed residue. It also was found that an increase in heating rate has a minor impact in the process. Model predictions were compared with experimental data, which showed fully good agreement.     

Kinetic study on the thermal degradation of heavy oil in presence of SBA-15 containing aluminum and cerium

In research for materials that can be applied in processing heavy oil (petroleum), this work proposes to synthesize mesoporous heterogeneous catalysts, type SBA-15, with the addition of cerium metal and aluminum. These catalysts were characterized by X-ray diffraction, scanning electron micrographs coupled to energy dispersive spectrometry, spectroscopy in the infrared region by Fourier transform, N₂ adsorption and desorption and thermal analysis-thermogravimetry. Thermal tests were performed to evaluate the thermal and catalytic degradation process with a sample of heavy oil (°API = 14). Through the non-isothermal kinetic model of Ozawa Flynn Wall (OFW) some parameters for determining the apparent activation energy of decomposition were obtained. The petroleum with 12% of Ce₅Al₅₀SBA-15 showed a catalytic activity for this material. It has been seen that there was a decrease in the Ea in model free of the order from 89.0 to 104.9 kJ mol^?1 in α = 50% ± 10%, and it was repeated from the first percentage until the last showing performance of Ce₅Al₅₀SBA-15 as a catalyst.     

油气生成过程实验研究的思考与展望

油气生成过程的研究是以热解实验为基础、动力学研究为工具、紧密结合盆地地质条件的系统研究方法。在总结现有研究成果的基础上,作者认为:1)加水热解适于模拟石油生成,限定体系热解可以很好地模拟石油与天然气生成/裂解实验体系,可进行含水热解实验;2)半封闭的幕式排烃热解设备尚待开发;3)压力对有机质成熟和生烃/原油裂解均有一定影响,但压力下二者的演化进程可能并不同步;4)以单一升温速率为基础的动力学研究将不被国内外同行认可;5)有压力的生烃、同位素演化动力学模型值得进一步研究;6)由于水的存在,除了水溶性催化剂外,大多数地质催化剂对生烃的影响可能并不显著,但对油气在储层中的裂解可能有作用;7)天然气的成分、同位素变化与聚集史密切相关,应给予足够的重视;8)无机质以及加水热解动力学研究、非烃气体生成与同位素演化的动力学具有潜在的科学研究价值。      

废弃印刷线路板热解油的分析

在固定床实验装置上进行 FR4型印刷线路板的热解,利用气相色谱-质谱、傅里叶变换红外光谱分析了热解油的组成,用氧弹式量热仪测定了热解油各馏分的热值,并初步探讨了溴化环氧树脂的热解机理。实验结果表明,FR4型印刷线路板热解产物中热解油的质量分数为18.23%。热解油由轻质馏分、重质馏分和石油蜡组成。轻质馏分中包括少量水和轻质油。轻质油的主要组分为苯酚、4-乙基苯酚、3-(1-甲基乙基)-苯酚、5-甲基-乙基苯,其他组分主要为烷基取代的苯和苯酚,还含有丙酮及少量其他含氧有机物(苯甲醚和苯并呋喃等),轻质油中溴含量较低。重质馏分和石油蜡所含官能团与轻质油基本相同。轻质油和重质馏分的低位热值分别为27 183 kJ/kg 和29 240 kJ/kg。溴化环氧树脂的热解反应存在 CH_2-O,C-C,CH-OH,C-Br 键的断裂。     

LIQUEFACTION OF CELLULOSIC WASTE V. WATER FORMATION AND EVALUATION OF PYROLYTIC CHAR AS A BY —PRODUCT OF PYROLYSIS REACTION

Liquid hydrocarbon oil and water have been produced from the liquefaction of cellulosic matter present in municipal solid wastes (MSW). Gases and residual char have also been produced as by-products resulting from the pyrolysis reaction of cellulose. Quantities of water and pyrolytic char were estimated at different conditions of the process (temperature pressure of hydrogen, carrier oil medium and concentration of boric acid). From the results obtained, it was suggested that the formation of water seems to be sensitive to the operational conditions which enhance a water-gas shift reaction (in which water molecules are consumed to produce carbon dioxide and hydrogen). Decreasing of the undesired chary by-product could be achieved by increasing the concentration of boric acid that catalyzes the liquefaction reaction. Two petroleum distillates, namely gas oil and residual fuel oil, were used as carrier media of a solid refuse. It was found that fuel oil is more efficient as a buffering medium that prevents cellulose macromolecules from a rapid and complete charing during the liquefaction process. The pyrolytic char was characterized and evaluated by means of different analytical procedures and solvent extraction using petroleum ether 40-60°C and methanol. Calorific value of the pyrolytic char was found to be 4.6 Kcal g^-1 which is quite close to that of a brown coal. Dropping point test of the extracted material by petroleum ether indicated that the extract can be utilized for producing lubricating greases via saponificattion with a salt of sodium or calcium.     

热聚法合成双环戊二烯石油树脂

采用热聚法,以乙烯裂解装置副产C5馏分分离出的双环戊二烯为原料,裂解C9馏分中140℃切割的组分为溶剂油合成了双环戊二烯(DCPD)石油树脂,考察了反应时间、恒温搅拌时间、溶剂种类、溶剂加入量等对DCPD石油树脂的影响。结果表明,制备DCPD石油树脂的最佳条件为:溶剂油质量分数50%～60%,热聚合温度240℃,恒温搅拌时间8h,老化反应时间22h。在上述条件下制备的DCPD石油树脂色相不大于8,软化点高于120℃,产品收率大于50%。     

Study on the fast pyrolysis of oil sludge by PY-GC/MS

Oil sludge is an organic solid waste produced in oilfield exploitation, transportation, and petroleum refineries. Pyrolysis is one of the most effective ways to reduce oil sludge and realize energy re-utilization. In the present work, the amounts and distributions of pyrolysis products at different reaction time and with different amounts of NiO catalyst were investigated with PY-GC/MS. The results suggest that the degree of the pyrolysis reaction increased and more macromolecules were degraded into smaller hydrocarbons as the reaction time prolonged. The addition of NiO catalyst effectively promoted the conversion of aromatic and paraffin products, and increased the production of small molecule olefins.     

Production of petroleum pitch from oil refinery residues

The possibility of obtaining petroleum pitches from heavy pyrolysis resin, the heavy distillate formed in production of pitch from heavy pyrolysis resin, and heavy catalytic gasoil is examined. The composition and physicochemical properties of the petroleum pitches obtained and the intermediate products from the process are investigated. The important possibility of obtaining isotropic fiber-forming petroleum pitches with a yield of 20–23.1 wt. % from heavy pyrolysis resin in a unit with an intermittent reactor is demonstrated.     

Catalytic distillation of an atmospheric petroleum resid using HZSM-5 and HY zeolites

This work presents a study of the reactive distillation of atmospheric petroleum residue (ATR) containing 10% in mass of HY or HZSM-5 zeolites. The process aims the upgrade of ATR in order to obtain valuable products. The fundamental characteristic of the process is the immediate separation under thermal conditions and subsequent reaction of the products generated by the zeolite catalysts, favoring the displacement of the equilibrium towards the desired reactions. Such reactions occurred in the heterogeneous form, adding the HY or HZSM-5 zeolites to the ATR charge, and heating the mixtures at temperatures in the range of 50 to 500°C. The heating promotes intense heat exchange, solid-liquid reactions, obtaining the desired products. In the reactive distillation process, in presence of the acid sites of the zeolites, the short contact time of the hydrocarbons thermally cracked at low pressures favored secondary cracking reactions, increasing the selectivity to lower weigh molecular hydrocarbons, in the range of liquid gases, naphta, gasoline, jet fuel, diesel and lubricants. The obtained results proved that catalytic or reactive distillation is a promising technology for waste recovery that is surplus to the atmospheric and vacuum distillation processes for the refineries.     

The chemical structure and the kinetics research of oil-wet oil sand from Kazakhstan during pyrolysis process

The pyrolysis experiments on the oil sands from Kazakhstan were carried out in a batch reactor. The FT-IR spectrum and the ¹H-NMR spectrum of pyrolysis oil under different temperatures were carried out to investigate the changes of functional group with temperature. The TGA experiments of oil sand were performed at different heating rates of 5, 10, 15, and 20°C/min up to 600°C. The Coats–Redfern method was accepted to calculate the kinetic parameters (apparent activation energy E and frequency factor A) of the desorption stage and the thermal cracking stage, respectively.     

Characteristic features of liquid-phase oxidation of vacuum tower bottoms in the presence of modifiers

The influence of modifiers affecting the structural organization of a petroleum system and the kinetics of oxidation of vacuum distillation bottoms have been studied. It has been shown that the introduction of modifiers into the petroleum feedstock alters the ratio of the dispersed phase to the dispersion medium, thereby affecting the rate of the oxidation process. It has been found that the main factor determining the performance of modifiers affecting the structure of the petroleum system is the modifier nature. The maximum concentration of modifiers in the vacuum tower bottoms (VTB) was 5.0 wt %. The dependence of the oxidation rate upon the duration of oxidation has been determined for the modifiers. It has been shown that brown-coal pyrolysis tar introduced into VTB has an inhibitory effect, and oil shale pyrolysis tar and a diamond blend initiate the oxidation process. For blown asphalts produced from modified and unmodified VTB, expressions relating the softening point and penetration have been obtained. The properties of different blown asphalts obtained from the feedstock modified with the test additives at optimal concentrations have been compared.     

最大反应速率法在生油岩生烃率计算中的应用

本文利用岩石评价仪对东濮凹陷埋深1801m的未成熟生油岩进行不同升温速率（2、5、10、15、20℃/min)的热解动力学模拟试验,得到热解反应速率最大时的不同温度T_max。根据这些温度值,用最大反应速率法模型进行回归,求得该生油岩的表观活化能E和指数前因子A分别为199.6KJ/mol,和2.803×10¹³sec^-1。根据这两个热解动力学参数,及东濮凹陷的沉降速率（0.26mm/y)和地温梯度（0.03℃/m),算得该凹陷不同埋深生油岩的生烃率。如埋深为2768m时,生烃率为0.05（可视为生油上限);埋深为3571m时,生烃率为0.95（可视为生烃下限);最大热解速率时埋深为3337m（可视为生油高峰值)。所得生烃率计算,较符合实际情况,可以认为,最大反应速率法模型是一种较简单可行的模拟方法,岩石评价仪是一种适宜于进行生油岩热解动力学的仪器,所得不同埋深的生烃率的计算结果对于油气资源的评价和石油的勘探开发有较大的意义。     

石油树脂催化剂脱除时出现乳化现象的处理方法

提供一种在石油树脂制备过程中催化剂脱除工序出现乳化时的处理方法。采用氧化铝固定床工艺,在温度250～260℃,压力2．3～2．5MPa,液体空速0．9-1．2h。的条件下,可以将石油树脂溶液氯含量降低到15～20wg／g,同时将乳化形成的AI（OH）,从石油树脂溶液中分离,保证了石油树脂产品的质量。