Evaluation of a two-temperature control structure for a two-reactant/two-product type of reactive distillation column

Several different control structures have been proposed for reactive distillation columns. The appropriate control structure depends on the flowsheet and on the type of reactions occurring in the column. If two reactants are involved and if it is desirable to operate the process without any excess of reactant, it is necessary to manage the fresh feed streams so that the stoichiometry is exactly balanced. A composition analyzer that measures an internal composition in the column is often required. However, if two products are produced, it is possible to avoid the use of an analyzer by using two temperatures in the column to adjust the two feed streams. This type of structure was proposed by Roat et al. [Roat, S., Downs. J., Vogel, E., Doss, J., 1986. Integration of rigorous dynamic modeling and control system synthesis for distillation columns. In: Chemical Process Control—CPC III. Elsevier, Amsterdam.] for the ideal reaction A+B↔C+D in one of the earliest papers dealing with reactive distillation control.The purpose of this paper is to explore the effectiveness of this two-temperature control structure for various column designs (number of reactive stages) to quantify the impact of design on controllability. We also discuss the issues of the selection of the trays whose temperatures are to be controlled and the tuning of the two interacting temperature controllers. Disturbances in production rate and fresh feed compositions are made to examine the rangeability of this control structure. Both an ideal reaction system and the methyl acetate system are studied. One of the main conclusions is that the locations of the temperature control trays should be made such that the two temperature controllers both have direct action (an increase in temperature increases feed), which requires negative openloop process gains for both loops.     

Multiple steady states in two-phase reactors under boiling conditions

In this paper, we analyze the nonlinear behavior of two-phase reactors under boiling conditions. First we focus on a simple nth-order reaction of the form A→B, which allows a rigorous analytical treatment. Three necessary conditions for the existence of multiple steady states have been identified: the reactant A has to be the light-boiling component, the difference in boiling point temperatures between the reactant A and the product B has to be sufficiently large, and the order of the reaction has to be less than some physical parameter α. This parameter α can be interpreted as a measure for the phase-equilibrium-driven self-inhibition of the reaction mechanism. Thus, we have found an elegant explanation for the occurrence of multiplicities. Analytical and therefore general quantitative criteria identifying the regions of multiplicity for the model system are presented. Practical relevance of our results is demonstrated by means of two examples, the Monsanto process for the production of acetic acid and the ethylene glycol reactive distillation system.     

Process alternatives for methyl acetate conversion using reactive distillation. 1. Hydrolysis

In a polyvinyl alcohol (PVA) plant, reaction stoichiometry indicates that equal molar of methyl acetate is generated for every mole of PVA produced. This work explores an alternative to convert methyl acetate back to acetic acid (raw materials of PVA plant), methyl acetate (MeAc) hydrolysis. The design and control of methyl acetate hydrolysis using reactive distillation is studied. Because of the small chemical equilibrium constant (∼0.013) and unfavorable boiling point ranking (MeAc being the lightest boiler), the reactive distillation exhibits the following characteristics: (1) total reflux operation and (2) excess reactant (water) design. The proposed flowsheet consists of one reactive distillation column with a reactive reflux drum, two separation columns, and one water-rich recycle stream. A systematic design procedure is used to generate the flowsheet based on the total annual cost (TAC). Two dominate design variables are: recycle flow rate (for the degree of excess in water) and the overhead impurity level of acetic acid in the product column (to avoid tangent pinch). Finally, the operability of the hydrolysis plant is evaluated. A plantwide control structure is developed followed by process identification and controller tuning. The results show that reasonable control performance can be achieved using simple temperature control for feed flow and feed composition disturbances.     

Design and control of reactive distillation–recovery distillation flowsheet with a decanter for synthesis of N-propyl propionate

Reactive distillation (RD) for the synthesis of n-propyl propionate (ProPro) is operated with an excess of the reactant n-propyl alcohol (ProOH). It is simulated as a two-column system which can be easily controlled compared with a single reactive column which is operated neat, because the recovery column acts conceptually as a composition analyzer. The optimal steady-state design of the two-column system with the minimal total annual cost (TAC) is screened first. Then, an effective control scheme is established to handle feed disturbances. Only tray temperatures are required in the dynamic control two-column process. The product purity is held close to the set value 99.5 mol% and large deviation is prevented.     

Controllable optimized designs of an ideal reactive distillation system using genetic algorithm

The steady state economic optimization to obtain the most economical controllable design of a double feed ideal reactive distillation (RD) column is demonstrated using real coded genetic algorithm. The novelty of the work is in the development of a simple procedure based on steady state criteria for controllability. The optimization is performed for four scenarios corresponding to a sequential increase in the number of design variables. Results show that limiting the optimization search space to only those designs that satisfy the controllability criteria leads to optimized designs that are only slightly (<2%) more expensive than the most economical design without controllability considerations. The former designs however exhibit much better controllability in terms of effectively handling a large through-put change using two-point temperature inferential control and avoiding a steady state transition under open loop operation. Results also show that the location of the fresh feeds is a dominant design variable with designs that do not constrain the feed tray location to be immediately above and below the reactive zone being substantially more economical.     

Hybrid Simulated Moving Bed Processes for the Purification of p‐Xylene

Abstract

A parallel two‐zone and four‐zone SMB hybrid process was developed for p‐xylene purification. By placing a high‐productivity parallel two‐zone SMB in front of an existing four‐zone SMB, feed was enriched in the parallel two‐zone SMB before it was fed to the four‐zone SMB, which allows a higher feed rate to the four‐zone SMB. A general design procedure for hybrid SMB‐SMB process was developed. Simulations were done with Aspen Chromatography and Aspen Plus. Overall adsorbent productivity was increased by more than 100%, but with 3–5% lower overall p‐xylene recovery. With overall recovery of the hybrid process matching the base case, the feed rate was doubled and the overall adsorbent productivity was 50% higher than the base case. The heat duties of distillation columns per unit product were similar for these hybrid processes compared to the base case. If a two‐feed raffinate distillation column was used, the heat duty of distillation columns per unit product in the hybrid process was 2–4% lower than the base case. Both parallel two‐zone and four‐zone SMBs were also developed for use in a hybrid SMB‐crystallization process for p‐xylene purification. SMB productivity can be increased from 31% to 75% by adding additional pumps between columns to operate columns at their pressure limits. Although additional pumps are useful for both systems, the productivities of the parallel two‐zone SMBs were 9% and 16% higher than the corresponding four‐zone SMBs with the same number of recycle pumps. For a four‐zone SMB with two columns per zone and eight recycle pumps, a 114% increase of productivity was achieved, which is 22% higher than a parallel two‐zone with one column per zone and four recycle pumps.     

Analysis of coal-derived liquid obtained by mild hydrogenation: 1. Neutral oil distilling at 186–343 °C

Taiheiyo coal (77% C) was hydrogenated under mild conditions to preserve the unit structure of the parent coal as far as possible. The n-hexane-solubles (yield, 49.8 wt% daf coal) were washed with acid and base and the neutral material separated into 7 fractions by vacuum distillation. The three lower boiling fractions, DS01 (7.3 wt% neutral oil), DS02 (3.6 wt%) and DS03 (4.8 wt%), were further separated by liquid chromatography into hydrocarbon subfractions which were analysed by g.c. and g.c.-m.s. Saturates are most abundant, especially the n-alkanes which comprise ≈9–13 wt% of each fraction. The saturates also contain isoprenoids (C₁₅, C₁₆, C₁₈, C₁₉ and C₂₀), branched alkanes, n-alkyl cyclohexanes, terpanes and others. With increasing boiling point, smaller amounts of monoaromatic ring hydrocarbons and more di- or triaromatic ring hydrocarbons are found. The alkyl side-chains of aromatic nuclei have a large carbon number, especially in the smaller rings. The existence of phenyltetralin or phenylnaphthalene shows a feature of bonding between aromatic nuclei.     

Effects of operation variables on the recovery of lactic acid in a batch distillation process with chemical reactions

In this study, the feasibility of recovery of lactic acid by batch reactive distillation using cation exchange resin as a catalyst was investigated. For the recovery of lactic acid, two reactions, esterification and hydrolysis, are involved and hence, an apparatus with two distillation columns was developed and operated in a batch mode to ensure enough residence time in the reboiler and column. The effects of operation variables such as catalyst loading, reactant mole ratio, feed concentration, type of alcohols and partial condenser temperature on the yield were studied. In this study, the reaction products of the esterification (methyl lactate and water) were distilled to the hydrolysis part to be recovered into pure lactic acid. The yield of lactic acid increased as catalyst loading in the esterification part increased and reactant mole ratio and feed lactic acid concentration decreased. Methanol as a reactant gave higher yield than any other alcohols. The yield of recovered lactic acid was as high as 90%. The yield of lactic acid was closely related to the boiling temperature of the reaction mixture in the esterification part     

Ultra-deep desulfurization of coker and straight-run gas oils: Effect of lowering feedstock 95% boiling point

Production of diesel fuels with ultra-low-sulfur levels by deep desulfurization of gas oil feeds has received considerable importance in the petroleum refineries in recent years. The type of the gas oil feed and its distillation temperature play a key role in the deep desulfurization process. In the present research project, the effect of lowering the 95% distillation temperature (T₉₅) of two gas oil feeds, namely, straight-run gas oil (SRGO) and coker gas oil (CGO), on deep desulfurization to ultra-low-sulfur levels was investigated. The results showed that for both types of feeds a higher degree of desulfurization was achieved with reduction of T₉₅ from > 360 °C to < 340 °C. The refractory alkyl dibenzothiophenes boiling above 320 °C were present in very low concentrations in the low-boiling cuts and deep HDS to ultra-low-sulfur levels (< 50 ppm) was achieved at low severity operating conditions. Among the two feeds, the CGO that contained high nitrogen content, high concentrations of sterically hindered alkyl DBTs and high aromatics content (low feed saturation) was more difficult to desulfurize than SRGO.     

Integrated design and control of reactive distillation processes using the driving force approach

Superior controllability of reactive distillation (RD) systems, designed at the maximum driving force (design-control solution) is demonstrated in this article. Binary or multielement single or double feed RD systems are considered. Reactive phase equilibrium data, needed for driving force analysis and design of the RD system, is generated through an in-house property prediction tool. Rigorous steady-state simulation is carried out in ASPEN plus in order to verify that the predefined design targets and dynamics are met. A multiobjective performance function is employed to evaluate the performance of the RD system in terms of energy consumption, sustainability metrics (total CO₂ footprint), and control performance. Controllability of the designed system is evaluated using indices like the relative gain array (RGA) and Niederlinski index (N_I ), to evaluate the degree of loop interaction, as well as through dynamic simulations using proportional-integral (PI) controllers and model predictive controllers (MPC). The design-control of the RD systems corresponding to other alternative designs that do not take advantage of the maximum driving force is also investigated. The analysis shows that the RD designs at the maximum driving force exhibit enhanced controllability and lower carbon footprint than the alternative RD designs.     

A fed-batch design approach of struvite system in controlled supersaturation

This paper focuses on struvite (MgNH₄PO₄·6H₂O) crystallization in controlled supersaturation. Struvite can be used as a slow-release fertilizer. Crystallization experiments were conducted using supersaturated solutions. The secondary focus of this paper is the design of a struvite recovery system in fed-batch-controlled supersaturation mode. The design and commissioning of fed-batch struvite crystallization included the determination of operating supersaturation of struvite crystallization, suitable seed materials and the composition of feed solution. Determination of operating supersaturation of struvite crystallization was conducted by two steps including thermodynamic simulation using gPROMS² (process simulation software) along with a set of batch experiments. Investigation of suitable seed materials was also conducted using set of batch experiments. Two types of seed materials including quartz sand and struvite seeds were used in the investigation of seed materials. Composition of feed solution included the investigation of struvite solution chemistry using PHREEQC³ thermodynamic modeling package. Based on the previously investigated design approach, struvite crystallization in fed-batch system was conducted using a 44-L of reactor with 15-L of initial reactant volume.     

Recovery of volatile compounds from butter oil

Three methods for the isolation of volatile compounds from oils and fats were compared using small concentrations (approximately 1 ppm) of added C_3-12 n-alkan-2-ones and C_2-10 n-alkan-1-ols in commercial butter oil. These were : high vacuum degassing, cold-finger molecular distillation and reduced pressure steam distillation. Several modifications were incorporated. The highest yields of all compounds were obtained by cold-finger molecular distillation but difficulties were encountered in subsequent analysis. It was more convenient to recover compounds boiling below 150C by either high vacuum degassing or reduced pressure steam distillation. The latter was more efficient for the higher boiling compounds. Extraction with organic solvents was not required in any of these techniques. The combination of high vacuum degassing and cold-finger molecular distillation was found to be the best method of analyzing the complete range of model compounds.     

Effect of Changes in Operating Variables on Stage-wise and Cumulative Separation in Binary Multistage Distillation

Abstract

The progressive separation that occurs stage-wise within a multistage distillation column is characterized by the cumulative extent of separation, ζ _N ; while the contribution of individual stages, δ _N , to the overall separation is given by the difference between ζ _N for successive stages. These indexes permit the “goodness” of separation for individual stages and for the entire column to be compared on an equivalent basis. This paper examines the effects of changing operating variables of reflux ratio, feed rate, feed composition, and feed stage location on the separation obtained in a distillation column containing a fixed number of ideal stages, and how the single-stage contribution changes when these variables are altered from the design value. The calculations show that the reflux ratio (R) is probably the most important variable in determining how well a column makes a separation. Separation declines rapidly as R is reduced below the design value, as the feed rate is increased at constant boil-up rate, and as the feed concentration drops below the design value. Changing the feed stage location of ±5 stages in a 50-stage column has a minimal effect on separation at all feed compositions. δ _N clearly shows how the contribution of individual stages changes when operating variables are varied from the design values.     

Reactive distillation-pervaporation hybrid column for tert-amyl alcohol etherification with ethanol

The etherification of tert-amyl alcohol with ethanol was carried out in a reactive distillation column inserted by a zeolite NaA membrane tube. Experimental tests were carried out in both of a pervaporation module and a reactive distillation column. Under suitable conditions, the pervaporation tests have shown higher than 99.9% H₂O mole fraction in the permeate. The design by the residue curve maps has shown the alleviation of azeotropes of H₂O-reaction components mixtures under pervaporation. The experimental study at standard conditions has shown a gain of 10% in tert-amyl ethyl ether (TAEE) yield when the zeolite membrane tube was inserted inside the distillation column. Further improvements in TAEE yield were realized when the feed location was separated and the time factor or the reflux ratios was increased.     

Optimization and control of a reactive distillation process for the synthesis of dimethyl carbonate

Dimethyl carbonate is an environmentally benign and biodegradable chemical. Based on integration of reactive distillation and pressure-swing distillation technologies, a novel process for synthesis of dimethyl carbonate through transesterification with propylene carbonate and methanol has been developed by Huang et al. In this work, the optimization of this process was performed by minimizing the total TAC. The results show that the op-timal design flowsheet can save energy consumption by 18.6％with the propylene carbonate conversion of 99.9％. Then, an effective plant-wide control structure for the process was developed. Dynamic simulation results dem-onstrate that the temperature/flow rate cascade control plus with simple temperature control can keep not only product purity but also the conversion of the reactant at their desired values in the face of the disturbance in re-actant feed flow rate and feed composition.     

Process Intensification for the Recovery of Hydrogen Cyanide in the Andrussow Process

The aim of this work was to determine a cost-optimal design of the distillation unit of the Andrussow process. For this purpose, a feed with a mass flow rate of 121 t h⁻¹ and a concentration of ca. 2 wt % hydrogen cyanide (HCN) was considered. An approach for a cost-optimal process intensification was developed with the goal to achieve the desired product qualities, while minimizing the organonitrile accumulation in the column. For this purpose, the simple distillation column of the established cost-optimal design of the base case was extended to a configuration with a side stripper with taking into consideration heat integration in the process. It was found that this new configuration allows a much smaller accumulation of organonitriles in the main column; reducing thereby the operation issues of the process while decreasing considerably the total annual cost of the distillation unit by 61 % as compared to that of the base case design.     

Reactive extraction of 2,3-butanediol from fermentation broth

Biochemical 2,3-butanediol is a renewable material, but the lack of an effective separation process limits its industrial application. We developed an effective separation process to recover 2,3-butanediol from fermentation broth by reactive-extraction with ion-exchange resin HZ732 as catalyst. n-Butylaldehyde was used as both reactant and extractant. Feasible operation conditions were obtained as follows: room temperature, C _cat =200 g·L^?1, three-stage cross-current extraction, with reactant ratio (V _{Butylaldehyde} : V _{fermentation broth} ) 0.05 for each stage. Reactive-extraction can recover over 98% of 2,3-butanediol in the form of 2-propyl-4,5-dimethyl-1,3-dioxolane from fermentation broth. Then 2,3-butanediol was obtained by hydrolyzing 2-propyl-4,5-dimethyl-1,3-dioxolane and purified by vacuum distillation. The total yield rate of 2,3-butanediol through the process was over 94% and purity of final product reached 99%.     

Structural design of fully thermally coupled distillation column using approximate group methods

The thermally coupled distillation column systems can save energy and capital cost compared with traditional distillation columns. Since the thermally coupled column system was introduced, the design concerns have been peeped out due to more degrees of freedom. This paper introduces a new design method that can be used to determine the structure of thermally coupled distillation column systems, namely the number of stages in all sections of the column system. The design method employs the approximate group methods. To explore the design performance of the proposed design method, three feed systems are analyzed to investigate its usefulness. The design procedure gives the optimum structure for a given ternary separation; with given product specifications various design methods can yield approximately the same results. Like structure designs, the optimal internal flow distributions are examined. The results indicate that the method works well for a variety of process conditions.     

A reactive distillation process with a sidedraw stream to enhance the production of isopropyl acetate

This paper designs an entrainer combined with a sidedraw to enhance the reactive distillation (RD) process of isopropyl acetate (IPAc). Acetic acid (HAc) reacts with isopropanol (IPOH) to generate IPAc and water (H₂O). The ratio of IPAc to H₂O in the products of esterification is smaller than that in the minimum boiling IPAc–IPOH–H₂O azeotrope, resulting in a mass of organic phase reflux to remove the surplus H₂O from the top of the RD column. This process consumes a high amount of energy. For better energy efficiency, a feasible design flowsheet includes an RD column, a stripper, a top decanter, a middle decanter, and a sidedraw stream to intensify the azeotropic separation where an entrainer is introduced to carry out the surplus water from the middle of the RD column in the form of a liquid phase. The key design variables in the proposed flowsheet are determined to obtain a minimal total annual cost (TAC). As a result, an optimal process design is drawn out while satisfying the stringent specifications for product purity. These results show that the energy requirements of the IPAc system can be decreased by 27.55%.     

Methodology for design and analysis of reactive distillation involving multielement systems

A new methodology for design and analysis of reactive distillation has been developed. In this work, the element-based approach, coupled with a driving force diagram, has been extended and applied to the design of a reactive distillation column involving multielement (multicomponent) systems. The transformation of ordinary systems to element-based ones and the aggregation of non-key elements allow the important design parameters, such as the number of stages, feed stage and minimum reflux ratio, to be determined by using simple diagrams similar to those regularly employed for non-reactive systems consisting of two components. Based on this methodology, an optimal design configuration is identified using the equivalent binary-element-driving force diagram. Two case studies of methyl acetate (MeOAc) synthesis and methyl-tert-butyl ether (MTBE) synthesis have been considered to demonstrate the successful applications of the methodology. Moreover, energy requirements for various column configurations corresponding to different feed locations are determined to verify whether the optimal design can be identified by following the proposed methodology.