A novel split-reflux policy in batch reactive distillation for the optimum synthesis of a number of methyl esters

YesThe production of a number of methyl esters such as methyl decanoate (MeDC), methyl salicylate (MeSC), and methyl benzoate (MeBZ) by esterification reactions of several carboxylic acids such as decanoic acid (DeC), salicylic acid (ScA), and benzoic acid (BeZ) with methanol, respectively, through a reactive distillation system (batch or continuous) is cost-intensive and operationally challenging operation. It is difficult to keep the reaction species together in the reaction section due to wide boiling point differences between the reactants. Methanol (in those esterification processes) having the lowest boiling temperature in the reaction mixture can separate easily from carboxylic acid as the distillation progresses, resulting in a severe drop in the reaction conversion ratio of the acid employing batch/continuous distillation system. In order to overcome this type of challenge and to increase the overall reaction conversion, a novel split-reflux conventional batch reactive distillation configuration (sr-BRD) is proposed/studied in detail in this investigation. The optimal performance of BRD/ sr-BRD column is determined in terms of maximum achievable conversion of acids, and highest concentration of the esters produced for each chemical reaction scheme. The results for given separation tasks are compared with those obtained using conventional batch distillation (BRD) process. The optimization results clearly show that the sr-BRD process significantly improves the process efficiency, the conversion ratio of acid, and the product purity of methyl esters compared to that obtained via the BRD process

Methyl lactate synthesis using batch reactive distillation: Operational challenges and strategy for enhanced performance

YesBatch reactive distillation is well known for improved conversion and separation of desired reaction products. However, for a number of reactions, the distillation can separate the reactants depending on their boiling points of them and thus not only reduces the benefit of the reactive distillation but also offers operational challenges for keeping the reactants together. Methyl lactate (ML) synthesis via the esterification of lactic acid (LA) with methanol in a reactive distillation falls into this category and perhaps that is why this process has not been explored in the past. The boiling points of the reactants (LA, methanol) are about 490 K and 337 K while those of the products (ML, water) are 417 K and 373 K respectively. Clearly in a conventional reactive distillation (batch or continuous) methanol will be separated from the LA and will reduce the conversion of LA to ML significantly. Here, first the limitations of the use of conventional batch distillation column (CBD) for the synthesis of ML is investigated in detail and a semi-batch reactive distillation (SBD) configuration is studied in detail where LA is the limiting reactant and methanol is continuously fed in excess in the reboiler allowing the reactants to be together for a longer period. However, this poses an operational challenge that the column has to be carefully controlled to avoid overflow of the reboiler at any time of the operation. In this work, the performance of SBD for the synthesis of ML is evaluated using model based optimization in which operational constraints are embedded. The results clearly demonstrate the viability of the system for the synthesis of ML

Synthesis of methyl decanoate using different types of batch reactive distillation systems

YesMethyl Decanoate (MeDC) is a Fatty Acid Methyl Ester (FAME) and is an important chemical compound with global production of 31 million tons per year. However, synthesis of methyl decanoate (MeDC) via esterification of Decanoic Acid (DeC) with methanol by reactive distillation is operationally challenging due to difficulty of keeping the reactants together in the reaction zone as methanol being the lightest component in the mixture can separate itself easily form the other reactant deteriorating significantly the conversion of DeC using either conventional batch or continuous distillation column. This is probably the main reason for not applying the conventional route for MeDC synthesis. Whether Semi-batch Distillation column (SBD) and the recently developed Integrated Conventional Batch Distillation column (i-CBD) offer the possibility of revisiting such chemical reactions for the synthesis of MeDC is the focus of this paper. The minimum energy consumption (Qtot) as the performance measure is used to evaluate the performances of each of these reactive column configurations for different range of methyl decanoate purity and the amount of product. It is observed that the use of i-CBD column provides much better performance than SBD column in terms of the production time and the maximum energy savings when excess methanol is used in the feed. However, the SBD column is found to perform better than the i-CBD column when both reactants in the feed are in equal amount. Also, the optimization results for a given separation task show that the performance of two-reflux intervals strategy is superior to the single-reflux interval in terms of operating batch time, and energy usage rate in the SBD process at equimolar ratio

Investigation about profitability improvement for synthesis of benzyl acetate in different types of batch distillation columns

YesIn this work, for the first time, the synthesis of benzyl acetate via the esterification of acetic acid and benzyl alcohol is investigated in the reactive distillation system using a middle vessel (MVD), inverted (IBD), and conventional batch reactive distillation columns. The measurement of the performance of these column schemes is determined in terms of profitability through minimization of the batch time for a defined separation task. The control variables (reboil ratio for MVD, IBD columns) and (reflux ratio in case of CBD column) are considered as piecewise constants over batch time. The optimization results obviously indicate that the CBD system is a more attractive process in terms of batch time reduction, and maximum achievable yearly profit as compared to the MVD, and IBD operations

Feasibility of Integrated Batch Reactive Distillation Columns for the Optimal Synthesis of Ethyl Benzoate

YesThe synthesis of ethyl benzoate (EtBZ) via esterification of benzoic acid (BeZ) with ethanol in a reactive distillation is challenging due to complex thermodynamic behaviour of the chemical reaction and the difficulty of keeping the reactants together in the reaction zone (ethanol having the lowest boiling point can separate from the BeZ as the distillation proceeds) causing a significant decrease in the conversion of BeZ in a conventional reactive distillation column (batch or continuous). This might be the reason of not reporting the use of reactive distillation for EtBZ synthesis although the study of BeZ esterification reaction is available in the public literature. Our recently developed Integrated Conventional Batch Distillation (i-CBD) column offers the prospect of revisiting such reactions for the synthesis of EtBZ, which is the focus of this work. Clearly, i-CBD column outperforms the Conventional Batch Distillation (CBD) column in terms of product amount, purity and conversion of BeZ and eliminates the requirement of excess use of ethanol. For example, compared with CBD column, the i-CBD operation can yield EtBZ at a much higher purity (0.925 compared to 0.730) and can convert more benzoic acid (93.57% as opposed to only 74.38%)

Feasibility of novel integrated dividing-wall batch reactive distillation processes for the synthesis of methyl decanoate

YesThe production of methyl decanoate (MeDC) through esterification of decanoic acid (DeC) with methanol by reactive distillation is operationally challenging and energy-intensive due to the complicated behaviour of the reaction system and the difficulty of retaining the reactants together in the reaction region. Methanol being the lightest component in the mixture can separate itself from the reactant DeC as the distillation proceeds which will cause a massive reduction in the conversion of DeC utilizing either a batch or continuous distillation process. Aiming to overcome this type of the potential problem, novel integrated divided-wall batch reactive distillation configuration (i-DWBD) with recycling from the distillate tank is established in this study and is examined in detail. This study has clearly demonstrated that the integrated divided-wall batch reactive distillation column (i-DWBD) is superior to the traditional conventional batch distillation (CBD) and both the divided-wall (DWBD), and split reflux divided-wall (sr-DWBD) batch reactive distillation configurations in terms of maximum achievable purity of MeDC and higher conversion of DeC into MeDC. In addition, significant batch time and energy savings are possible when the i-DWBD is operated in multi-reflux mode

Optimisation of semi-batch reactive distillation column for the synthesis of methyl palmitate

YesSynthesis of methyl palmitate (MP) has not been considered in the past using a reactive distillation process (continuous or batch) due to the challenge of keeping the reactants palmitic acid (PA) and methanol (MeOH) together in the reactive zone. MeOH, being the lightest in the reaction mixture, travels up the distillation column as distillation proceeds and will be removed from the system via the distillate in a conventional batch reactive distillation (CBRD) column and thus will limit the conversion of PA. Therefore, in this work semi-batch reactive distillation (SBRD) column is proposed where additional methanol will be fed at the bottom of the column in a continuous mode allowing the chemical reaction to continue. However, as water (H2O) is one of the reaction products and is the second lightest component in the mixture, it will travel up the column next and will be removed in the distillate tank. Also due to wide difference in the boiling points of the reaction products and due to diminishing amount of water in the reboiler, the backward reaction will not be a dominating factor and therefore ignored in this work. With this backdrop, optimal performance of the SBRD column is evaluated in terms of conversion of PA to MP and energy consumption via minimization of the operating batch time for a wide range on MP purity

Process simulation and assessment of crude oil stabilization unit

YesCrude oil is an unrefined petroleum composed of wide range of hydrocarbon up to n‐C40+. However, there are also a percentage of light hydrocarbon components present in the mixture. Therefore, to avoid their flashing for safe storage and transportation, the live crude needs to be stabilized beforehand. This paper aims to find the suitable operating conditions to stabilize an incoming live crude feed to maximum true vapor pressure (TVPs) of 12 psia (82.7 kPa) at Terengganu Crude Oil Terminal, Malaysia. The simulation of the process has been conducted by using Aspen HYSYS. The obtained results illustrate that the simulation data are in good agreement with the plant data and in particular for the heavier hydrocarbons. For the lighter components, the simulation results overpredict the plant data, whereas for the heavier components, this trend is reversed. It was found that at the outlet temperature (85–90°C) of hot oil to crude heat exchanger (HX‐220X), the high‐pressure separator (V‐220 A/B) and the low‐pressure separator (V‐230 A/B) had operating pressures of (400–592 kPa) and (165–186 kPa), respectively, and the live crude was successfully stabilized to a TVP of less than 12 psia. The impact of main variables, that is, inlet feed properties, three‐phase separators operating pressure, and preheater train's performance on the product TVP, are also studied. Based on the scenarios analyzed, it can be concluded that the actual water volume (kbbl/day) has greater impact on the heat exchanger's duty; thus, incoming free water to Terengganu Crude Oil Terminal should be less than 19.5 kbbl/day (9.1 vol%) at the normal incoming crude oil flow rate of 195 (kbbl/day)

Evaluation the performance of the tin (IV) oxide (SnO2) in the removal of sulfur compounds via oxidative-extractive desulfurization process for production an eco-friendly fuel

YesCatalysts play a vital role in petroleum and chemical reactions. Intensified concerns for cleaner air with strict environmental regulations on sulfur content in addition to meet economic requirements have generated significant interests for the development of more efficient and innovative oxidative catalysts recently. In this study, a novel homemade nano catalyst (manganese oxide (MnO2) over tin (IV) oxide (SnO2)) was used for the first time as an effective catalyst in removing dibenzothiophene (DBT) from kerosene fuel using hydrogen peroxide (H2O2) as oxidant in catalytic oxidative-extractive desulfurization process (OEDS). The catalyst was prepared by impregnation method with various amount of MnO2 loaded on SnO2. The oxidation step was carried out at different operating parameters such as reaction temperature and reaction time in batch reactor. The extractive desulfurization step was performed by using acetonitrile as solvent under several operating conditions (agitation speed and mixing time). The activity of MnO2/SnO2 catalyst in removing various sulfur compounds from kerosene fuel at the best operating conditions was investigated in this work. The results of the catalyst characterization proved that a high dispersion of MnO2 over the SnO2 was obtained. The experiments showed that the highest DBT and various sulfur compounds removal efficiency from kerosene fuel under the best operating conditions (oxidation: 5% MnO2/SnO2, reaction temperature of 75 0C, and reaction time of 100 min, extraction: acetonitrile, agitation speed of 900 rpm, and mixing time of 30 min) via the catalytic oxidative-extractive desulfurization process was 92.4% and 91.2%, respectively. Also, the MnO2/SnO2 catalyst activity was studied after six consecutive oxidation cycles at the best operating conditions, and the catalyst prove satisfactory stability in terms of sulfur compounds removal. After that, the spent catalyst were regenerated by utilizing different solvents (methanol, ethanol and iso-octane), and the experimental data explained that iso-octane achieved highest regeneration efficiency.This study was supported by College of Petroleum Processes Engineering, Tikrit University, Iraq and Ministry of Oil, Iraq

Economic feasibility of an integrated semi-batch reactive distillation operation for the production of methyl decanoate

NoThe formation of methyl decanoate (MeDC) by esterification reaction of decanoic acid with methanol through batch/continuous reactive distillation columns is operationally challenging, energy intensive and thus cost intensive operation due to complex thermodynamic behaviour of the reaction scheme. Aiming to overcome the equilibrium restriction of the decanoic acid (DeC) esterification operation, to improve the process efficiency and to reduce the total annualised cost (TAC), the semi-batch distillation column (SBD) and the recently proposed integrated semi-batch distillation column configuration (i-SBD) are investigated here. The performances of each of these column operations are evaluated in terms of minimum TAC for a given separation task. In both column configurations, additional operating constraints are considered into the optimization problem to prevent flooding of still pot due to the continuous charging of methanol into it. This study shows the superiority of i-SBD mode of operation over SBD operation in terms of TAC. Also, the optimization results for a defined separation task indicate that the performance of multi-interval control policy is overwhelmingly superior to the single-interval control operation in terms of operating batch time, and overall annual cost in the i-SBD system providing about a time saving of 82.75%, and cost (TAC) saving of 36.61% for a MeDC (product) concentration of 0.945 molefraction