气体搅拌萃取过氧化氢实验研究

在内径为50 mm的筛板塔内,研究了空气-水-蒽醌工作液三相体系萃取过氧化氢过程.萃取温度为40℃,空气和分散相的表观流速分别为(1.31～3.22)×10-3m·s-1和(1.27～1.70)×10-3 m·s-1,分散相和连续相的表观流速之比为50:1.结果表明,在普通液-液萃取过氧化氢过程中引入气体作搅拌,可减小分散相的液滴直径,增大相际接触面积,明显提高萃取效率,降低萃余相中过氧化氢的含量.传质单元高度随气体表观流速的增加而降低,传质系数随气体表观流速的增加而增大.     

Experimental investigation and simulation of gas-liquid-liquid reactive extraction process for the production of hydrogen peroxide

The gas-liquid-liquid reactive extraction system for the production of hydrogen peroxide via anthraquinone route was investigated. The oxidation of the hydrogenated anthraquinone working solution by oxygen and the extraction of hydrogen peroxide from the working solution with deionized water were carried out simultaneously in a sieve plate column of 50 mm in diameter. The effects of the superficial velocity of oxygen on the conversion of 2-ethylanthrahydroquinone and the extraction efficiency of hydrogen peroxide were investigated, separately. The results showed that the oxidation and the extraction do not hamper each other, on the contrary, the presence of gas in the column can promote the transfer of hydrogen peroxide from the organic phase to the aqueous phase, therefore, the conversion of 2-ethylanthrahydroquinone and the extraction efficiency of hydrogen peroxide increased with the increase of gas superficial velocity. In addition, a mathematical model for the simulation of the gas-liquid-liquid reactive extraction process was developed. The predicted values were compared with the experimental data at different conditions and the agreement was found to be quite satisfactory for the production of hydrogen peroxide in a sieve plate column.     

气-液-液喷射反应萃取制备过氧化氢的过程

引　言过氧化氢 (H2 O2 )是一种性能优良的氧化剂 ,因其以水为还原产物而备受绿色化学与化工研究领域广泛关注 .以过氧化氢为氧化剂的氧化过程具有反应条件温和、选择性高、无污染等优点 ,因此被广泛地用于纺织品和造纸的无氯漂白、化学合成、污水处理等领域 ,应用前景十分广阔 ,市场潜力非常大 .蒽醌衍生物自动氧化法 (AO )是过氧化氢的主要生产方法 ,基本原理是[1] :烷基取代的蒽醌 (主要是 2 乙基蒽醌 )和四氢蒽醌 (主要是四　氢 2 乙基蒽醌 )溶解在适当的溶剂中配制成工作液 ,循环交替氢化和氧化工作液 ,即工作液中的蒽醌与氢气反应…     

Reactive extraction for preparation of hydrogen peroxide under pressure

The preparation of hydrogen peroxide from anthrahydroquinone by reactive extraction was investigated. The integration process of oxidation of anthrahydroquinone by air and extraction of hydrogen peroxide from the organic phase with water was carried out in a sieve plate column under pressure. The conversion of anthrahydroquinone increased with increasing pressure resulting in an increase of hydrogen peroxide concentration in the aqueous phase. However, no change in extraction efficiency of hydrogen peroxide was observed. A mathematical model for gas-liquid-liquid reactive extraction was established. In the model, the effects of pressure and gas superficial velocity on reaction were considered. With increasing gas superficial velocity, the conversion of anthrahydroquinone increased, and the fraction of hydrogen peroxide extracted reached a plateau with a maximum of 72.94%. However, both the conversion of anthrahydroquinone and the fraction of hydrogen peroxide extracted decreased with increasing organic phase superficial velocity.     

GAS-AGITATED LIQUID AND OXIDATIVE EXTRACTION IN THE ALKYL ANTHRAQUINONE PROCESS FOR THE PREPARATION OF HYDROGEN PEROXIDE

As preliminary investigations on oxidative extraction in the alkyl anthraquinone process for the production of hydrogen peroxide, the air-agitated liquid extraction of hydrogen peroxide from the working solution was studied and the dynamics of the extraction was measured as a function of the oil/water ratio and gas flow rate. The investigations were carried out either in an empty column or in a packed column. The results proved that the use of gas-agitated oxidative liquid extraction was a good way to integrate the oxidative operation unit with the extraction unit in the alkyl anthraquinone process for the preparation of hydrogen peroxide.     

气体喷射筛板萃取塔的滞液率和气含率

以水和蒽醌法生产过氧化氢的工作液为研究物系,在内径为50 mm的筛板萃取塔内,模拟工业操作条件,研究了空气-水-蒽醌工作液三相物系的分散相滞液率和气含率. 讨论了气相、分散相和连续相流速对分散相滞液率和气含率的影响,并提出了用于预测气-液-液三相萃取系统的分散相滞液率和气含率的关联式. 结果表明,滞液率关联式的预测值与实验结果的平均相对偏差为7.3%,气含率关联式的预测值与实验结果的平均相对偏差为7.1%.     

Reactive extraction for preparation of hydrogen peroxide under pressure

The preparation of hydrogen peroxide from anthrahydroquinone by reactive extraction was investigated. The integration process of oxidation of anthrahydroquinone by air and extraction of hydrogen peroxide from the organic phase with water was carried out in a sieve plate column under pressure. The conversion of anthrahydroquinone increased with increasing pressure resulting in an increase of hydrogen peroxide concentration in the aqueous phase. However, no change in extraction efficiency of hydrogen peroxide was observed. A mathematical model for gas-liquid-liquid reactive extraction was established. In themodel, the effects of pressure and gas superficial velocity on reaction were considered.With increasing gas superficial velocity, the conversion of anthrahydroquinone increased, and the fraction of hydrogen peroxide extracted reached a plateau with a maximum of 72.94%. However, both the conversion of anthrahydroquinone and the fraction of hydrogen peroxide extracted decreased with increasing organic phase superficial velocity. __________ Translated from Petrochemical Technology, 2007, 36(1): 49–54 [译自: 石油化工]     

蒽醌法过氧化氢合成中喷射萃取过程研究

在自行设计的喷射萃取塔中,以纯水为萃取剂,进行蒽醌法过氧化氢生产中H2O2的液液萃取、气液液喷射萃取实验研究。结果表明,在一定萃取比范围内,萃取剂用量对液液萃取过程H2O2的萃取率影响很小。喷射萃取过程中塔的传质单元高度随喷射气体及分散相流量的增加而减小。在相同分散相流量下,喷射萃取的传质单元高度比液液萃取低2—3倍。喷射萃取过程中H2O2的萃取率比液液萃取提高2—3倍。研究结果将为工业化设计提供依据。     

蒽醌法过氧化氢萃取塔板效率计算及改进研究

应用两相互不溶逆流萃取模型,对蒽醌法过氧化氢萃取塔板效率(Murphree级效率和总塔效率)和萃取过程进行计算,并与实验结果比较;对萃取塔板进行了改进研究。结果表明:萃取过程的模型计算结果与实验结果一致。与改前萃取塔板相比,改进后塔板Murphree级效率提高49%、总塔效率提高65%;在总板数44块、氧化效率7.0g/L时,可直接制备质量分数35%过氧化氢产品。     

气体搅动的筛板萃取塔性能实验研究

在筛板萃取塔中引入气体搅动,既能明显提高装置的传质效率,又能大幅提高装置处理能力。筛板塔的通量随气速的变化规律与填料塔有显著区别,其性能研究有重要意义。利用煤油(苯甲酸)-水-空气体系,考察了气体搅动和筛孔直径对萃取塔流体力学和传质性能的影响。结果表明,随着表观气速的增加,气含率、分散相含率、液泛速率和传质效率均明显增加。但过高的气速也会导致分散相的过于分散和乳化,传质性能下降,直至液泛。不同直径的筛孔相比,较小的筛孔使分散相停留时间延长,分散相含率和传质效率提高,但液泛速率和处理能力降低。     

装配水平筛板的气升式反应器中气液传质特性的数值模拟

利用Turbulent–Lehr组合模型对装配水平筛板的气升式反应器进行了计算流体力学(CFD)模拟,研究水平筛板对气含率、气泡直径、体积传质系数(kLa)和气液流速的影响。结果表明,筛板对气相的囤积作用和对液相的阻碍作用增加了反应器的整体气含率。筛板对气相的二次均布作用减弱了筛板和液面之间区域的气泡聚并过程,筛板筛孔对气泡的破碎作用产生了大量小于初始直径的气泡,增加了气泡比表面积(a);筛板对液相的阻碍作用提高了筛板附近的气–液相流动速度差,从而提高了该区域的液膜传质系数(kL),强化了反应器内的气液传质效果。     

Kinetic Model of Gas‐Liquid‐Liquid Reactive Extraction for Production of Hydrogen Peroxide

The kinetic aspects of the gas‐liquid‐liquid reactive extraction process for the production of hydrogen peroxide were investigated in a batch reactor. It was observed that the gas‐liquid reaction rate is strongly affected by mass transfer of oxygen across the liquid film and the reaction can be simplified to pseudo‐first order. The extraction rate is governed by both reaction and liquid‐liquid mass transfer, and is slightly lower than the reaction rate. In addition, a kinetic model of the reactive extraction process for the production of hydrogen peroxide was developed. Kinetic parameters under different conditions were determined by experiments. The data calculated from the kinetic model match experimental data well under different conditions for hydrogen peroxide production in gas‐liquid‐liquid reactive extraction.     

Column Dust Scrubber Based on an Orifice Plate to Intensify Gas‐Liquid Mixing

A column dust scrubber based on an orifice plate is developed for small and medium‐sized enterprises in China, which urgently need small‐volume, large‐flow scrubbers. The scrubber uses an orifice plate to evenly distribute the gas flow, which forms a uniform and stable impact on the liquid phase. As a result, dust removal via intensified gas‐liquid mixing can be achieved. A laboratory orifice plate scrubber model is developed, prototyped, and preliminarily studied considering the working process of the scrubber (mixed gas‐liquid flow pattern), liquid level, gas flow rate, pressure drop characteristics, dust removal efficiency, etc. The scrubber can achieve a good gas‐liquid mixing state when it is in a stable liquid column flow pattern. The drag coefficient of the scrubber is affected by the discharge of the gas stream to the liquid phase.     

Heat transfer modelling of sieve trays

A heat transfer model that accounts for both gas and liquid phase resistance was developed for sieve trays where the overall heat transfer coefficient is expressed as a function of Sauter-mean bubble diameter. These diameters, obtained from pilot plant data, were correlated and used to predict point efficiencies on production plant trays. Applying the appropriate liquid flow distribution model allows the prediction of overall tray efficiencies. Predicted temperature profiles have agreed well with measured plant profiles and tray changes at the production plant have resulted in steam savings that were adequately predicted by the model.     

A study on hydrodynamic characteristics in a Φ38 pulsed extraction column by four‐sensor optical fiber probe

Accurate prediction of dispersed phase droplet behavior is crucial to the design and scaling‐up of an extraction column. In this article, the dispersed droplet velocity algorithm and the diameter algorithm in a liquid–liquid two‐phase flow have been developed based on the bubble velocity model in gas–liquid two‐phase flow of Lucas [Measurement Science & Technology. 749, 758(2005)] and Shen [International Journal of Multiphase Flow. 593, 617(2005)]. Hydrodynamic characteristics, including droplet diameter, holdup and droplet velocity, were measured using a self‐made four‐sensor optical fiber probe in a 38 mm‐diameter pulsed sieve‐plate extraction column. Water and kerosene were used as continuous and dispersed phases, respectively. The influences of the pulsed intensity, the continuous and dispersed phase superficial velocities on the hydrodynamic characteristics were investigated. The experimental results show that it is reliable to use a four‐sensor optical probe to measure the hydrodynamic characteristics of a pulsed extraction column. © 2016 American Institute of Chemical Engineers AIChE J, 63: 801–811, 2017     

分散降液筛板塔传质性能

在筛板塔的基础上,研发了一种新型板式塔--分散降液筛板塔,将传统筛板塔的弓形降液管改为均布于塔板筛孔间的多降液管结构,使整个塔板面成为均匀降液和受液的传质区,并新增淋降和喷溅传质区,在全塔空间内实现立体、连续的微分接触式气液传质过程,另外,塔板之间可以加装填料来强化传质,或装填催化剂以促进伴随化学反应的传质过程。以“氧气-空气-水”为体系,初步研究了分散降液筛板的传质性能及其影响因素,并与传统筛板进行比较,结果表明:分散降液筛板气液分布均匀,接触充分,在同等条件下传质效率比传统筛板提高了8.4%~9.7%。     

气液两相并流下行通过堆叠筛板填料的压降特性

堆叠筛板填料已在核电站放射性气体除气塔中得到成功应用。针对这一新型填料的应用设计,在较广泛的气液流量下,对气液并流下行通过不同规格堆叠筛板填料的阻力特性进行了系统的实验。实验填料共6种规格,孔径参数包括6、10和14 mm,不同孔径填料对应不同的孔间距、板间距,每种孔径填料具有正方形和正三角形两种筛孔分布方式。通过压降数据分析,研究了流动参数和几何参数（孔径、开孔率、布孔方式、板间距）对气液两相并流通过填料的流动行为及压降特性的影响;结合多孔板阻力系数经验公式提出了堆叠筛板填料干板阻力系数的计算模型,模型很好地反映了不同几何参数对干板阻力系数的影响,预测偏差在5%范围以内;基于均相流模型提出了堆叠筛板填料气液两相压降的预测模型,模型预测偏差在10%范围以内。研究工作对堆叠筛板填料塔的应用设计及进一步的传质动力学研究有一定参考价值。     

蒽醌法制H_2O_2工艺过程强化

在蒽醌法工艺全流程模试装置上,采用含四丁基脲工作液、富氧空气在筛板氧化塔氧化及带聚凝板筛板塔萃取等技术,对蒽醌法氧化、萃取工艺过程进行了强化研究。结果显示:氧化塔H2O2生产能力提高至32kg/(m3.h);萃取液中过氧化氢质量分数可达50%。与空气鼓泡塔氧化相比,采用筛板塔和富氧空气进行氧化,均可提高氧化塔生产能力;在萃取塔内添加聚凝板,可增强萃取效果。     

改进的Scheibel萃取塔的性能研究

Scheibel萃取塔是一种常用的多级逆流搅拌萃取装置,它的主要缺点是存在比较严重的返混。为了减少返混,提高Scheibel萃取塔的萃取效率,本文设计了一种改进的Scheibel萃取塔,在传统的Scheibel萃取塔的填料两端各添加一块筛板,这样可以降低返混,减少转动流体对分层段的影响。本文用丙醇-水-庚烷体系研究了开孔率,搅拌速度,进料流量对改进的一级Scheibel萃取塔萃取效率的影响。得到了较佳的筛板开孔率10%和较佳的操作条件。在较佳的筛板开孔率和操作条件下用改进的三级Scheibel萃取塔和传统的三级Scheibel萃取塔进行萃取效率的对比,结果显示改进的Scheibel萃取塔的萃取效率要远好于传统的Scheibel萃取塔。     

Prediction of Concentration Profiles in an L‐Shaped Pulsed Extraction Column

The L‐shaped extraction pulsed plate column is believed to be able to perform under operating conditions between those of the vertical and the horizontal pulsed plate columns. It has an extraction efficiency similar to the vertical pulsed plate column. Here, the mass transfer performance of this novel column type was investigated and the application of three different models, i.e., the plug flow, the axial dispersion, and the back flow models, was evaluated to predict the solute concentration profile along the column length. The water‐acetone‐n‐butyl acetate and the water‐acetone‐toluene systems were used. The influence of the operational parameters on the height of the mass transfer unit and the back flow coefficients was evaluated using the back flow model. New correlations were proposed to predict the height of the mass transfer unit along with the back flow coefficients in each phase, which were in satisfactory agreement with the experimental data.