Pt-Re催化剂重整高温F-T合成石脑油的催化性

选用SB粉制得γ-Al₂O₃载体,采用共浸渍法制备Pt-Re催化剂,并对其进行BET、XRD、NH₃-TPD、H₂-TPR和ICP表征。以高温F-T合成石脑油为原料,在反应温度500 ℃、反应压力1.0 MPa、空速2.0 h^-1和氢油体积比1 000条件下,考察Pt-Re催化剂的重整活性及其稳定性。结果表明,Pt-Re催化剂能高效催化重整高温F-T合成石脑油,240 h重整过程中,高温F-T合成石脑油液体收率79.89%,芳烃质量分数61.60%,直链烷烃质量分数降低了28.15%,重整转化率达200.53%,研究法辛烷值提高35个单位,表明Pt-Re催化剂能有效催化重整高温F-T合成石脑油,使之转化为汽油调和组分成为可能。     

Evaluation of activity,selectivity and stability of catalysts for naphtha reforming

A method to evaluate naphtha-reforming catalysts has been developed and the equipment and its operation is described here in detail. The octane number computed by chromatographic analysis is similar to the one derived using the motor method and is proportional to the total aromatic concentration. The aromatic concentration is a quick and easy method to evaluate catalyst activity. The liquid yield and selectivity were also measured chromatographically. The efficiencies of commercial and prepared catalysts were compared by plotting octane number vs liquid yield. The catalysts were Pt/Al₃O₃-Cl and the process variables were similar to those used in industry. The feed was n-heptane or C₆-C₈ naphtha. Accelerated deactivation tests at lower pressure and hydrogen : hydrocarbon ratios were performed to study stability in shorter times.     

高稳定性甲醇自热重整制氢Zn-Cr催化剂

研制了一种甲醇自热重整制氢Zn-Cr催化剂.催化荆甲醇制氢活性高,稳定性好.可在723～923K较宽温度范围和大空速下运行.使用时无需预还原处理,完毕无需钝化处理,易于操作.避免了铜基甲醇制氢催化剂稳定性差,责金属催化剂氢选择陛低的缺点.MOR-67催化剂在1000h长时间连续运行下,催化荆活性和选择性变化不大.而且在频繁启动停工的操作下,也具有良好的稳定性,表明适合于车载甲醇重整制氢燃料电池氢源使用.     

On-stream stability enhancement of HZSM-5 based fluid catalytic cracking naphtha hydro-upgrading catalyst via magnesium modification

On-stream stability of fluid catalytic cracking (FCC) naphtha hydro-upgrading catalysts that convert olefins into high-octane isoparaffins and aromatics is crucial for guaranteeing the long-term operation of industrial units, and therefore suppressing catalyst deactivation due to coking becomes the focus of FCC naphtha hydro-upgrading process and catalyst development. Here we report a simple and novel strategy to enhance the on-stream stability of a HZSM-5 based FCC naphtha hydro-upgrading catalyst by magnesium modification. The characterization and catalytic test results showed that the incorporation of a suitable amount of MgO can adjust the ratio of Lewis acid sites to Brönsted ones and thereby significantly improve stability of the resulting catalyst.     

钾碱对烧结型烃类蒸汽转化催化剂活性及稳定性的影响

利用常压微反-色谱装置,考察了烧结型烃类蒸汽转化催化剂钾碱加入方式和加入量对活性及稳定性的影响。结果表明,钾碱以钾的复盐(KAlSiO4)形式加入为好。它虽对活性有一定的抑制作用,但加入适量的钾,在对初活性影响不太大的情况下,有利于提高活性稳定性。     

Mg改性L分子筛负载Pt重整催化剂的制备及其石脑油芳构化性能

为克服常规氧化铝型重整催化剂氯离子流失及对设备产生腐蚀等问题，通过离子交换法制备了Mg²⁺改性的L分子筛，采用浸渍法制备了不含氯离子的Pt/MgL重整催化剂，对分子筛载体进行了XRD、N₂吸附-脱附、NH₃-TPD和Py-IR等表征，并以硫含量0.50μg/mL工业精制石脑油为原料在固定床微反装置上评价了催化剂重整芳构化性能。结果表明，Mg²⁺离子交换对L分子筛的骨架结构没有破坏，Mg²⁺的存在提高了载体的酸量和酸强度，Mg²⁺改性的Pt/MgL催化剂重整芳构化性能明显提高，适当强酸性对L分子筛重整催化剂芳构化反应起到显著的促进作用。     

分子筛重整催化剂研究进展

催化重整是芳烃的主要来源,但目前所用的重整催化剂存在对直链烷烃选择性差、生产过程中需不断补氯的缺点,国内外纷纷转向分子筛重整催化剂的研究。本文概述了国内外ZSM-5重整催化剂、载铂丝光沸石、β沸石以及L型分子筛重整催化剂的研究进展,详细分析了各种分子筛重整催化剂的优缺点。着重对ZSM-5和L型分子筛重整催化剂的反应性能和芳构化反应机理进行了系统概述,并对分子筛重整催化剂的发展趋势进行了探讨。指出分子筛重整催化剂代替传统重整催化剂是重整领域发展的必然趋势,结合失活机理对分子筛进行合理改性,提高催化剂的稳定性是分子筛重整催化剂发展的关键。另外,还应开发新型分子筛用于重整催化剂中,从而加快分子筛重整催化剂的工业化进程。     

连续重整催化剂研究及应用进展

介绍主要的连续重整催化剂研发机构,综述美国环球油品公司、法国石油研究院和中国石油化工股份有限公司石油化工科学研究院在连续重整催化剂的研发及工业应用方面的进展,重点介绍不同机构催化剂的进步途径,对连续重整催化剂未来的发展方向进行推测。     

Detailed description of kinetic and reactor modeling for naphtha catalytic reforming

Kinetic and reactor modeling of catalytic reforming of naphtha is described in the present work. The development of a kinetic reforming model is reported with detail. The validation of the developed kinetic model with bench-scale isothermal reactor experiments is also carried out. The kinetic and reactor models are applied for the simulation of commercial semi-regenerative reforming unit. The effect of benzene precursors in the feed in both laboratory and commercial reactors is also simulated, and the use of the reactor model to predict other process parameters is highlighted.     

Fluidizable catalyst for methane reforming

Fluidizable catalysts are developed in this study for advancing an integral approach towards a new methane reforming process. With this end, catalysts constituted by nickel supported on -alumina, NaY, and USY were developed using the incipient wetness technique producing bulk nickel loadings in the 0–20 wt.% range. These catalysts were also tested under relevant conditions for industrial operation in a novel Riser Simulator. It was found that, for the case of ‘dry’ reforming of methane, nickel deposited in zeolites is a promising catalyst given that it allows for close control of metal dispersion–redispersion process. In fact, when this catalyst was exposed to repeated oxidation and reduction cycles, nickel dispersions remained stable at 25% for NaY zeolite and at 15% for USY zeolite. This catalyst offers, however, limited application for steam reforming of methane given the potential collapse of the zeolite structure under steam atmosphere. As an alternative and for cases where steam reforming of methane is preferred, nickel on -alumina catalyst was considered. In these cases, optimum catalytic activity was achieved with 2.5 wt.% of nickel on -alumina with 3–6% nickel dispersion.     

氧化物催化剂上石脑油催化裂解制乙烯的研究

使用固定流化床,考察了氧化物催化剂催化裂解石脑油制乙烯的反应。研究结果表明,温度、空速和水油比对裂解产物分布有直接影响。在反应温度700 ℃、空速0.75 h^－1和水油质量比3∶1条件下,得到最大的乙烯收率为32.93%。     

Methane steam reforming in large pore catalyst

In this work we have studied the performance of catalyst extrudates of Ni-Al₂O₃ promoted with potassium for steam methane reforming. The most interesting property of this catalyst is the presence of large pores (average diameter of 8×10^?4 m) to reduce diffusional limitations. We have determined the true kinetics using catalyst powder in the temperature range covering 757–804 K. Furthermore, experiments using a fixed bed filled with extrudates were performed in the temperature range covering 701–800 K at constant methane/steam ratio for different feed flowrates.In the true kinetic experiments using catalyst powder it was observed that this catalyst has a very high CO₂ selectivity against CO. The conversion of the catalyst is smaller than other commercial materials due to the smaller content of Ni (10%).Experiments using catalyst extrudates showed that the reaction suffers from strong mass and heat limitations: diffusion of reactants/products and heat transfer in the gas/solid interface. The presence of large pores has an important contribution in decreasing the resistance to mass transfer in particles with 1.1×10^?2 m diameter. At 800 K and 2 bar the effectiveness factor was about 0.43 for the steam methane reforming reaction and 0.41 for the global reaction.     

煤基石脑油半再生催化重整制芳烃的工艺

采用工业铂铼双金属重整催化剂Pt-Re/γ-Al₂O₃开展了煤基石脑油半再生固定床催化重整单因素实验,并采用响应面法对工艺参数进行了优化与分析,最后对优化工艺条件下实验产物进行了分析。结果表明：加权平均入口温度（WAIT）、压力（P）、液时空速（LHSV）等操作条件对煤基石脑油芳烃型半再生重整产品质量、芳烃收率和C₅₊液体收率有很大的影响。煤基石脑油重整合适工艺参数区间：WAIT（500~520℃）、P（1.2~1.6MPa）和LHSV（2.0~3.0h^-1）;最佳工艺条件：WAIT为516℃,P为1.4MPa,LHSV为2.3h^-1。优化工艺条件下芳烃收率达到了79.81%,响应面实验操作条件区间内,WAIT、P和LHSV对芳烃收率影响大小顺序为：P > LHSV > WAIT。相比于石油基石脑油重整,煤基石脑油重整不仅纯氢产率和氢气纯度更高,还可获得更高的苯-甲苯-二甲苯（BTX）产率,其中苯收率：甲苯收率：二甲苯收率近似为1：3：2。     

DZAs-1石脑油加氢脱砷剂的研制和工业应用

介绍了DZAs-1加氢脱砷剂的实验室研制和工业应用情况,并对脱砷剂的脱砷活性和容砷性能进行了实验室评价。研制的脱砷剂在炼油厂石脑油脱砷装置中首次工业应用结果表明,其脱砷效果良好,工业应用获得成功。     

Prediction of surface tension of naphtha reformate using UNIFAC

The surface tension of naphtha reformate cuts (60?170°C) were predicted using a modified UNIFAC group contribution method. The naphtha was distilled into eleven cuts of 10°C intervals to obtain narrow boiling range cuts. The surface tensions were determined in the temperature range 10?50°C and were compared with predicted values. A standard deviation of 5.9% was found using this method, versus 3.7% when the corresponding states method was used over the temperature range of 60?170°C. However, for the higher temperature range of 140?170°C, this method gave a standard deviation of 2.9% versus 7.6% for the other method.     

基于混合遗传算法的催化重整过程多目标优化

为实现催化重整过程生产指标的综合优化,基于已实现工业应用的催化重整17集总反应动力学模型和催化重整过程机理模型,考虑相应的多种约束条件,建立了以最大化总芳烃收率和最小化重芳烃收率为目标的多目标操作优化模型。提出了一种将遗传算法与局部优化方法相结合的多目标混合遗传算法HNAGA,并用于多目标操作优化模型的求解。现场工业数据的仿真研究表明,HNAGA在寻找Pareto最优解前沿方面比原遗传算法具有一定的优越性。将该多目标优化模型和求解方法应用于工业催化重整装置的操作优化,可以有效提高决策的准确性。     

On the deactivation of bimetallic reforming catalyst

Highly dispersed bimetallic catalysts in reforming are known to present scientific challenges. In this context, it has been recently demonstrated (Jothimurugesan and co-workers, 1985a) that modern techniques which have been derived from Proton Induced X-ray Emission (PIXE) and Rutherford Backscattering Spectrometry (RBS) offered a much wider prospect of obtaining structural effects in dispersed bimetallic catalysts.In this investigation, PIXE and RBS (together with electron microscopy) are used to study the function of sulfur on Pt-Re-Al₂O₃ catalyst performance. It is found that the sulfur is bound to platinum.     

Modeling of naphtha reforming unit applying detailed description of kinetic in continuous catalytic regeneration process

Naphtha reforming is one of the most important processes in refineries in which high value-added reformate for gasoline pool and aromatics such as benzene, toluene, and xylene are produced. It is necessary to establish new naphtha reforming units and develop the traditional units to increase the efficiency of the processes. In this study, according to the recent progresses in the naphtha reforming technology, mathematical modeling of this process in continuous catalyst regeneration mode of operation is accomplished in two dimensions (radial and axial) by considering cross flow pattern. In addition, a new catalyst deactivation model has been proposed and a new reaction network model based on 32 pseudo-components with 84 reactions is investigated. Then, this model has been validated by comparing with industrial data, and its results have acceptable agreement.     

负载型骨架镍催化剂催化轻质石脑油加氢脱苯

针对当前对溶剂油中苯含量的严格要求,研究负载型骨架镍催化剂在轻质石脑油加氢脱苯反应过程中的加氢性能,并考察反应温度、反应压力、空速以及氢油体积比等对轻质石脑油加氢脱苯反应的影响。结果表明,骨架镍催化剂具有较高的低温加氢活性,适宜条件为:反应温度140℃,反应压力0.2 MPa,空速2 h~(-1),氢油体积比120,此条件下,苯转化率达到99%。     

掺炼焦化汽油的重整预加氢催化剂研究

掺炼焦化汽油是扩大重整装置原料的重要途径之一。针对焦化汽油的特点,采用镁铝水滑石对氧化铝载体进行改性,一方面提高其比表面积和孔容从而提高其加氢活性;另一方面降低氧化铝载体酸含量,从而降低焦化汽油中不饱和烃类结焦的倾向。浸渍液中添加柠檬酸作为分散剂以提高金属组分在浸渍液中的分散性,通过添加硝酸调整pH值至1.5促进浸渍液中的金属组分与载体结合以提高其分散性。将自制催化剂与参比剂进行对比,自制催化剂的金属成本低于参比剂,且通过对掺炼焦化汽油的油品进行预加氢试验发现在低温度(280℃)、低氢油比(100)和低压力(2.5MPa)的工艺条件下,自制催化剂的活性优于参比剂。通过1 000 h的稳定性实验发现,自制催化剂的加氢活性仍具有较高的稳定性和活性,产物均能满足工业要求。