长庆原油不同馏分的催化裂化性能研究

在固定流化床装置上进行了长庆原油的常压渣油、脱沥青油和减压渣油的催化裂化反应,考察了反应温度对产物分布、氢转移反应及柴汽比的影响。结果表明:常压渣油的裂化性能最好,脱沥青油次之,减压渣油的裂化性能最差。相同的反应条件下,脱沥青油的转化率比减压渣油高约6百分点,总液收高20百分点以上,而焦炭产率则只有减压渣油的2/3。对不同的原料,反应温度对氢转移反应和柴汽比的影响趋势不同。减压渣油的氢转移和柴汽比受反应温度的影响较大。     

常压渣油催化裂化装置技术改造

采用新工艺、新设备对盐城市石油液化气厂５０ｋｔ／ａ常压渣油催化裂化装置进行技术改造,使装置处理能力提高到９０ｋｔ／ａ,取得了显著的经济和社会效益。     

渣油型合成氨气化原料路线改造工艺探讨

简述炼油-化肥资源整体优化化肥原料路线改造——“渣油溶剂脱沥青-脱油沥青气化-脱沥青油催化裂化组合工艺”的研究及工业应用情况。实践证明该组合工艺的应用,提高了炼油企业的原油深度加工能力,降低了化肥原料成本,改善了产品结构,提高了企业的整体经济效益。     

渣油催化裂化的技术进展

渣油的催化裂化（称为渣油FCC）是催化裂化技术进展的主要方面之一，本文将简要介绍国内外在这一方面的成熟工艺及其改进。     

溶剂脱沥青-脱油沥青气化-脱沥青油催化裂化组合工艺研究及应用

介绍了渣油溶剂脱沥青-脱油沥青气化-脱沥青油催化裂化组合工艺的研究及应用情况.该组合工艺的应用提高了企业的劣质渣油加工能力,改善了产品结构,提高了企业的经济效益.     

在ZSM—5分子筛催化剂上常二线油和常三线油的催化裂化芳构化性能的研究

本文以常二线油（220－350℃）和常三线油（350－400℃）为原料，研究了HZSM0－5和ZnZSM－5两种分子筛催化剂的催化裂化芳构化性能。结果表明：ZnZSM－5催化剂的催化芳构化性能优于HZSM－5催化剂，常三线油比常二线油更易于芳构化。实验条件下，在ZnZSM－5催化剂上常三线油的裂化芳构化反就的最佳温度为470℃，加入水蒸汽和采用低空速进料可以维持催化剂良好的催化性能。     

页岩油作催化裂化原料的研究

通过对页岩油氧化、络合,脱出原料油中的碱氮成分和降低总氮含量,从而满足页岩油进行催化裂化的进料要求。经过TYPEZD-2自动电位滴定仪和REN-1000B化学发光定氮仪对单因素试验与正交试验的检测,确定了在反应温度70℃、反应时间20min、m(氧化剂)/m(油)为0.068∶1的条件下,通过简单的试验方法和少量的试剂能够将页岩油中氮含量降低到3925.29μg/g,能够达到催化裂化进料标准,但预处理后原料油的损失尚未达到理想状态。     

上海高桥炼油厂催化裂化优化控制

介绍了相关积分法的优化控制系统在上海高桥炼渍厂2号催化裂化装置的应用状况和最新进展。     

渣油催化裂化的物理化学模型

在专门设计和建造的具有原料油液喷雾蒸发单元的下引式催化裂化中型装置内,对渣油催化裂化初期的物理和物理化学过程,如原料油的喷雾、蒸发,与催化剂的接触状态及化学反应等过程动力学进行了研究,提出了液滴群在蒸发单元中蒸发的数学模型,并编制出其计算软件,提出渣油催化裂化的物理化学模型阐明了渣油催化裂化过程初期反应条件与减少生焦率的关系。     

炼油厂催化裂化油浆的综合利用

重油催化裂化装置抽出油浆已成为当前改善催化裂化操作的有效手段,目前油浆主要作为燃料油的调合油,这种利用油浆的方式效益低,而且油浆中含有少量固体颗粒,易造成炉嘴结焦。本文从实际应用的角度出发,介绍了催化油浆在炼油方面的几种应用途径,这些方法简单易行,且灵活性大,在现有炼油装置上即可实现,科学地利用催化油浆对于提高企业的经济效益具有重要意义。     

不同基属蜡油的催化裂化性能研究

为了拓宽催化裂化原料来源并探索不同基属蜡油的催化裂化性能,选取了5种蜡油进行催化裂化实验,考察原料性质和反应温度对转化率和产物产率以及选择性的影响。结果表明:蜡油性质影响转化率和产物分布。苏丹蜡油转化率和汽油、液化气的产率最大,但是柴油的产率最低;新海焦化蜡油的转化率和汽油、液化气的产率最低,但柴油产率最高。性质相近的胜利蜡油和绥中蜡油具有相近的催化裂化性能,但新海蜡油和新海焦化蜡油的裂化性能差别较大。反应温度对5种蜡油的裂化性能影响相似,在490—520℃范围内,随着温度增加,柴油产率逐渐下降,液化气产率逐渐增加,汽油的产率先升后降。     

Production of steam cracking feedstocks by mild cracking of plastic wastes

In this work the utility of new possible petrochemical feedstocks obtained by plastic waste cracking has been studied. The cracking process of polyethylene (PE), polyethylene-polypropylene (PEPP) and polyethylene-polystyrene (PEPS) has been carried out in a pilot scale tubular reactor. In this process mild reaction parameters has been applied, with the temperature of 530 °C and the residence time of 15 min. The produced hydrocarbon fractions as light- and middle distillates were tested by using a laboratory steam cracking unit.It was concluded that the products of the mild cracking of plastic wastes could be applied as petrochemical feedstocks. Based on the analytical data it was determined that these liquid products contained in significant concentration (25-50 wt.%) of olefin hydrocarbons. Moreover the cracking of polystyrene containing raw material resulted in liquid products with significant amounts of aromatic hydrocarbons too. The steam cracking experiments proved that the products obtained by PE and PEPP cracking resulted in similar or better ethylene and propylene yields than the reference samples, however the aromatic content of PEPS products reduced the ethylene and propylene yields.     

Catalytic cracking of n-octane over zeolites with different pore structures and acidities

Catalytic cracking of n-octane has been studied over FAU, FER, MWW, MFI, BEA and MOR zeolites in order to investigate the effects of pore structure and acidity on their catalytic properties. The conversion of n-octane was largely dependent on the number of strong acid sites, while their pore structure determined the rate of catalyst deactivation due to carbon deposit. Continuous and high catalytic activity, therefore, was obtained on the MFI zeolite with sinusoidal pores and small Si/Al molar ratio, because its pores suppress the formation of large intermediate and its large number of strong acid sites accelerates the cracking of n-octane     

Studies on thermal cracking behavior of residual feedstocks in a batch reactor

Thermal cracking of residual fractions has gained interest of refiners due to increasing demand of middle distillates and at the same time decline in demand of fuel oils. The present study is an attempt to gain deeper insight into the thermal cracking behavior of residual feedstocks in terms of certain key characteristics. Laboratory scale experiments on a 400 ml capacity stainless steel batch reactor were conducted with four residual feedstocks of Indian and Middle East origin—North Gujarat short residue (NGSR), Visbreaker feed from Mathura refinery (MVBF), Bombay High short residue (BHSR) and Asphalt from Haldia refinery (HRA), with asphaltene content varying in the range 1.85-10.15 wt%. The cracked products were separated by distillation up to 500 ^°C. The distillate (500 ^°C-) was analyzed by ASTM D2887 (SIMDIST) method and obtained data were classified into lumps, namely Gas (C₅-), Gasoline (IBP-150 ^°C), Light Gas Oil (150-350 ^°C) and Vacuum Gas Oil (350-500 ^°C) prior to detailed data analysis. The analysis of results reveals that the thermal cracking of petroleum residues follows first order kinetics. The rate constants and activation energies have also been estimated.     

富集石脑油中正构烷烃,降低乙烯原料及能耗

考察了裂解原料中不同正构烷烃浓度对裂解乙烯、丙烯和丁二烯收率的影响.裂解产物中乙烯、丙烯和丁二烯收率均与裂解原料中正构烷烃的浓度在一定范围内呈现良好的线性关系.裂解烯烃收率随裂解原料中正构烷烃浓度增加而提高,但当正构烃浓度超过90%时,裂解烯烃收率随正构烃浓度增加的趋势变缓.吸附分离适宜的分离精度为生产正构烷烃含量为90%左右的脱附油作为乙烯裂解原料,吸余油作为催化重整原料或高辛烷值汽油调和组分.本文对90万吨乙烯裂解装置的原料调配方案进行了初步探讨,同时对固定床和模拟移动床两种石脑油吸附分离工艺进行了对比.     

不同模板剂合成的SAPO-34分子筛催化丁烯裂解

受下游产品的影响,丙烯需求量逐年上升,提高丙烯生产能力显得尤为重要。SAPO-34分子筛具有八元环孔道结构,在丁烯裂解中可有效提高低碳烯烃选择性,尤其是丙烯选择性。以二乙胺、四乙基氢氧化铵和二乙胺+四乙基氢氧化铵为模板剂合成SAPO-34分子筛,采用XRD、NH3-TPD和SEM等进行表征,并在固定床反应器上考察模板剂对分子筛催化性能的影响。结果表明,模板剂种类对制备的SAPO-34分子筛的晶粒大小、酸强度、酸量以及催化性能有重要影响。以四乙基氢氧化铵为模板剂合成的分子筛酸量最少,酸性最弱;以二乙胺为模板剂合成的分子筛酸量最大且酸性最强,双模板剂发挥加和效应。将SAPO-34分子筛用于丁烯裂解反应时,酸量越少,酸性越弱,丙烯收率越高,丙烯最高收率为33.61%。     

Catalytic reforming of hydrocarbon feedstocks into fuel for power generation units

The feasibility of realization of the multifuel operation principle, specifically, production of a hydrogen-containing gas from various types of hydrocarbon feedstocks using the same catalyst under similar reaction conditions is considered. The steam reforming of two types of hydrocarbon mixtures, namely diesel fuel satisfying GOST (State Standard) R 52368-2005 (EN 590:2004) and a methane-propane mixture imitating the composition of associated petroleum gas, has been investigated to clarify this issue. These hydrocarbon feedstocks were chosen for the reason that they are universally used as a fuel for various types of power generation units. Experiments have been carried out in a catalytic flow reactor at 250–480°C (for the methane-propane mixture) and 500–600°C (for diesel fuel) and pressures of 1–15 atm using a nickel-containing catalyst (NIAP-18). This catalyst has been demonstrated to ensure conversion of different types of hydrocarbon feedstocks into synthesis gas and methane-hydrogen mixtures usable as a fuel for power generation units based on high-temperature fuel cells and for spark-ignition, diesel, and gas-diesel engines.     

Catalytic deoxygenation of unsaturated renewable feedstocks for production of diesel fuel hydrocarbons

The liquid-phase deoxygenation reaction of unsaturated renewables has been investigated in a semi-batch reactor. The reactants examined were the monounsaturated fatty acid, oleic acid, the diunsaturated fatty acid, linoleic acid and the monounsaturated fatty acid ester, methyl oleate. The reactions were carried out over a Pd/C catalyst under constant pressure and temperature in the following domain, 15-27 bar and 300-360 °C, respectively. The influence of carrier gas was additionally investigated. The impact as solvent (mesitylene) was studied as well and reaction pathways were proposed. Furthermore, continuous deoxygenation experiments were conducted, facilitating understanding of the catalyst stability and catalyst deactivation. The deoxygenation catalyst was characterized by physisorption, temperature programmed desorption (TPD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM).     

Catalytic cycles for hydrocarbon cracking on zeolites

Catalytic cracking of hydrocarbons takes place via elementary reactions such as initiation processes to form carbenium ions, olefin adsorption/desorption steps, isomerization, β-scission, oligomerization, and hydride ion transfer steps. These elementary steps involving reactive carbenium ion surface intermediates are the essential components of catalytic cracking that lead to various catalytic cycles and their corresponding stoichiometric reactions. This review outlines methods used to quantify reaction kinetics for catalytic cracking and describes how the rates of specific catalytic cycles are controlled by catalyst treatment (e.g., steaming) and process conditions (e.g., conversion and temperature). This revised version was published online in June 2006 with corrections to the Cover Date.