煤加氢液化制取芳烃可能性探讨及当前进展

从煤的结构特点、液化机理等方面,对煤加氢液化制取芳烃,进行了可行性探讨,并简述了其当前的发展状况。     

煤直接液化粗油提质加工工艺研究现状

分析对比了煤直接液化油的汽油和柴油馏分与石油基汽油和柴油馏分杂原子含量和族组分的差异,指出煤直接液化油中氮和芳烃含量高,需要经过苛刻的加工改质,才能作为车用内燃机燃料使用。介绍了煤液化粗油提质加工的研究现状,讨论了油品加氢催化剂和不同馏分产物的加氢提质工艺,展望了该工艺的发展趋势。     

由苏联褐煤液化油制取运输燃料

煤直接液化的主要目的是由煤制取合成原油,增加石油替代资源,并且用石油炼制工艺技术,生产优质汽油、喷气燃料、柴油和芳香烃化工原料。煤直接液化制取的合成原油与石油的物理和化学性质有较大的差异,煤液化油特点是:     

油煤浆中溶剂的黏度与油煤浆黏度关系的研究

安庆芳烃萃取油是理想的煤液化起始溶剂的原料,常压,100℃以下用德国Haake旋转黏度仪测定了不同加氢次数安庆芳烃萃取油的黏度,神华煤液化循环溶剂的黏度及其相对应的干煤浓度为45%的煤浆黏度变化,提供了油煤浆中溶剂的黏度与油煤浆黏度关系的一种方法。     

煤直接液化低分油加氢脱硫脱氮反应动力学研究

为了进一步了解煤直接液化油中硫氮化合物的形态和性质,采用石油研究中的先进分析手段GC-PFPD和GC-NCD,对煤直接液化低分油进行了分析,获得了详细的硫氮化合物组成含量。结果发现:煤直接液化低分油中含有大量的杂环化合物,S主要以苯并噻吩类和二苯并噻吩类化合物存在,N主要以五元环化合物形式存在。在高压釜中进行了催化剂添加量和不同温度条件下的加氢实验,对总硫总氮的加氢反应动力学进行了研究。通过计算得到了高压釜煤液化油加氢脱硫反应的一级反应动力学模型,且通过模型计算的S含量与反应实测的S含量相对误差仅为7.8%;对实验得到的震荡式高压釜中煤液化油加氢脱氮反应的一级反应动力学模型进行验证,发现相对误差也仅为0.97%。     

神府煤液化油石脑油馏分重整生产芳烃的研究

由于煤液化油石脑油馏分(200℃)中芳烃潜含量较高,利用煤液化油石脑油馏分为原料,进行加氢精制,将原料中的硫氮含量降至1 mg/kg左右,满足重整进料要求,然后在小型固定床连续反应器上进行加氢重整生产芳烃试验。着重考察重整反应前、后族组成的变化及主要芳烃化合物的产率。结果表明,加氢重整过程中发生正构烷烃异构化反应;环烷烃主要发生脱氢芳构化反应转化为芳香烃;煤液化油石脑油馏分适宜进行催化重整,C_1~C_4烃气产率6.03%,氢气产率3.60%;重整后,芳烃含量达83.20%,其中C_6~C_8芳烃含量61.03%,是提取BTX的良好原料。石脑油的馏程对芳烃的组成和产率有一定影响,适宜的馏程为60~160℃。     

煤与重质油共处理制取液体燃料的研究现状简介

本文简要叙述了国内外在煤与石油基重质油共处理制取液体燃料方面的研究状况.指出煤油共处理工艺结合了传统的煤直接液化工艺和重油加氢裂解工艺的特点,有可能成为第三代煤液化新工艺,为煤的转化利用提供一条新的合理途径.     

煤炭直接液化技术研究

我国煤炭直接液化技术研究已达到国际先进水平．兖州、天祝、神府烟煤和先锋．沈北、东胜褐煤都是较好的直接液化原料煤。煤直接液化的馏分油最适宜生产高辛烷值汽油、优质喷气燃料和催化重整制取芳烃原料油．两段催化液化由1t无水无灰煤生产5bb1馏分油．煤油共炼与直接液化相比较，简化了工艺过程，改进了馏分油产率和质量。我国煤直接工艺发展方向是煤油共炼或两段催化液化工艺。     

由煤制取芳烃化合物的研究进展

综述了国内外由煤制取芳烃化合物的三种思路：一是通过将煤直接进行液化获取,或者先将煤液化再从产物中获得芳烃化合物;二是先对煤进行溶剂抽提,然后对产物分类加工制取芳烃化合物;三是将煤进行氧化处理来获得高价值的芳烃化合物。分析了由煤制取芳烃化合物的所面临的产物分离困难、污染环境等问题,并指出了今后需要在分离工艺和催化剂以及如何实现煤的定向转化等方面进行重点研究。     

煤炭直接液化溶剂的研究

讨论了煤炭直接液化过程中溶剂的特点、作用及质量要求,煤液化溶剂具有一般溶剂的功能,同时还具有良好的供氢和传递氢的功能特点,起到溶解、分隔煤裂解生成的自由基的作用,溶剂必须具有一定的分子结构和分子大小。初步讨论了表征煤液化循环溶剂供氢性的指标,指出普通溶剂如四氢萘和二氢萘等部分饱和的芳香化合物可直接用作煤液化溶剂,多环芳烃含量较高的煤焦油和石油系重质油,经过预加氢处理提高溶剂的供氢性后,可作为煤液化过程的起始溶剂或替代溶剂。     

两种煤气甲烷化反应器的模拟和比较

建立了耐硫甲烷化外冷列管式反应器的拟均相二维模型和外循环式反应器的拟均相一维模型，考察了设备参数和操作条件对反应床层的影响．从反应工程角度考虑，外冷列管式反应器优于外循环式：外冷列管式反应器在近于等温条件下进行；外循环式反应器存在大量产品气的返混，降低了有效气（CO和H2）含量．     

Sorption enhanced hydrogen production by steam methane reforming using Li2ZrO3 as sorbent: Sorption kinetics and reactor simulation

The kinetics of CO₂ sorption on a solid adsorbent, namely lithium zirconate, have been studied in an oscillating microbalance. The solid sorbent has been prepared by a novel route resulting in a high capacity, good stability and much improved sorption rates, making it suitable for its application in sorption enhanced hydrogen production by steam methane reforming. A kinetic equation for the sorption kinetics as a function of CO₂ partial pressure and temperature has been developed. The hydrogen production by sorption enhanced reaction process has been simulated by a dynamic one-dimensional pseudo-homogenous model of a fixed-bed reactor, where a hydrotalcite-derived Ni catalyst has been used as steam reforming catalysts. Simulation results show that hydrogen purer than 95% with a concentration of carbon monoxide lower than 0.2 mol% can be produced in a single step.     

Kinetics of combined noncatalytic and catalytic hydrolysis of jute fiber under ultrasonic–far infrared energy synergy

Hydrolysis of pretreated waste jute fiber was intensified for maximizing reducing sugar (RS) yield deploying a novel reactor equipped with ultrasonic–far-infrared-waves (US–FIRW). At optimal 70°C temperature, 2.5 wt% Amberlyst-15 catalyst concentration, 15 min hydrolysis time and 10 (wt/wt) water loading; US–FIRW rendered significantly greater RS yield (74.82 mol%) compared to other reactors provided with far-infrared-wave (69.63 mol%), ultrasonication (50.34 mol%), and conventional thermal system (48.16 mol%). Kinetic models were developed considering noncatalytic-pseudo-homogenous (NCPH) in addition to the combined catalytic-pseudo-homogeneous (CPH) and catalytic heterogeneous (CHE) hydrolysis pathways. The results revealed that pseudo-homogenous–heterogeneous Eley–Rideal (PHHER) model could represent the hydrolysis kinetics most accurately. Remarkably, the lowest activation energy [16.75 kJ mol⁻¹ (NCPH), 13.82 kJ mol⁻¹ (CPH), 40.01 kJ mol⁻¹ (CHE)] required in US–FIRW evidently established its greater energy-efficiency among investigated reactors. The novel reactor and the simulated kinetic models can be applicable to other lignocellulosic biomass conversion for sustainable biorefinery.     

Dynamic optimization of membrane dual-type methanol reactor in the presence of catalyst deactivation using genetic algorithm

This paper presents a study on optimization of a membrane dual-type methanol reactor in the presence of catalyst deactivation. A theoretical investigation has been performed in order to evaluate the optimal operating conditions and enhancement of methanol production in a membrane dual-type methanol reactor. A mathematical heterogeneous model has been used to simulate and compare the membrane dual-type methanol reactor with conventional methanol reactor. An auto-thermal dual-type methanol reactor is a shell and tube heat exchanger reactor which the first reactor is cooled with cooling water and the second one is cooled with synthesis gas. In a membrane dual-type reactor the wall of the tubes in the gas-cooled reactor is covered with a pd–Ag membrane, which is only hydrogen-permselective. The simulation results have been shown that there are optimum values of reacting gas and coolants temperatures to maximize the overall methanol production. Here, genetic algorithms have been used as powerful methods for optimization of complex problems. In this study, the optimization of the reactor has been investigated in two approaches. In the first approach, the optimal temperature profile along the reactor has been studied and then a stepwise approach has been followed to determine the optimal profiles for saturated water and gas temperatures in three steps during the time of operations to maximize the methanol production rate. The optimization methods have enhanced 5.14% and 5.95% additional yield throughout 4 years of catalyst lifetime for first and second optimization approaches, respectively.     

A numerical study on the effects of acidic catalyst on the polymerization of nylon-6

The effects of acetic acid on the polymerization characteristics of nylon-6 are investigated in a reactor model that consists of a continuous flow stirred tank reactor (CSTR) and a tubular reactor connected in series. Mathematical models for the CSTR and the tubular reactor have been established and solved by numerical methods. In the CSTR, the monomer conversion and the molecular weights are increased as the feed acetic acid concentration is increased. In the tubular reactor, the acid acts as both a catalyst and a modifier for the polymerization reaction. The effects of the feed acetic acid content on the zeroth, first and second moments and the polydispersity index of the polymer have been discussed.     

SCALE-UP OF HOLLOW FIBER REACTOR SYSTEMS

Hollow fiber reactors have been developed for many biochemical and biomedical applications. In the study of these reactor systems, we have used single fiber reactors as a prototype for the larger hollow fiber cartridges. Experiments using single fibers have been conducted to obtain conversion data for reactor scale-up. We present a model for predicting conversions in bench-scale hollow fiber cartridges using these single fiber data. The model is compared to experimental conversion data and is shown to be a valuable design tool.     

Experimental investigation and modeling of the dissolution of polymers and filled polymers

Dissolution of Polymers is important in various areas, including microlithography, controlled drug and herbicide/fertilizer delivery, and recycling. The dissolution rates of an oxetane polymer in ethyl acetate were obtained and well correlated with a quasi-stationary dissolution model. Equilibrium solubility values obtained from the mathematical model on the basis of the best fit to the dissolution data were found to be in good agreement with equilibrium solubilities obtained in independent experiments. Mass transfer coefficients were also obtained from the mathematical model on the basis of the best fit, and the calculated activation energies were typical for diffusion controlled dissolution. The dissolution of highly filled polymers in various solvents was also investigated using the oxetane polymer filled with ammonium sulfate and aluminum fillers. The dissolution rates for the highly filled polymer were well correlated with a pseudo-homogenous diffusion model.     

Mathematical modeling for chemical vapor deposition in a single-wafer reactor: Application to low-pressure deposition of Tungsten

A mathematical model for low pressure chemical vapor deposition in a single-wafer reactor in stagnation point flow has been developed to investigate the reactor performance. The transient transport equations for a simulated reactor include continuity, momentum, energy, and gaseous species balances. The model equations are simultaneously solved by using a numerical technique of orthogonal collocation on finite element method. Simulation studies have been performed to gain an understanding of tungsten low pressure chemical vapor deposition process. The model is then used to optimize the deposition rate and uniformity on a wafer, and the effects of operating conditions on deposition rate are studied to examine how system responses are affected by changes in process parameters. Deposition rate and uniformity calculated at the steady state are observed to be very sensitive to both temperature and total pressure. In addition, the model predictions for tungsten deposition from hydrogen reduction of tungsten hexafluoride have been compared with available experimental data in order to demonstrate the validity of the model.     

The electrochemical recovery of iron in a two-compartment batch electrochemical reactor

A model has been developed for a two-compartment batch electrochemical reactor in which simultaneous iron deposition and hydrogen evolution occur at the cathode, the anodic reaction being the production of hydrogen ions. The model incorporates ionic diffusivities through the diaphragm and a composite kinetic parameter for the cathodic reactions. In order to apply the model to data from a small batch reactor, the diffusivities have been obtained under conditions in which hydrogen alone is evolved at the cathode. The value of the kinetic parameter has been chosen to provide the best agreement between the model predictions and the experimental results. Satisfactory predictions of the current efficiency for iron deposition and the final concentrations in the reactor has been obtained, the largest discrepancies between predicted and actual concentrations being at high anolyte hydrogen ion concentrations. Reasons for these discrepancies are discussed.     

A novel slurry bubble column membrane reactor concept for Fischer–Tropsch synthesis in GTL technology

Fischer–Tropsch synthesis (FTS) plays an important role in the production of ultra-clean transportation fuels, chemicals, and other hydrocarbon products. In this work, a novel combination of fixed-bed and slurry bubble column membrane reactor for Fischer–Tropsch synthesis has been proposed. In the first catalyst bed, the synthesis gas is partially converted to hydrocarbons in a water-cooled reactor which is fixed bed. In the second bed which is a membrane assisted slurry bubble column reactor, the heat of reaction is used to preheat the feed synthesis gas to the first reactor. Due to the decrease of H₂/CO to values far from optimum reactants ratio, the membrane concept is suggested to control hydrogen addition. A one-dimensional packed-bed model has been used for modeling of fixed-bed reactor. Also a one-dimensional model with plug flow pattern for gas phase and an axial dispersion pattern for liquid-solid suspension have been developed for modeling of slurry bubble column reactor. Proficiency of a membrane FTS reactor (MR) and a conventional FTS reactor (CR) at identical process conditions has been used as a basis for comparison in terms of temperature, gasoline yield, H₂ and CO conversion as well as selectivity. Results show a favorable temperature profile along the proposed concept, an enhancement in the gasoline yield and, thus a main decrease in undesirable product formation. The results suggest that utilizing this type of reactor could be feasible and beneficial. Experimental proof of concept is needed to establish the validity and safe operation of the proposed reactor.