二氧化碳协助强化对二甲苯氧化的连续过程实验与模拟

利用连续实验装置考察了气相CO₂浓度和反应温度对PX氧化反应的影响,并通过反应器建模对连续实验过程进行了模拟计算。研究结果表明,当气相CO₂浓度介于40%～60%时,CO₂能显著提高反应器出口PX转化率以及主产物收率,并且可以降低液相中主要杂质的含量;温度高于192℃后对反应器出口指标的影响比低温时明显。本文建立的全混流反应器模型能够预测气相CO₂含量以及温度等不同反应条件下氧化反应器出口的PX转化率、主产物收率以及液相主要杂质随停留时间的变化。相关研究结果可为当前工业PX氧化过程效率提高以及节能降耗提供新的思路。     

温度和停留时间对煤热解挥发分二次反应的影响

在两段固定床反应器中考察了温度和停留时间对煤热解挥发分二次反应产物分布的影响. 结果表明,温度和停留时间对二次反应的影响相互关联. 温度≤600℃、停留时间小于2 s时,挥发分基本不发生气相二次反应. 随温度升高和停留时间延长,挥发分二次反应加剧,焦油产率下降,气体产率和积碳产率增加. 温度低于700℃时,焦油主要转化为气体产物,气相二次反应由二次裂解反应控制;高于700℃时,焦油转化为气体和积碳,气相二次反应由裂解反应和结焦反应共同控制. 提高二次反应温度和延长停留时间,热解气中的H2, CH4和CO产率增加,CO2产率减少,焦油中杂原子化合物及其中的酚、甲酚和二甲酚产率降低,大于3环的重质多环芳烃(PAHs)产率增加,H/C和O/C原子比降低,特别是在900℃时,随停留时间延长,H2和重质PAHs产率快速增加.     

微反应器中环戊烯催化氧化制备戊二醛的研究

以C5副产物制备出的环戊烯为原料,在微通道反应器内以钨酸为催化剂,在叔丁醇溶剂体系下经双氧水催化氧化制备戊二醛产品,重点考察了钨酸加入量、反应温度、停留时间以及助剂对实验结果的影响。优化实验条件为：催化剂钨酸的物质的量浓度为0.02mol/L,反应温度40℃,停留时间为4.5h;添加助剂KBr物质的量浓度0.02mol/L,停留时间缩短为2h,环戊烯转化率大于98%,选择性达93%以上。研究表明,应用微通道反应器提高此反应的选择性是由于反应器的独特结构控制了中间产物的生成和转化过程,对于此类中间产物过程复杂的反应通过控制停留时间可以使反应达到理想的效果,完成了在普通反应器中不可实现的难题。     

自吸式搅拌鼓泡反应器中硝酸还原反应的研究

本文在自吸式搅拌鼓泡反应器中进行硝酸还原反应研究,即一氧化氮与硝酸和甲醇反应生成亚硝酸甲酯的反应研究,实验考察了不同的反应温度、压力以及液相停留时间对NO转化率和MN收率的影响,并通过离子色谱分析反应后的液相组成。结果表明,在0.5bar,温度为65℃,硝酸浓度为10%,气相中NO浓度为15%,液相停留时间为4h的条件下,NO转化率可达85%,MN收率约89%,由离子色谱可知有一部分NO与HNO3反应生成了HNO2,在大量甲醇存在的溶液环境下,可稳定存在。     

波形隔板对平板式生物反应器传质及混合性能的影响

对带波纹隔板的平板式生物反应器,利用计算流体动力学进行流场模拟,验证模型可靠性后,系统分析波纹隔板高/波长(L/l)和波幅/波长(A/l)两个波纹隔板结构参数对反应器传质及流动混合特性的影响. 结果表明,当L/l=12时,传质及流动混合性能较好,液相体积传质系数(kLa)、平均湍动能(Em)、下降区停留时间占循环一周时间之比(q)等表征传质及混合的参数值均较大,得到的液体流速在微藻生长的最佳流速附近. 当A/l=0.8时,反应器的传质性能最优,kLa比采用平直隔板时增加了约10%;当A/l=0.4时,反应器的混合效果最佳,Em比采用平直隔板时增加14.7%.     

微泡强化臭氧传质及其对产生羟基自由基的影响

为提高臭氧在水中的传质效率,设计了微泡反应器强化臭氧传质,考察了在该反应器中不同压力、温度、臭氧进口浓度及流量对液相中臭氧浓度以及羟基自由基产生的影响。结果表明,液相中臭氧浓度受压力影响较小,反应器压力增加可使液相中羟基自由基产生量增大;进口臭氧浓度及流量的增加,可使液相中臭氧浓度以及羟基自由基产生量增大;液相温度升高导致液相中臭氧浓度降低,但可以提高液相中羟基自由基产生量。同时还将该微泡反应体系与传统鼓泡反应器进行对比研究,结果表明,微泡反应器能有效地提高传质效率,液相中臭氧浓度达到稳定状态时约为14 mg/L,比鼓泡反应器高约10%。微泡加压反应器中羟基自由基产生效果更好,臭氧通入5 min,微泡反应器中羟基自由基浓度高达121.45×10~(-6)mol/L,比鼓泡反应器提高了约11倍,且微泡反应器中废水脱色及矿化效率都高于传统鼓泡反应器。     

超重力旋转填充床氧解吸过程的数值模拟

基于旋转填充床流体流动的可视化结果,建立了超重力旋转填充床气液传质过程的数学模型,模拟氮气解吸水中溶解氧的传质过程。模拟结果表明,缩短液相停留时间、提高液相扩散系数都能增大液相传质分系数k_L;总体积传质系数K_La随超重力因子的增加而增大、随温度的上升而增大、随气相流率的增加略有下降、随液相流率的增加明显增大;空腔区传质贡献率随空腔区的增大而增大,随超重力因子的增大而减小;且短暂的停留时间是超重力旋转填充床对传质过程强化的本质原因。模型较好地符合文献的实验数据,误差在±16%以内。     

圆盘反应器中的PET缩聚过程

利用薄膜实验研究了PET缩聚过程反应和传质规律 ,建立了链增长、链降解反应动力学模型和泡沫脱挥时的传质速率方程 ;通过冷模实验研究了圆盘反应器中PET的混合、流动、成膜、膜表面更新以及传质规律 ;综合了反应和反应器研究结果 ,建立了圆盘反应器中的PET缩聚过程模型 ,对圆盘反应器中的PET缩聚过程进行了仿真分析 ,考察了温度、压力、停留时间、转速、催化剂浓度、负荷大小等各种因素的影响     

微通道反应器合成聚乙二醇400连续流工艺研究

对微通道反应器合成聚乙二醇400连续流工艺进行研究，采用乙二醇、环氧乙烷为原料，加入固体碱催化剂，按照固定反应物料比和催化剂用量，通过对反应停留时间、反应温度等条件的考察获得最佳工艺条件。结果表明：当n(乙二醇)∶n(环氧乙烷)=1∶4.0、反应温度120℃、反应停留时间200s时，得到的产品分子量分布系数最小，反应效果最佳。此工艺充分利用连续流微通道反应器优良的传质传热特点，缩短了反应时间，提高了反应效率，降低分子量分布。     

双氧水氧化乙二醛合成乙醛酸的连续流工艺

以乙二醛和双氧水为原料,在微通道反应器中考察了液相氧化合成乙醛酸的连续流工艺。考察了物料比、催化剂用量、双氧水浓度、停留时间、温度等对反应的影响。确定该法最佳工艺条件为,n(乙二醛)∶n(H_2O_2)∶n(FeSO_4)=1.0∶1.0∶0.13,双氧水浓度1.67 mol/L,停留时间10 min,反应温度30℃。在该条件下,乙二醛转化率达到94.7%,乙醛酸选择性达到85.4%。该工艺充分利用微通道反应器优良的传质传热特点,大大缩短了反应时间,提高了反应速率,扩大了工艺条件选择区间,实现了对氧化反应过程的有效控制,增加了安全系数。     

Modeling and analysis of a gas sweeping process for polycarbonate polymerization

This article deals with (1) the development of a mathematical model for the finishing polycarbonate polymerization process with a horizontal, rotating disk‐type reactor with countercurrent gas sweeping and (2) the performance analysis of the reactor system with the model. We propose a model describing a reactor system consisting of two phases in which the byproduct (phenol) is removed from the polymer melt phase to the countercurrently flowing vapor phase to facilitate the forward reaction and, therefore, produce a high molecular weight polymer compatible with the products of commercial grades. The vapor phase is represented by the tanks‐in‐series model, whereas the polymer melt phase is regarded as a plug flow reactor. The major concerns here are the influences of the reactor operating conditions, including the catalyst concentration, reaction temperature, mass‐transfer rate, melt‐phase residence time, and vapor‐phase velocity, on the polymer molecular weight, the melt‐phase concentrations of various components, and the molar fraction of phenol in the vapor phase. To corroborate the validity of the proposed model and investigate the complex phenomena of the process, we have conducted a series of simulation studies with various operating policies, and we compare the performance of the process with the performances of the cocurrent process and the vacuum process. According to the results of this study, this new type of reactor system shows satisfactory performance and is sometimes even better than the conventional high‐ vacuum process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1010–1021, 2003     

Dynamics of a continuous stirred tank reactor for styrene polymerization initiated by a binary initiator mixture. II: Effect of viscosity dependent heat transfer coefficient

The dynamic behavior of the solution polymerization of styrene in a continuous stirred tank reactor is analyzed with a mixture of tert-butyl perbenzoate and benzoyl peroxide as an initiator system. In the modeling of the reactor, a viscosity dependent reactor wall heat transfer coefficient is used to account for the changing heat transfer efficiency as monomer conversion and polymer molecular weight increase. The steady state and bifurcation behaviors have been investigated with the reactor residence time, initiator feed composition, initiator concentration, feed solvent volume fraction, and coolant temperature as bifurcation parameters. Unlike the reactors with constant heat transfer coefficient, the present system exhibits relatively simple steady state and dynamic bifurcation behaviors. Oscillatory behavior is observed only when the solvent volume fraction in the feed exceeds 0.2. The dynamic simulation of the reactor also indicates that a feedback temperature controller may fail to maintain the reactor temperature when the heat transfer coefficient changes as a result of process disturbances.     

The radiation-induced emulsion copolymerization of vinyl chloride with vinyl acetate in an engineering flow system

A flow reactor system was used to study the radiation-induced emulsion copolymerization of vinyl chloride with vinyl acetate. The emulsion was recirculated from a stirred vessel through transfer lines to a tubular reactor located within a high-intensity Co-60 source. The effects of physical chemical variables such as soap concentration, phase ratio, reaction temperature and residence time distribution on the molecular weight properties were investigated. The rate of copolymerization was found to be proportional to the 0.17 power of the soap concentration. Variation of the monomer-water ratio produced no significant change in rate. The rate increased with an increase in temperature over the range 5–50°C, while the average molecular weights of the copolymer increased with decreasing polymerization temperature. The molecular weight distribution in this engineering system was found to be essentially similar to those produced in a batch system.     

聚酰胺酸溶液成膜过程中的传质行为

为了研究聚酰胺酸溶液成膜过程中的传质行为,采用自制液膜干燥实验装置在线测定聚酰胺酸溶液质量的变化.假设气、液两相传质通量相等的条件下,计算了溶剂气相传质系数和液面蒸气压.在此基础上考察了干燥温度、液膜厚度、溶液相对分子质量对液膜表面蒸气压的影响.结果表明,成膜过程中存在溶剂蒸发与聚酰胺酸溶液亚胺化反应的相互竞争.干燥初期溶剂蒸气压迅速升高,液膜表面溶剂的扩散为控制步骤;而干燥后期溶剂蒸气压较小,溶剂在膜内部扩散成为控制步骤.同时随着液膜厚度的增加、干燥温度的升高及溶液相对分子质量的减少,液面蒸气压的最大值呈现增大趋势.     

管式反应器液相循环反应制备二甘醇乙烯基醚

以乙炔和二甘醇为原料,二甘醇钾为催化剂,采用管式反应器液相循环反应制备二甘醇乙烯基醚。研究了催化剂用量、反应温度、反应压力和停留时间等因素对乙炔转化率的影响,得到较为适宜的反应条件为：催化剂二甘醇钾用量为二甘醇质量的4%、反应温度175℃、反应压力6MPa、停留时间175s。在该条件下进行了液相连续循环反应,反应达到稳态时,二甘醇的转化率为76.03%,二甘醇单乙烯基醚收率为59.03%,二甘醇双乙烯基醚的收率为15.10%,合计二甘醇乙烯基醚总收率为74.13%。单位反应体积二甘醇乙烯基醚的产率为143.2g/（h·mL）。二甘醇与乙炔反应符合一级反应动力学方程,反应的指前因子k₀=1.20×10⁸s^–1,反应的活化能E=86.86kJ/mol。管式反应器中无气相乙炔,克服了高温高压下气相乙炔易燃易爆的危险。     

联苯二甲酸共聚改性PET的合成及热性能研究

以4,4′-联苯二甲酸(BPDA)、对苯二甲酸和乙二醇为单体采用直接酯化法工艺制备了不同BPDA含量的共聚酯;借助核磁共振氢谱表征了共聚酯的组成;利用差示扫描量热法和热重分析法研究了共聚酯的热性能。结果表明:共聚酯的组成符合理论预期值,其粘均相对分子质量为26 400～27 600;随着BPDA含量的增加,共聚酯的结晶能力先增强后减弱,而玻璃化转变温度和热分解温度都有所提高。     

Enhancement of Ozone Mass Transfer by Stainless Steel Wire Mesh and Its Effect on Hydroxyl Radical Generation

ABSTRACT

In order to improve the mass transfer efficiency of ozone in water, stainless steel wire mesh (SSWM) corrugated structure was packed into a microbubble ozone reactor to enhance the mass transfer efficiency. The results showed that the SSWM/O₃ system could effectively improve the mass transfer efficiency. When the concentration of ozone in the liquid phase reached a stable state, it was about 21 mg/L, which was about 14% higher than that of ozone alone; the apparent mass transfer coefficient (K_La) was 0.7255 min^?1, which was about 51% higher than that by ozone alone systems. The hydroxyl radicals in the SSWM/O₃ system were more generated than that of ozone alone. After 6 min of operation, the concentration of hydroxyl radicals increased by 60 µmol/L compared with that in ozone alone system. The Chemical Oxygen Demand (COD) removal efficiency of biologically treated leachate by SSWM/O₃ system was about 10% higher than that of ozone alone system after 120 min of reaction. The effects of pressure, temperature, ozone inlet concentration, and flow rates on the ozone concentration in the liquid phase and the generation of hydroxyl radicals were also investigated. The results indicated that reactor pressure has little effect on ozone concentration in liquid phase, but increasing pressure helps to generate ·OH; ozone concentration and ·OH generation in liquid phase increase with the increase of inlet ozone concentration and flow rate; ozone concentration in the liquid phase decreases with the increase of temperature, but ·OH generation increases with the increase of temperature. Our results indicate that the system consisting of SSWM and microbubble column reactor is an efficient process for the intensification of ozone-based advanced oxidation processes.     

CFD analysis of hydrodynamic, heat transfer and reaction of three phase riser reactor

Catalytic cracking reaction and vaporization of gas oil droplets have significant effects on the gas solid mixture hydrodynamic and heat transfer phenomena in a fluid catalytic cracking (FCC) riser reactor. A three-dimensional computational fluid dynamic (CFD) model of the reactor has been developed considering three phase hydrodynamics, cracking reactions, heat and mass transfer as well as evaporation of the feed droplets into a gas solid flow. A hybrid Eulerian-Lagrangian method was applied to numerically simulate the vaporization of gas oil droplets and catalytic reactions in the gas-solid fluidized bed. The distributions of volume fraction of each phase, gas and catalyst velocities, gas and particle temperatures as well as gas oil vapor species were computed assuming six lump kinetic reactions in the gas phase. The developed model is capable of predicting coke formation and its effect on catalyst activity reduction. In this research, the catalyst deactivation coefficient was modeled as a function of catalyst particle residence time, in order to investigate the effects of catalyst deactivation on gas oil and gasoline concentrations along the reactor length. The simulation results showed that droplet vaporization and catalytic cracking reactions drastically impact riser hydrodynamics and heat transfer.     

TPA和EG连续生产PET的第一酯化反应器操作模拟

对乙二醇(EG)和对苯二甲酸(TPA)连续生产对苯二甲酸乙二酯(PET)的第一酯化反应器进行了数学模拟。数学模型中包括了反应动力学方程、气液平衡和气液传质方程,使模拟结果接近于工厂实践。此外对不同停留时间、不同的反应器操作温度及压力、不同的进料 EG/TPA 的 mol比,进行了模拟计算,得出了反应器出口各种产物的组成随操作参数的变化,并对各操作参数的范围和对反应的影响进行了评述。     

CFB air-blown flash pyrolysis. Part I: Engineering design and cold model performance

The objective of this work was to design, construct and test a novel circulating fluid bed fast pyrolysis reactor system for production of liquids from biomass. The novelty lies in incorporating an integral char combustor to provide autothermal operation of the reactor. A reactor design methodology was devised which correlated input parameters to process variables, namely temperature, heat transfer and gas/vapor residence time, for both the char combustor and biomass pyrolyser. From this methodology, a CFB reactor was designed with integral char combustion for 10 kg/h biomass throughput. A full-scale cold model of the CFB unit was developed and tested to derive suitable hydrodynamic relationships and performance constraints. The hot CFB reactor was constructed, its operability was tested and appropriate modifications were accomplished prior to the commissioning.A major requirement for the desired dual-mode operation of the reactor system conceived was the close coupling of the two reactor subsystems, namely the pyrolysis riser (medium temperature) and char combustor (high temperature). The basic CFB reactor design was proven effective in providing the high heat transfer rates – expressed as low voidage values in the riser and high solid circulation rates – to biomass particles in the very short vapor residence times (VRTs) required. The understanding of the complicated aspects related to two-phase gas–solids flow in the standpipe resulted in a smooth, stable transfer of solids over a wide range of operating parameters during cold CFB reactor operation. In the hot CFB unit testing, the use of two and three cyclones in series was proved insufficient to capture char and unconverted wood particles, especially during the reactor start-up phase. These problems were partially faced by adopting a configuration of a primary cyclone and inertia impinger in series, but further development is still required. A variety of configurations for the product collection system were built and tested, the most efficient being a combination of a shell-and-tube heat exchanger (condenser) and a cotton wool filter. However, the liquid recovery configuration gave rise to a number of problems, the most important being gradual plugging of the heat exchanger due to the formation of sticky solid–liquid agglomerates.