Dehydration of ethanol with different salts in a packed distillation column

This work aimed the evaluation of a saline extractive distillation for the ethanol production. A thermodynamic model was used to predict the influence of the salts in the liquid–vapor equilibrium of the system water–ethanol and inside the packed column. The experiments were done in a distillation unit, with an internal diameter of 5.9 cm and a packing section with 37 cm of height, packed with raschig rings with 0.73 cm of characteristic inner made of glass. All the bottom and top samples were analyzed by refractive index. Two synthetic charges with the same composition of ethanol that are produced in the refinery (0.02 and 0.25 mol.L^-1) were distilled under atmospheric pressure. Sodium chloride, calcium chloride, potassium acetate, calcium nitrate and a mixture of sodium and potassium acetates were added to the synthetic charges and the results were compared to the experiments already done without the presence of the salts, revealing the ethanol enrichment in the top product of the distillation unit, for all the systems analyzed. Another charge from the refinery, known as load of wine without yeast, was evaluated and the results indicated the same behavior, enriching the ethanol with the application of the saline extractive distillation.     

Liquefaction of sawdust in hot compressed ethanol for the production of bio-oils

Direct liquefaction of lignocellulosic waste (sawdust) has been conducted in hot-compressed ethanol at temperatures from 150 to 250 °C. It was found that polyols such as glycerol, glycol and polyethylene glycol (PEG) promoted liquefaction process assisted with hot ethanol treatments seemed promising for production of bio-oils from lignocellulosic materials. Effects of different solvents and catalysts on liquefaction of sawdust were investigated. The results showed that the optimum operating condition for catalytic liquefaction is at 250 °C, 1 h of reaction time using glycerol and ethanol as solvent where operating at this condition realized the highest conversion of sawdust which is 97.8%. After reaction, the liquified product was separated by vacuum distillation. Two fractions were obtained, namely light oil and heavy oil. The properties and compositions of these two fractions were characterized in terms of Fourier transform infrared spectroscopy (FT-IR), gas chromatography–mass spectrometry (GC–MS), size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR).     

A multi-criteria approach to screening alternatives for converting sewage sludge to biodiesel

The search for cheaper feedstock for use in the production of biofuels such as biodiesel has turned attention to various forms of waste products including animal fats, waste oils and now lipids in sludge. With the potential of obtaining sludge at a reduced cost, free, or possibly with incentives, sewage sludge is being investigated as a potential feedstock for biofuel production. For the extraction of oils from the sewage sludge and the subsequent processing, there are various alternatives that should be designed, analyzed, and screened. In developing and screening these alternatives, it is necessary to have a consistent basis for comparing alternatives based on key criteria. While most of the design studies focus on techno-economic criteria, it is also important to include safety metrics in the multi-criteria analysis. In this work, a detailed economic analysis and a safety evaluation are performed on a process involving extraction of triglycerides and fatty acids, pre-treatment of fatty acids (direct conversion to biodiesel), and transesterification of triglycerides to biodiesel. Four solvents, toluene, hexane, methanol and ethanol, are individually used in the extraction process. The resulting triglycerides and fatty acids from each extraction are modeled in the pre-treatment process. ASPEN Plus software is used to simulate the detailed process. Economic analysis is performed using ASPEN ICARUS, and scale-up of a previously analyzed process is used to estimate the cost of the biodiesel portion of the process. A new safety metric (referred to as the Safety Index “SI”) is introduced to enable comparison of the various solvent extraction processes. The SI is based on solvent criteria as well as process conditions. A case study is presented to demonstrate the insights and usefulness of the developed approach. The results of the techno-economic analysis reveal that of the four solvents used for the initial extraction, hexane and toluene were least costly (2.89 and 2.79 $/gal, respectively). Conversely, the safety analysis utilizing the SI reveals that methanol and ethanol are the safer solvent options. The issue of cost/safety tradeoffs is also discussed.     

Inherently safer design of solvent processes at the conceptual stage: Practical application for substitution

The implementation of inherently safer design concepts is considered beneficial to avoid hazards during early stages of design. The application of existing process design and modeling techniques that aid ‘substitution’, ‘intensification’ and ‘attenuation’ has been shown in this work. The techniques have been applied to solvent processes because of the inherent hazards associated with them, such as large inventories, and presence of highly toxic and flammable materials. For ‘substitution’, computer aided molecular design technique has been applied to select inherently safer solvents for a solvent operation. For ‘intensification’ and ‘attenuation’, consequence models and regulatory guidance from EPA RMP have been integrated into process simulation. Combining existing techniques provides a design team with a higher level of information to make decisions based on process safety. A case study has been shown for liquid extraction of acetic acid–water mixture. Suitable solvents were identified using ICAS 11.0-ProCAMD, and consequence models were integrated into Aspen plus simulator using a calculator sheet. Solvents such as 5-nonanone, 2-nonanone and 5-methyl-2-hexanone provide inherently safer options, but conventionally-used solvent, ethyl acetate, provides higher degree of separation capability. A conclusive decision regarding feasible solvents and operating conditions would depend on design requirements, regulatory guidance, and safety criteria specified for the process. Inherent safety has always been an important consideration to be implemented during early design steps, and this paper presents a methodology to incorporate the principles and to obtain inherently safer alternatives.     

Safety assessment of potential supercritical solvents for Fischer–Tropsch Synthesis

Fischer–Tropsch Synthesis (FTS) is a primary pathway for gas-to-liquid (GTL) technology. In order to overcome commercial problems associated with reaction and transport phenomena, the use of supercritical solvents has been proposed to enhance conversion, catalyst stability and improve temperature control in fixed-bed reactors. One of the major challenges in designing the supercritical FTS reactor unit is selecting appropriate solvents of critical properties within the required reaction operating conditions. Numerous alternatives exist and should be screened based on relevant criteria. The main aim of this paper is to develop a screening methodology to identify an optimum supercritical solvent or a mixture of solvents that meet the aforementioned criteria while minimizing the cost and more importantly satisfying the safety constraints. A safety metric system was developed in order to compare the risk issues associated with using different solvents. In addition, an economic analysis of using the different solvents was performed. Finally, a case study was solved to illustrate the use of the proposed metrics and the selection of solvents based on safety and techno-economic criteria.     

PLS-based EWMA fault detection strategy for process monitoring

Fault detection (FD) and diagnosis in industrial processes is essential to ensure process safety and maintain product quality. Partial least squares (PLS) has been used successfully in process monitoring because it can effectively deal with highly correlated process variables. However, the conventional PLS-based detection metrics, such as the Hotelling's T² and the Q statistics are ill suited to detect small faults because they only use information from the most recent observations. Other univariate statistical monitoring methods, such as the exponentially weighted moving average (EWMA) control scheme, has shown better abilities to detect small faults. However, EWMA can only be used to monitor single variables. Therefore, the main objective of this paper is to combine the advantages of the univariate EWMA and PLS methods to enhance their performances and widen their applicability in practice. The performance of the proposed PLS-based EWMA FD method was compared with that of the conventional PLS FD method through two simulated examples, one using synthetic data and the other using simulated distillation column data. The simulation results clearly show the effectiveness of the proposed method over the conventional PLS, especially in the presence of faults with small magnitudes.     

鱼体中硝基苯残留量测定方法的改进研究

为了监测自然水体中鱼体内硝基苯的残留量,对硝基苯的环境污染程度做出准确的评估,试验优化了鱼体中硝基苯残留量的测定方法.在比较索氏提取法和水蒸气蒸馏提取法的基础上,采用改进的水蒸气蒸馏提取法,结合苯反萃取,最后用气相色谱法检测,最终形成了改进后的鱼体中硝基苯残留量的检测方法.与索氏提取法和水蒸气蒸馏提取法相比,该方法所需时间短、有机溶剂消耗量少、操作简便、回收率高.在质量比3.0～500.0μg·kg~(-1)内线性关系良好,线性方程为Y=0.161 3X-0.527 8,r=0.999 9.方法检出限为3 μg·kg~(-1),加标同收率为75%～110%,相对标准偏差为3.64%～6.13%.结果证明该方法适用于鱼体中硝基苯残留量的检测.     

先进控制软件(APC)在精馏装置的应用

为进一步提高甲醇精馏装置的综合自动化水平,稳定工艺指标,根据装置安全稳定运行的重要性,采用先进控制技术,应用预测控制、智能控制、软测量等先进控制技术,研究模型预测和反馈控制。结果表明:精馏装置相关工艺参数波动明显变小,工艺参与运行趋于更加平稳,产品质量也得到提升。     

Optimizing safety-constrained solvent selection for process systems with economic uncertainties

Solvents are very commonly used in industrial facilities for a multitude of reasons. Traditionally, solvent selection has been based on minimizing the process operating cost while satisfying a set of operational requirements. Regrettably, safety considerations have typically been overlooked during the design phase. In this paper, a systematic approach is introduced to integrate safety issues into solvent selection and provides a computationally effective method for establishing tradeoffs between the economic and safety objectives. In order to quantify the risk associated with the solvent, we focus on the potential spillage of the solvent and introduce a risk index that is a function of the amount of solvent used and stored, as well as the Permissible Exposure Limit (PEL) dictated by regulatory directives. An optimization formulation is developed and the associated mathematical program solved to select optimal solvents and blends while incorporating economic, technical, and safety considerations. Tradeoff (Pareto) curves are developed to represent the multi-objective optimization results and tradeoffs. Furthermore, economic-data uncertainty and variability over expected ranges are included in the optimization formulation to conduct an insightful sensitivity analysis. Finally, an illustrative case study is considered via increasing levels of complexity in order to evaluate the proposed optimization method which considers both operating cost and safety risk implications in the presence of economic uncertainties.     

Tools for an enhanced solvent properties screening in the early stages of pharmaceutical process development

The objective of this research was the implementation of tools for the evaluation of solvents trough property screening in the early stages of process development. An important feature of the tools is that the implementation of indexes, scores, or weights is avoided. Information already available from the literature was stored in a database in order to turn raw data into decision making information. As a result, a solvent radar chart, a solvent representation table, and a solvent telescopying tool were developed in an ASP.NET application. The synthesis of Propranolol was used as study case in order to explore the selection of solvents in the early stages of process development. The replacement of diethyl ether was possible in the extraction step, while solvent choices were detected for potential telescoping for extraction and crystallisation steps. Solubility was found as a critical parameter in telescoping analysis. The methodology proposed enhanced the view towards a more holistic perspective and a more robust solvent screening process. As a consequence, the next steps into solvent evaluation and process development can be reduced.     

储油条件下拱顶油罐的油气爆炸实验

为研究储油条件下拱顶油罐油气爆炸的发展过程,设计了中尺度拱顶油罐油气爆炸实验台架,并完成了储油条件下油罐油气爆炸试验。实验结果表明:储油条件下油气爆炸会导致罐顶破坏,超压发展分为多个阶段,并出现强烈的超压振荡和二次爆炸现象,最大超压由二次爆炸所产生;爆炸最大超压随着初始油气体积分数的降低而升高;在储油条件下,油罐油气爆炸后会诱导产生二次爆炸现象,第2次爆炸超压峰值和升压速率均远大于第1次爆炸的数值,且二次爆炸对外场的影响更加明显;火焰强度随时间的变化曲线具有2个明显的峰值,其形成原因分别为第1次爆炸和第2次爆炸。     

Study of dry ice formation during blowdown of CO₂-CH₄ from cryogenic distillation column

Cryogenic distillation columns are generally subjected to high-pressure loadings during the natural gas purification process. The high-pressure conditions inside the column cause safety risk e.g. rupture. When an emergency arises, blowdown is a typical way of minimizing the failure hazard. However, blowdown at the cryogenic conditions involves dry ice formation due to the rapid decrease in temperature driven by the Joule-Thomson effect. The dry ice formation intensifies the failure hazard due to the orifice blockage. Therefore, optimization of blowdown parameters is necessary to avoid the dry ice formation. So far, very limited studies are available in the literature for the blowdown of CO₂-CH₄ mixture, especially at the cryogenic conditions. In this study, a computational investigation followed by the experimental validation is accomplished to analyze the dry ice formation during blowdown of CO₂-CH₄ binary mixture from the cryogenic distillation column. The composition of mixture, orifice size, and initial conditions inside vessel have a high impact on blowdown path. A 3.00 mm orifice is the most suitable size for the blowdown at cryogenic conditions as it doesn't promote solidification and discharges the inventory quickly. Based on the experimental observation, an empirical correlation is also developed to instantly find out the optimum blowdown parameters.     

医药行业蒸馏系统蒸气云爆炸模型的研究

医药行业对药品生产的纯度控制相当重要,蒸馏操作是医药行业普遍运用的工艺手段之一.但由于蒸馏工序所涉及的物料常伴随具有较强燃爆性的危险化学品,且闪点以上操作加剧了物料的燃爆危险,因此医药行业蒸馏系统便成了事故多发的工艺单元之一.通过对某公司蒸馏系统的危险性分析,找出了蒸馏系统存在燃爆危险的主要因素,再进一步采用蒸汽云爆炸事故模拟评价方法,结合拉乌尔定律和道尔顿分压定律对该公司蒸馏系统进行安全评价,确定蒸馏系统二元混合物蒸气云爆炸冲击波损害半径.     

Solvent design and inherent safety assessment of solvent alternatives for palm oil recovery

The concept of inherent safety is important in developing an inherently safer and user-friendly process. This paper discusses a new integrated approach of computer-aided product design and inherent safety assessment. Computer-aided Molecular Design (CAMD) approach was utilized in this work to identify potential alternative to n-hexane, the widely used industrial solvent in extracting residual palm oil from pressed palm fibre. The formulation of solvent mixtures was optimized to meet the targeted physical properties before being tested using the Soxhlet Extraction method. Inherent safety assessment to assess the solvent's flammability, toxicity, reactivity, and explosiveness was conducted on the new solvent mix, Mixture 1 (n-hexane + ethanol), Mixture 2 (n-hexane + acetone) and Mixture 3 (n-hexane + n-butanol). It was found that Mixture 1 and 3 are safer than n-hexane and able to extract more oil than n-hexane and Mixture 2. However, the utilization of the solvent is dependent on the end product from the residual palm oil.     

Optimal control of distillation column using Non-Dominated Sorting Genetic Algorithm-II

Many control problems involve simultaneous optimization of multiple performance measures that are often non-commensurable and competing with each other. The presence of multiple objectives in a problem usually gives rise to one set of optimal solutions, largely known as Pareto-optimal solutions. In this paper, the Non-Dominated Sorting Genetic Algorithm-II (NSGA-II) has been successfully applied to optimization of dynamic state of simple distillation process. This paper presents the tuning of Proportional-Integral-Derivative (PID) controllers by minimizing of three objective functions (overshoot, response time, and Integral of Absolute Error (IAE)) through NSGA-II. A MATLAB code for real-parameter NSGA-II has been coupled with HYSYS v.3.1 process simulator for simulation and optimization of process. Optimization numerical results show that genetic algorithm is more suitable method for optimal control of distillation columns than traditional methods.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.     

芳香酯类富勒烯衍生物的制备及光电性能研究

以PCBM为初始原料,经过水解、酯化反应,生成3类富勒烯衍生物,采用红外光谱(FT-IR)、核磁共振(1H NMR和13C NMR)、元素分析仪、质谱(MS)对产物结构进行了表征;并通过紫外可见光谱、循环伏安法等手段研究了目标物的光学与电化学性能,结果表明,目标物PCBTE、PCBBE、PCB(4-MOB)M的LUMO能级分别为-3.91 V、-3.88 V、-3.94 V。     

Occurrence of pyrophoric iron immune to chemical washing in vacuum distillation columns

Pyrophoric iron deposits on vacuum distillation column internals can become immune to water and chemical washing, by coating with asphaltenes entrained in the flash zone vapors. This hypothesis was confirmed by obtaining and inspecting samples of a vacuum distillation column mist eliminator on which pyrophoric iron ignitions were observed that were not affected by the conventional washing procedures. Three conditions are highlighted whose fulfillment significantly increases the probability of persistent pyrophoric iron occurrence on vacuum distillation column internals. A handling strategy is outlined which was based on the experience gained from the described incident.     

Evaluation of Eremurus spectabilis for production of bio-oils with supercritical solvents

Eremurus spectabilis samples were liquefied in organic solvents (methanol, ethanol and acetone) with (sodium hydroxide and ferric chloride) and without catalyst in a cylindrical reactor at temperatures of 270, 290 and 310 °C under supercritical conditions. The effects of liquefaction parameters such as temperature, catalyst and solvent on product yields were investigated. The liquid products were extracted with diethyl ether and benzene using an extraction procedure. The product yields in supercritical methanol, ethanol and acetone were found to as 41.6%, 53.8% and 64.3% in the non-catalytic runs at 310 °C, respectively. The highest conversion was obtained in supercritical acetone in the presence of ferric chloride (10%) at same temperature in the catalytic runs. The produced liquids in acetone were analyzed and characterized by elemental, Fourier transform infrared spectroscopy (FT-IR), gas chromatography–mass spectrometry (GC–MS). The liquid products (bio-oils) obtained with acetone contained various types of components including aromatics, nitrogenated and oxygenated compounds. As the bio-oils obtained exhibit high heat values, E. spectabilis is presented as a potential feedstock candidate for production of bio-fuels or valuable chemicals.     

Improving Energetic Performance and Water Usage in an Industrial Ethanol Distillery

In this paper, a case study based on an industrial process of ethanol distillation was undertaken. It was aimed to improve the energy and water usage in the process. Pinch Analysis concepts were used to propose a new heat exchanger network and a study was undertaken to the water reuse. The minimization of wastewater is achieved through the exploitation of recycle and reuse opportunities by process modifications. Through these studies, a new streams circuit was obtained, which resulted in a lower consumption of steam and in a reduction in the volume of water collecting of 12 m³ to 1 m³ per tons of crushed sugar cane. Process changes and economical viability were presented. Two kinds of equipment were studied, cooling towers and aspersion tanks.