Professional Documents
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Evaluation of PROSYN
ISPT Techno project CS-02-06
Authors: Kees de Weerd (PDC) Johan Romme (PDC) Raf Roelant (PDC) Bhaskar Patil (TUD) Jorge Andres Moncada (TUD)
Stichting Public Private Partnership-ISPT Visiting and postal address Groen van Prinstererlaan 37 3818 JN Amersfoort The Netherlands +31 (0)33 700 97 97 info@ispt.eu www.ispt.eu Accounting postal address ISPT, Accounting Dept. P.O.Box 247 NL-3800 AE Amersfoort The Netherlands KvK 09156999
Distribution: A. ten Cate (ISPT Amersfoort) P. Hauwert, F. Vergunst (Frames Gas Processing B.V. Alphen aan den Rijn) E. Poiesz (Cosun Food Technology Center - Roosendaal) M. Eppink, Mrs. M. Liu (Synthon - Nijmegen) A.J. Zeeuw, E. Keane (Huntsman - Everberg, Belgium) R. Noordman, J. Risselada (Heineken Zoeterwoude)
November 2011
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TABLE OF CONTENTS
1 2 3 4 5 6 SUMMARY .................................................................................................................................... 3 INTRODUCTION ........................................................................................................................... 4 MOTIVATION ................................................................................................................................ 4 PROJECT OBJECTIVE ................................................................................................................ 5 SCOPE OF WORK ....................................................................................................................... 5 RESULTS AND EVALUATION .................................................................................................... 6 6.1 6.2 6.3 6.4 7 Evaluation Criteria ................................................................................................................ 6 Results ................................................................................................................................. 8 Conclusions ........................................................................................................................ 10 Recommendations ............................................................................................................. 11
CASE STUDIES .......................................................................................................................... 12 7.1 7.1.1 7.1.2 7.1.3 7.1.4 7.1.5 7.1.6 7.1.7 7.1.8 7.2 7.2.1 7.2.2 7.2.3 7.2.4 7.2.5 7.2.6 7.2.7 7.2.8 7.3 7.3.1 7.3.2 7.3.3 7.3.4 CASE 1 - Huntsman Separation of MDA / Aniline / water mixture .................................. 12 Process description ......................................................................................................... 12 Design objective .............................................................................................................. 12 Basic Assumptions .......................................................................................................... 12 Results ............................................................................................................................ 13 Evaluation of results ........................................................................................................ 14 Assessment of the Design Process ................................................................................ 16 Conclusions ..................................................................................................................... 17 Recommendations .......................................................................................................... 17 CASE 2 - Frames Removal of Sulfur from Water by using solvent ................................ 18 Process description ......................................................................................................... 18 Design objective .............................................................................................................. 18 Basic Assumptions .......................................................................................................... 18 Results ............................................................................................................................ 18 Evaluation of the results .................................................................................................. 21 Assessment of the Design Process ................................................................................ 22 Conclusions ..................................................................................................................... 23 Recommendations .......................................................................................................... 23 CASE 3 - Synthon production and separation of antibodies ........................................... 24 Process description ......................................................................................................... 24 Design objective .............................................................................................................. 24 Basic Assumptions .......................................................................................................... 24 Results ............................................................................................................................ 24
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Evaluation of results ........................................................................................................ 27 Assessment of the Design Process ................................................................................ 28 Conclusions ..................................................................................................................... 29 Recommendations .......................................................................................................... 29
7.4 CASE 4 - Cosun Treating of wastewater containing: Nitrogen, Phosphate and Potassium from wastewater. ......................................................................................................................... 30 7.4.1 7.4.2 7.4.3 1.1.1 7.4.4 8 9 Process description ......................................................................................................... 30 Design objective .............................................................................................................. 30 Results ............................................................................................................................ 31 Assessment of the Design Process ................................................................................ 32 Conclusions ..................................................................................................................... 33
REFERENCES ............................................................................................................................ 34 APPENDICES ............................................................................................................................. 35 9.1 9.1.1 9.1.2 9.1.3 9.1.4 9.1.4.1 9.1.4.2 9.1.4.3 9.2 9.2.1 9.3 9.3.1 9.3.2 9.3.3 9.3.4 9.4 9.4.1 9.4.1.1 9.4.1.2 9.4.1.3 9.4.2 9.4.3 Appendix 1: Huntsman case .............................................................................................. 35 MEMPERT: Membrane Processes ................................................................................ 35 LILEX and SOLPERT: Liquid-Liquid Extraction with reflux: ............................................ 36 CRYSPERT: to simulate and evaluate Crystallization .................................................... 37 TEAGPERT: Conventional distillation and extractive distillation .................................... 41 Simple distillation of nonideal mixtures ........................................................................ 42 Homoazeotropic distillation with internal recycle ......................................................... 42 Extractive distillation with mass agent.......................................................................... 43
Appendix 2: Frames case .................................................................................................. 45 PROCEDURE used for SOLPERT: ................................................................................ 45 Appendix 3: Synthon case ................................................................................................. 47 Step: 1 General Reactor Type: .................................................................................... 47 Step: 2 Operating conditions. ......................................................................................... 48 Step: 3 TECHNICAL REACTOR: .................................................................................... 49 Step: 4 - The HEAT TRANSFER can be investigated. ................................................... 51 Appendix 4: Cosun case .................................................................................................... 52 BIKOM Module ................................................................................................................ 52 Regeneration of Nitrogen: ............................................................................................ 52 Removal of phosphate ................................................................................................. 52 Regeneration of potassium .......................................................................................... 54 BIKOM - WASTE water treatment steps ......................................................................... 55 MEMPERT Module.......................................................................................................... 56
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SUMMARY
The project objective is to evaluate the current opportunities for the commercial use of PROSYN in Conceptual Process Design. The evaluation of PROSYN is carried out by relatively inexperienced designers using the PROSYN software package in its current state of maintenance. In order to achieve this objective, 4 industrial case studies from 4 different sectors of the chemical industry have been used. The case studies are given by Huntsman, Frames gas processing B.V., Synthon and Cosun. The results obtained for these case studies using PROSYN have been evaluated according to the following evaluation criteria; Design method, user friendliness, time and effort spent, and efforts needed for improvement and update of the PROSYN. PROSYN generated four alternatives to separate the mixture MDA-aniline-water described in the Huntsman case study. By implementing pervaporation and crystallization it is possible to reach the specifications of purity required. Regarding the Frames case study, where it is needed to remove sulfur from water, PROSYN was able to find a list of promising solvents, but PROSYN was unable to rank the solvents. The Synthon case is focused on the generation of reactor and separation options for a biochemical reaction. PROSYN was able to generate the list of suitable reactor configurations for the given reaction conditions, but it was not able to generate separation sequences for the separation of the very complex molecules such as antibodies and proteins mainly because of lack of data and absence of a PROSYN module for downstream processing. In the Cosun case study a method for the recovery of nitrogen, phosphate and potassium from a wastewater is required. PROSYN produced a list of suitable processes such as: gas stripping for the nitrogen recovery and sequences such as: electrodialysis followed by ion exchange for the potassium. PROSYN is a very valuable tool for the initial stage of conceptual process design that can be used by relatively inexperienced designers and it guides the designer through the conceptual design steps. Different feasible alternatives were proposed in a very short time and few efforts were required for each case study. PROSYN has an large database, generic knowledge, rules of thumb, heuristics, and numerical system for process synthesis. The PROSYN tool however needs to be updated for the content and some modules have to be patched to provide full functionality. PROSYN requires serious efforts in its further development and improvement before it can be sold to clients, especially its user interface needs improvement
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INTRODUCTION
In 2011 a Techno Project was initiated by ISPT to assess the value of the PROSYN software tool of PDC for the chemical process industry. Emphasis was put on the significance for the industry related to the food and pharmaceutical sector. A number of industrial participants were invited to join this project. This Techno Project will serve as a pre-project for a new ISPT project in 2012 which will have a broader focus. Also more industrial participants will participate in this latter project. PROSYN is a process synthesis software tool for an optimal conceptual process design. PROSYN contains heuristics, rules of thumb, databases and numerical tools, to assist in creating more resource and energy efficient process designs. PROSYN has been developed in the 1990s in Dortmund University, Germany, mostly in an academic environment. PROSYN has 15 different modules with 1 central PROSYN manager for process design. PROSYN has been used in more than 100 industrial projects [1]. This ISPT Techno Project deals with the evaluation of PROSYN for different type of processes given by future industrial end users of this software. Four industrial case studies from four different sectors of chemical industry have been used to evaluate PROSYN. This includes case studies from Huntsman, Frames gas processing B.V., Synthon and Cosun. Objective of Huntsman case study is to generate separation schemes for ternary mixture of MDA-Water and Aniline. The Frames case objective is to select the solvent to remove sulfur from waste stream. Objective of the Synthon case study is to generate the reactor and separation options for the enzymatic reaction. The case study from Cosun has the objective to recover the components containing N, P, K from a waste stream. Detailed descriptions about each case study containing case description, obtained results, evaluation of results and experiences in the design process are given in detail in the case study section of this report.
MOTIVATION
The PROSYN expert system is quite unique in the world of Computer Aided Process Engineering. Conventionally new processes are developed by reusing existing ideas, usually based on company preferences or personal judgments. These do not necessarily lead to the best, i.e. most economical production plant. Even in highly constrained situations, PROSYN lowers the risk that the value of fruitful ideas is not captured. PROSYN is a very valuable tool for the initial stage of conceptual design to generate large number of feasible process options. PROSYN requires a serious initial development effort to be able to properly access all existing PROSYN knowledge rules & modules next to the embedding of additional knowledge rules in existing modules or new modules.
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PROJECT OBJECTIVE
The project objective is to evaluate the current opportunities for the commercial use of PROSYN in Conceptual Process Design. Focus of the current project is to assess the technical feasibilities of using PROSYN by third parties without the intervention of PDC. Evaluation criteria are the use of PROSYN by relatively inexperienced designers and the current state of maintenance of PROSYSN. Previously PROSYN was not directly used by industrial companies but only with the mediation of special designers experienced in the use of PROSYN. Good state of maintenance of PROSYN is a prerequisite for third party use.
In the current project 2 Professional Doctorate in Engineering (PDEng) trainees are used to carry out a number of specially selected case studies. By means of the case studies they will establish whether it is possible to obtain meaningful design results with the aid of PROSYN. The results are discussed with the owner of the case study. Moreover they will establish the area of application of PROSYN.
SCOPE OF WORK
Scope of this project is to evaluate and report PROSYN performance for four case studies obtained from four different industries i.e. Huntsman, Frames, Synthon, and Cosun. The scope of the project is divided into overall scope of the project and the scope of the individual case studies. The overall scope of work comprises: Learning to work with PROSYN Defining a framework for evaluation Evaluation criteria Defining a common layout for reporting all case studies Individual Case studies Combined evaluation Reporting Presentation at NPS11
For the individual case studies the work comprises: 1. Preparing a Process Description: Defining the state of the art Identifying the challenges, bottlenecks and opportunities for innovation in the process 2. Performing a PROSYN session: Defining the case components Selection physical properties method Selecting the PROSYN Module Intermediate Design Decisions Evaluation of results (with PDC) Reporting 3. Presentation of results and discussion with the case owner 4. Final evaluation and formal reporting
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6.1
In order to assess the feasibility of application of PROSYN by third party designers a number of criteria have been defined. The first set of criteria is related to the primary qualities of PROSYN. Does it deliver what it is designed to do? Generate the design options for conceptual process design and assess their feasibility. In order to get meaningful criteria the design structure of the Delft Design Matrix was used. Different steps generally followed in the conceptual process design according to the Delft Design Matrix [2] are: 1. Definition 2. Synthesis 3. Analysis 4. Evaluation 5. Reporting In the conceptual design for case studies, above mentioned design steps are used as the evaluation criteria for the PROSYN operations and results obtained. A second set of criteria is related to the secondary qualities of PROSYN. These qualities are more practical and related to the ease of use. User friendliness Time and effort needed Effort for improvement and update Design Method: A brief description of how PROSYN helps to designer to go through these stages is given below: 1. Definition: In this first stage of design, the scope and objective of design is established. PROSYN implicitly guides through defining the given problem. E.g. in all the cases, PROSYN asked to define the components, composition and process objective (reaction or separation scheme), etc. In the Huntsman case study, PROSYN manager asked about the selection between reaction and separation option. Clearly defining the design problem helps to evaluate and analyze the PROSYN results. 2. Synthesis: After defining the design problem, in this step of the design possible options for the given problem are synthesized. PROSYN came up with a number of surprising options in synthesizing all the possible options. For instance, in the Huntsman case PROSYN came up with 8 different unit operations. Similarly in the Frames case, PROSYN was able to generate list of potential solvents. In the Synthon case study, PROSYN proposed a number of potential reactors based on the conditions specified for the reaction. The spectrum of possibilities for process synthesis is not only limited to reaction and separation sections, but also wastewater treatment options can be generated. In the Cosun case, where the recovery of nitrogen, phosphate and potassium was needed, PROSYN provided a list of suitable processes and/or sequences. 3. Analysis: In the analysis stage of the conceptual design, all the synthesized options are analyzed by performing simulations. PROSYN is able to perform simulations for all of the alternatives generated. E.g. in both the Huntsman and the Cosun case studies it was possible to generate numerical results for all of the synthesized schemes. PROSYN is however not able to perform a sensitivity analysis.
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4. Evaluation: The performance of the schemes generated is investigated in the evaluation step of conceptual design. PROSYN facilitates evaluation of the synthesized schemes or equipment almost in all the modules. PROSYN can evaluate the generated options, but in some modules PROSYN does not give the complete information. E.g. in distillation design, it does not give the number of stages and energy consumption. 5. Reporting: The design decisions, rationales and results are documented by the designer in a final report. The heuristics for process synthesis used by PROSYN to generate the different schemes in all the case studies are unknown to the designer. So, reporting these heuristics is not possible, but PROSYN gives an overview of the design decisions and results at the end of the design process, which can be used for the purpose of documentation and reporting.
User Friendliness: User friendliness means ease of use of software and ease to navigate through it while designing a process. E.g. number of windows popping up when operating the program, possibility of saving the program in middle of the simulation. PROSYN is not very user friendly like windows, Aspen, etc. Time and Efforts needed: Software is helpful if it reduces the time and efforts of designer drastically, hence results and performance of PROSYN has been evaluated in terms of the time and efforts spend by the designer to reach the final solution. Using PROSYN, it is possible to reach the final solution in very short time and with relative little effort. E.g. the designer can select the suitable solvent in few hours using PROSYN, which would take weeks of manual work. Efforts for improvement and update: these criteria are used to evaluate the design process and PROSYN as whole to suggest improvements (operational and patching in modules) and updates (data, rules and models, etc). E.g. PROSYN is still using data, correlations, thermodynamics, laws and costing data which is 10-20 years old, therefore it must be updated.
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6.2
Results
Detailed results and evaluation for individual case study can be found in the case studies section. Only the summary of the results for the four case studies is given here. HUNTSMAN CASE: PROSYN identified a number of potential alternatives for the separation of MDA-Water-Aniline mixture such as pervaporation, liquid-liquid extraction, crystallization and distillation, etc. Rating of these separation processes by PROSYN manager is presented in table 1. Table 1 Rating of Unit Operations for MDA Water separation Unit Operations Rating
In principle it is possible to separate all the components of the mixture with 100% purity by using pervaporation. However, both the energy requirement (vacuum pump) and capital costs (membrane area) were high for the separation of MDA-Aniline mixture for pervaporation method. As an alternative for the second stage of pervaporation, liquid-liquid extraction and crystallization were used to separate the binary mixture of MDA and Aniline. Although the energy requirement was low for LLE, it was not possible to achieve the purity required. Finally, distillation processes which are indicated as less promising by PROSYN were studied to separate the ternary mixture. In the case of conventional distillation it is possible to achieve the required purity. However, both capital costs (number of stages) and operational costs (reboiler duty) were not indicated by the PROSYN TEAGPERT (close boiling components) module. On the other hand, the energy requirement can be improved by using extractive distillation, though another separation unit is needed to recover the solvent. FRAMES CASE: PROSYN identified a number of potential solvents for the removal of sulfur from water. This selection was realized based on criteria such as: boiling point, azeotropy, miscibility and polarity. Following these criteria PROSYN identified as promising solvents those found in the group V of Berg classification. The components selected from this group are listed in Table 2.
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Although the list of components generated by PROSYN for the removal of sulfur from water are feasible from technical point of view, other parameters such as biocompatibility, efficiency, and toxicity have not been considered in the solvent selection process. The solvent selection should fulfill both technical and environmental criteria. SYNTHON: PROSYN suggested some potential alternatives for reactor selection after analyzing the given reaction sequence by applying number of criterion such as reaction type, recycle structure, operation mode, feed options, product removal, heat supply/removal, pressure levels, yield, concentration of reactant feed, temperature levels, etc. Based on these criteria PROSYN generated a list of possible reactors to carry out the following assumed enzymatic reaction: A+B+E EAB EP P+E
The list of possible proposed reactors is presented below: 1. Tubular reactor 2. Reformer 3. Sulzer mixer-reactor 4. Draft tube 5. Stirred tank 6. Reactive distillation column 7. Multichamber tank 8. Falling-film reactor 9. Reactive crystallization, separation function In order to obtain feasible results for these kinds of biochemical reactions it is needed to supply data for the all components. However, it was not possible to generate the separation sequence for the given feed stream by using PROSYN because of the absence of data on the complex components and modules on downstream separation operations such as chromatography (adsorption chromatography, ion exchange chromatography, size exclusion chromatography, affinity chromatography, hydrophobic interaction chromatography, reversed phase chromatography, ion exchange chromatography), Adsorption, electrophoresis, etc.
COSUN: PROSYN provided a list of suitable processes and/or sequences and it suggests the
most preferred one for the recovery of nitrogen, phosphate, and potassium. Since PROSYN can handle streams with only one solute component, an analysis was done for each solute. The results are presented in Table 3:
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Also, it is possible to incorporate a membrane process as alternative for the recovery of the solutes. PROSYN suggested nanofiltration and reverse osmosis as the best potential option and pervaporation as less promising option. The PROSYN BIKOM (waste water treatment) module was able to generate the economic calculations for all the separation options produced, although the data in BIKOM is based on the German legislation on waste water for the year 1995. Moreover all prices are based on the DM currency.
6.3
Conclusions
Based on the Delft design matrix, it is concluded that PROSYN is a valuable tool that helps the designer in conceptual process design. PROSYN guides through the different steps of conceptual design such as analysis, synthesis, evaluation and reporting. In all 4 case studies PROSYN has generated number of ideas and concepts for separation, reactions and equipment, which are then evaluated and ranked by PROSYN according to the suitability.
PROSYN generated a list of plausible alternatives to separate the ternary mixture of MDAAniline-Water in a short time, which are energy efficient (i.e. pervaporation and crystallization) and are available for implementation. Although the information reported by PROSYN does not allow concluding which is the best alternative among all, it gives enough information for preliminary screening and necessary data for conceptual design stage and allows the designers to narrow down the spectrum of possibilities in the initial design process. Similarly in the Frames case PROSYN generated a list of interesting potential suitable solvents for extracting elementary sulfur from water. Hence it is concluded that using PROSYN, the procedure of conceptual process design is accelerated and many alternatives could be generated in very little time and relatively little efforts. Since PROSYN was designed to deal with problems of chemical and petrochemical industry, the solutions generated for problems from biochemical or food industry are less relevant. Moreover, because of the absence of modules on downstream separation processes in PROSYN, it is not possible to generate alternatives for separation regarding this specific sector of the chemical industries. In the Cosun case study PROSYN was not able to handle waste streams containing more than one contaminant. Also, the economic viability of the options found by PROSYN could not be compared directly as these options assumed different parameters for the economic calculations. So it is concluded that PROSYN needs more information technology (IT) effort to improve the available knowledge database and also it needs to be extended with data on current developments within the field (e.g. use of ionic liquids). PROSYN contains a relatively large amount of physical property data on chemical components, heuristics, rules of thumb and correlations. This helps a designer to generate and evaluate the plausible options, which reduces the time and efforts of a designer on searching literature and doing preliminary calculations. However, the PROSYN user interface is unattractive and the designer needs to put substantial efforts initially to understand the options and the flow of the program. It is concluded that the design process using PROSYN could be accelerated if a user-friendly interface, similar to Aspen Plus and windows, was implemented.
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6.4
Recommendations
During the case studies it appeared that it is relatively difficult to keep track of the decisions taken during the design process. The only way of keeping track of your navigation and design decisions is to separately make notes. This however disrupts the creative process of design and therefore it is recommended that PROSYN is adapted to keep track of the decisions by itself and show a decision tree visually on a separate tab sheet. As the designer needs to put some efforts initially to understand the options and flow of program it is recommended that PROSYN is extended with a user-friendly interface. Since PROSYN contains cost data, component data, correlations and thermodynamic models developed approximately 20 years back, it is recommended to upgrade all of this information to present status.
During the analysis of the case studies using PROSYN, it was found that some of the options in the main menu for some modules are not working. Hence, it is recommended that these modules should be implemented within PROSYN. Generating separation options for biochemical processes is not possible with the aid of PROSYN. It is recommended to build modules in PROSYN for unit operations such as chromatography and adsorption. Since the evaluation of all the modules built in PROSYN was not covered, it is recommended to carry out an evaluation of the modules that were not tested in this study such as: HEN (heat exchanger networks), HEATPERT (pinch technology), and others.
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7.1
CASE STUDIES
CASE 1 - Huntsman Separation of MDA / Aniline / water mixture
Huntsman produces MDA by a reaction of Formaldehyde with Aniline in the presence of Hydrochloric acid. From the process, a stream of MDA, Aniline and water has to be separated into a water / Aniline stream to be recycled and a MDA product stream to be purified. The separation is traditionally done with the aid of distillation and is very energy intensive. The challenge is to come up with separation technologies that makes step change in energy consumption and suggest a design which is energy efficient and which is available for implementation.
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7.1.2
Design objective
The current case study aims at generating different separation process options for the separation using PROSYN and to evaluate different PROSYN modules.
7.1.3
60 wt% MDA; 36.5 wt% Anilne; 3.5 wt% water 60 ton/h Ambient
Temperature 90C
Table 6: Product specifications Composition [ppm] Components < 200 Water < 50 Aniline Water/aniline < 1000 MDA Stream MDA
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7.1.4
Results
To generate different separation process options for separating the mixture of MDA-Water-Aniline using PROSYN, first the feed stream specification is entered in the PROSYN manager, which is capable of developing/synthesizing the complete flow-sheet and it can be used separately to develop reaction and separation sections. The main aim of the PROSYN manager is identify the potential separation options. Depending on the simulation results of the PROSYN manager, other modules (LILEX, MEMPERT, CRYSPERT, TEAGPERT, etc.) have been used and the results of all the modules used are summarized one by one in this section.
1. PROSYN Manager: All other PROSYN modules are connected to PROSYN manager and PROSYN manager calls the PROSYN modules (READPERT, LILEX, MEMPERT, CRYSPERT, TEAGPERT, etc) depending upon the problem requirement. PROSYN Manager allows evaluating many process alternatives in short time narrowing the spectrum of possibilities in the design process. This feature permits designers to focus on the most promising processes, saving time and resources. The results of determining the promising processes for given mixture separation are presented below:
Stream input data for feed Stream: temperature [K] 363.15 pressure [MPa] 0.1013 phase liquid flow [kg/h] 60000/533.3=112.5 [kmol/h] Table 7 gives the preliminary screening results given by the PROSYN manager based on the Phase conditions of the feed stream:
Next PROSYN manager starts the related modules to further investigate each of the unit operations. The result of this investigation by the PROSYN manager is given in the following table. Also a rating is provided by PROSYN:
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Detail results obtained using modules MEMPERT, LILEX, CRYSPERT and TEAGPERT are given in the Appendix A.
7.1.5 Evaluation of results
Pervaporation process; PROSYN MEMPERT (membrane separation) suggested that the first stage where water is removed from ternary mixture is feasible. For a hydrophilic membrane, water will have a stronger molecular affinity than aniline and MDA. Therefore, a separation of water from the ternary mixture (water-aniline-MDA) is possible and hence it is logical. On the other hand, PROSYN suggested that the second stage, where aniline has to be removed from MDA, is less promising. This result is accepted since MDA and aniline have the same molecular groups, the molecular affinity between the membrane and each component will be similar. Therefore, a sharp separation between those two components is not possible and it is less promising. PROSYN is able to calculate both operation and capital costs for the pervaporation process, but it was surprising that MEMPERT did not suggested the type of membrane for either of the separation stages. Also, the membrane database could not be accessed in the MEMPERT module. It is worth noting that mass transfer flux through membrane was calculated based on rules of thumb and not on the membrane properties. Since the membrane area depends on the mass transfer flux; capital costs predicted by PROSYN could be either underestimated or overestimated. MEMPERT provides an option to enter manually all the cost data and other parameters of membrane, so it is possible to perform calculations accurately if the relevant membrane data are known by the user. Liquid-Liquid extraction: as an alternative to separate the mixture MDA-aniline, a liquid-liquid extraction with reflux was proposed. 1-Octadecanol was selected as a solvent based on technical criteria such as: azeotrope formation, boiling points, polarity, etc. Environmental criteria were not implemented in the selection. Criteria such as: toxicity, biocompatibility among others should however be considered in the solvent selection. In order to evaluate the validity of the results obtained by PROSYN in the design of liquid-liquid extraction with reflux, one of the most important
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parameters such as: solvent/feed ration was compared with the results reported in the literature for another system [3]. It was found that this parameter is similar to values reported in the literature. In principle, the results reported by PROSYN are plausible. PROSYN selected the best scheme to carry out a liquid-liquid extraction with reflux. However, this evaluation was only based on technical criteria. Economic considerations were not taken into account. Crystallization: the results obtained by CRYSPERT (crystallization module) are very useful in the first stage of checking feasibility of this process. As melting point of MDA is relatively high (T=92.5oC), it apparently seems that crystallization is possible and has been confirmed by the CRYSPERT results. But, to check the applicability of crystallization, experiments are required. The eutectic diagram and data generated by CRYSPERT are very useful in doing the detailed calculations later on. The CRYSPERT module does not calculate the capital and operating cost for the crystallization process. Distillation: The option of homoazeotropic distillation with internal recycle generated by TEAGPERT (close boiling components) was a surprising result and in first instance it was omitted by the users. In extractive distillation, the SOLPERT module was used to select the solvent. Environmental criteria were not considered in selecting and screening of the solvents. Although in principle, both simple distillation and homoazeotropic distillation seem to be the best option for schemes generated by TEAGPERT module, no conclusions can be drawn since both capital and operative costs could not be calculated by the PROSYN TEAGPERT module. Energy consumption and economical evaluation options need to be implemented in this module. PROSYN is a useful tool for process designers in the initial stages of design since it allows evaluating many process alternatives in short time. Also, the results obtained by the system expert are plausible. This feature permits designers to focus on the most promising processes, where more specified criteria (economic, environmental, and HSE) must be applied in later stage.
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7.1.6
PROSYN has a vast physical properties database of compounds and contains many correlations. This enables fast and easy calculations of options available. Ultimately it saves time and effort in the design process. PROSYN allows generating and evaluating process in a short time (2-3 hours), however to input the information to PROSYN we have to follow number of repetitive steps which are tedious and time consuming. Many times the PROSYN interface does not show a button for going back or undo. If a user makes a mistake, the case has to be restarted. It is not possible to check the results obtained when you reopen the design case. Hence, it is necessary to save the results in word file by pasting the results obtained by PROSYN. It is not possible to export information to other software such as: Aspen Plus, Matlab, etc. PROSYN provides a powerful command called UNKNOWN. With the aid of this command PROSYN makes a suggestion for the decision to take in case the user does not have enough information to do it himself. This command saves considerable time when running a session because the user does not have to interrupt the session to find information through other sources. However all modules of PROSYN need to be redesigned with attractive and user-friendly interfaces focusing mainly on the improvement of the fully functioning HELP and WHY buttons in order to guide the user throughout the session.
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7.1.7
Conclusions
PROSYN generated a list of alternatives to separate the ternary mixture of MDAAniline-Water in a short time. The processes from the list are energy efficient (i.e. pervaporation and crystallization) and are available for implementation. Although the information reported by PROSYN does not allow concluding which is the best alternative among all, it gives enough information for ranking of the unit operations for preliminary screening in the conceptual design stage. It allows the designers to narrow down the spectrum of possibilities in the initial design process. Only the MEMPERT module gives the investment and operating cost details, but for other modules i.e. CRYSPERT, LILEX and TEAGPERT an algorithm for preliminary economic estimations needs to be implemented. In the case of extractive distillation and liquid-liquid extraction with reflux a solvent was selected by using SOLPERT module. Since SOLPERT selects solvents based only on technical criteria and not on the basis of environmental (HSE) criteria, PROSYN is not able to generate environmental friendly schemes where the addition of a mass agent is involved. Also, TEAGPERT does not perform any calculations on the energy requirement of the suggested scheme.
7.1.8
Recommendations
PROSYN should show the decision tree to show the user the navigation through the design procedure and the choices he made during the navigation. The time required to design a process by using PROSYN would be considerably reduced with a user-friendly interface and by improving features such as: help, why and undo. It is evident that the selection of an appropriate thermodynamic model is the basis of the process design. PROSYN has a limited number of thermodynamic models to predict liquid phase properties. For the gas phase, ideal gas model is the only available model which is applicable for this specific case. However, if the system includes non-ideal behavior in the gas phase, this model should not be used. It is recommended to update and extend the thermodynamic model library in PROSYN.
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7.2
Case owner: Frames Gas Processing B. V., Alphen aan de Rijn 7.2.1 Process description
This case concerns the removal of sulfur from an aqueous waste stream by solvent extraction. In this stream sulfur is present as a very finely dispersed solid form. The temperature of the waste stream is considered to be ambient, although the actual temperature might be around 80C in the process. Currently Frames makes use of CS2 and/or xylene as a solvent to remove the very finely dispersed sulfur particles. 7.2.2 Design objective The objective of this case study is to identify more benign alternative solvents for sulfur extraction and to test the PROSYN module, SOLPERT (solvent selection module). 7.2.3 Basic Assumptions
The feed stream consists of the water and very finely dispersed sulfur (S8) particles. These very finely dispersed sulfur particles are very difficult to separate by using mechanical operation and as Frames currently uses the extraction technique to extract sulfur, efforts has been put only to identify other potential solvents for sulfur extraction. 7.2.4 Results
Name of module used: SOLPERT, P^3. Short description of the modules Module SOLPERT was used in this case. SOLPERT is an abbreviation which stands for solvent selecting expert system. This module concerns an expert system which combines knowledge from databases, heuristic rules and numerical methods. The design of SOLPERT was mainly focused on the use of suitable solvents in extractive or azeotropic distillations, although it can also be applied for the screening of solvents for LLE operations. PROSYN SOLPERT was not able to give the solid-liquid interaction for sulfur-water-solvent system. A detailed description of SOLPERT was provided by Bieker [4]. In the following table the procedure, consisting of 4 screening steps, as applied in SOLPERT is shown.
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According to the literature, sulfur can be separated from water by using solvents [6]. Frames are currently using a solvent to separate sulfur from the waste stream. Frames were interested to identify other potential solvents by using the SOLPERT module. Besides the SOLPERT module, P^3 module was used for the estimation of the component physical properties. This module is connected to SOLPERT and it starts automatically when it is required by SOLPERT. Table 10 shows the components selected from each of the groups i.e. Group III, IV and V as probable solvents based on the polarity and boiling points. Table 9 also shows that group III as well as group IV solvents are not suitable in view of their miscibility with water. Therefore only group V solvents are appropriate.
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7.2.5
Evaluation of the results The solvent list generated by the module SOLPERT is logical as it generated the components like glyme and longer chain hydrocarbons which are currently used as the sulfur extraction solvents in industries. Frames suggested making use of a solvent such as glyme, or dimethoxyethane [110-71-4]. This component is present in the SOLPERT database and it is classified as a group III compound. Nevertheless it is not suggested as a solvent since its boiling point is only 358 K (85C) and it is soluble in water. Probably a di-, tri-, or tetra-glyme would be more suitable. Also it was suggested by SOLPERT that heavy diesel can be used as a solvent. After discussion with Frames it was understood that some of the companies are using heavy diesel component as sulfur removal solvent, SOLPERT suggests them as the best solvent (see table:2, Group V). After selecting the solvent, the next step is to check the efficiency of solvents in terms of distribution coefficient and that can be done by generating LLE ternary diagram for three components involved, i.e. water, sulfur and the solvent. For cases where the equilibrium data is not present in the database they are estimated based on the Modified-UNIFAC theory. For water and the identified solvents UNIFAC parameters are available, but for sulfur they are unknown and hence it was not possible to generate the LLE diagram for this ternary mixture. Another problem was that as sulfur is a solid at room temperature, ternary LLE diagram cannot be constructed. PROSYN SOLPERT module is not able to analyze the solid-liquid interaction. An attempt was made to mimic the sulfur-water system by considering the system CS2-water and to make use of xylene as a solvent. Although UNIFAC group contribution parameters are present for CS2, the LLE diagram could not be generated by SOLPERT. Surprisingly the solvent carbon disulfide (CS2) is not identified as a suitable solvent, because of the temperature range specified. However, the solvent xylene (dimethyl-benzene) is identified by the expert system. PROSYN does not have criteria for screening solvents on HSE aspects.
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7.2.6
1. Screening a suitable solvent for extraction consumes lot of time, but the PROSYN SOLPERT module can decrease this time with a little effort required by the user. 2. For Data/property calculation for the components, SOLPERT links with P^3 which contains a big physical properties database. It also can predict properties of components if data is not available. 3. The user interface needs to be improved in order to make it more user-friendly. 4. The Help function does not work properly. It does not return the desired information. 5. The Valuation and solvent mixture option from investigation menu bar is not implemented yet. 6. The Component structure input option does not work, so in some cases it will be difficult to define the molecule if it is not present in the database. 7. The module asks lot of questions and it repeats some questions, which is annoying for the user. 8. The flow of decisions made should be shown in the form of decision tree and short path should be provided in the form of a hyperlink to go back to any stage of decision/design. 9. The user interface should be designed to make it more attractive and improve the use. 10. Update latest research (correlations and component properties) in the software to provide more accurate and updated results.
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7.2.7
Conclusions
The PROSYN expert system module SOLPERT is capable of generating a list of interesting potential suitable solvents for extracting elementary sulfur from water in very little time and effort, which is one of the design objectives.
The list contains both water miscible and water immiscible solvents; an extra step needs to be taken to verify whether the solvent can be used in extraction. Due to lack of sufficient physical property data, the LLE equilibria of the two phase system cannot be estimated. Hence efficiency of solvent in terms of solute capacity cannot be calculated. Therefore further ranking of the proposed solvents is not possible. Similarly no option was found for the SLE analysis.
PROSYN cannot check whether the screened solvents are environmentally benign as compared to the currently used solvents. PROSYN is not able to comply with the second objective.
7.2.8
Recommendations
In the component screening (third step in selection process) filtering of results is managed by the questions on respectively minimum azeotropy, miscibility, and polarity. In the selection on miscibility the solubility is estimated component by component, which can be a time consuming effort. The selection on polarity however runs automatically and takes just seconds. Therefore it would be advantageous that the user can choose the order of the three filter questions discussed above. In SOLPERT a menu option valuation is present for validation of the selected solvent. This option however is not implemented yet. The same holds for the menu option solvent mixtures for finding a suitable solvent mixture. It is not known how the polarity of the solvents is estimated. Since this is a crucial selection criterion some background information within PROSYN should be appropriate. An option for the user to monitor the progress in the decision process (may be in the form of decision tree diagram) is recommended. Also an option to re-start from a given point in the process would be of great interest. In view of graphics an option to just define a solvent and plot a phase diagram is suggested. The application can be improved by adding an undo option or a go back button. Help options should be improved/detailed explanation in order to guide users through-out the simulation. In order to improve efficiency it is advised to offer documentation as well as courses on the use of PROSYN.
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7.3
7.3.1
Process description
This case is divided into the two parts; Reaction and separation sections, the details problem description is given below. Production bioreactor: Mode and scale: Fed-batch, 250L At the beginning of the production, 180 L of production media and 50L of inoculation (cells) are added to the reactor. The production media is purchased from another company and the composition of the media is unknown. After a few days of cultivation, Feed A, B and glucose are added to the reactor continuously. What is in Feed A and B is also not known. The temperature in the bioreactor is kept at 37 C. The pressure in the bioreactor is 30mbar. The yield of the antibody is 2 g/L. Separation section: The separation consists of a sequence of chromatographic separations in obtaining antibody material at a relevant purity. 7.3.2 Design objective
To generate a list of reactors for the given reaction and to synthesis separation options for the given mixtures.
7.3.3
Basic Assumptions
For the given problem definition, following bi-substrate reaction is assumed and given as input to the PROSYN READPERT module to generate the potential reactor list. A+B+E EAB EP P+E
7.3.4
Results
A. Reaction Section: to make a proper choice of reactor in the early stage of process design, PROSYN has the heuristic-numeric consulting system READPERT i.e. Reactor Development, Selection and Design Expert System. At the start of chemical process design definite values concerning the kinetics of the reaction system are usually not known. Thus READPERT starts with mainly qualitative criteria derived from initial experiments and reasonable assumptions to ascertain the proper reactor and its operating conditions. The whole task is divided into a variety of sub problems, In order to obtain the useful and clearly arranged knowledge bases, these sub-problems are collected into four different modules; 1. General Reactor Type, 2. Operating Conditions, 3. Technical Reactor, 4. Heat Transfer Equipment [7]. The summary of the results obtained and conditions specified in different sub-problems/modules is presented in the following table 11.
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Table 11 Summary of conditions specified during investigating reactor type and results
Summary of conditions specified in Investigation steps: Module:1- General Reactor Type; 1) A + B <===> EAB desired reaction 2) EAB <===> EP desired reaction 3) EP <===> P desired reaction Reactants to be fed to the reactor: A, B. Desired product: P (Antibody) Reaction path leading to product: reaction 1, then reaction 2, then reaction 3 Location of equilibrium: - reaction 1): mostly on the side of the products - reaction 2): totally on the side of the products - reaction 3): totally on the side of the products Goal for reactor selection: - yield Module: 2 - Selection of Basic Reactor Conditions: Reaction group main reaction 1 a. Temperature profile: constant (as low as possible) b. Backmixing characteristic: total backmixing c. Residence time distribution: without influence d. Qualitative concentration level of A and B: medium e. Reaction rate vs. conversion plot: monotonic decreasing f. Conversion rate: incomplete conversion for all reactants [A,B] g. Supply of reactants: slow supply of some reactants [A,B] h. Recycle streams: no recycle streams [] Reaction group main reaction 2 a. Temperature profile: constant (as low as possible) b. Backmixing characteristic: total backmixing c. Conversion rate: complete conversion of all reactants [EAB] d. Supply of reactants: slow supply of some reactants [A,B] e. Recycle streams: no recycle streams [] Reaction group main reaction 3 a. Temperature profile: constant (as low as possible) b. Backmixing characteristic: total backmixing c. Conversion rate: complete conversion of all reactants [EP] d. Supply of reactants: slow supply of some reactants [A,B] e. Recycle streams: no recycle streams [] Supply of reactants: - supply of reactants for reaction path 1: slow supply of some reactants applicable for: A,B constraints: [none] Removal of components: - main reaction 1: no special component removal - main reaction 2: no special component removal - main reaction 3: no special component removal
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Module: 2- Selection of operating conditions.continue Recycle streams: - no recycle streams in front of subsystem: 1 - no recycle streams in front of subsystem: 2 - no recycle streams in front of subsystem: 3 Conversion rate(s): - reaction 1: incomplete conversion for all reactants applicable for: A,B - reaction 2: Equilibrium conversion of all components - reaction 3: Equilibrium conversion of all components Ratio of reactants: - not stoichiometric, if possible excess of: A,B Pressure level(s): - reaction 1: without influence - reaction 2: without influence - reaction 3: without influence
Module: 3 - Technical Reactors (GHN) Suggested Reactors from GHN reactor Library of READPERT; 1. Tubular reactor 2. Reformer 3. Sulzer mixer-reactor 4. Draft tube 5. Stirred tank 6. Reactive destillation column 7. Multichamber tank 8. Falling-film reactor 9. Reactive crystallization, separation function
Reactor Ranking Criteria used in READPERT: 1. Mixing liquid: Plug / Mixed 2. Development effort: High / Low 3. Capacity: Yes / no 4. Interstage feeding: Yes / no 5. Viscosity: Low / medium 6. Gaseous products: Yes / no
B. Separation Section: The given feed stream for separation is a mixture of complex components (Antibody, DNA, RNA, Proteins, etc.) and PROSYN does not have these molecules in its database library. The idea was to mimic these components by components available in the component database, but since no information on Antibody and Protein structure and chemical formula was available, it was not possible to provide required input for PROSYN. Therefore it was not possible to generate the separation sequence for the given feed stream using PROSYN.
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7.3.5
Evaluation of results
Reactor options generated by the READPERT based on the input specifications (such as reaction type, operation mode, mixing characteristics, etc.) supplied to READPERT seem to be plausible. E.g. stirred tank reactor, tubular reactor, Sulzer mixer reactor, etc. Reactor options such as reformer, Sulzer mixer reactor and falling film reactor, reactive distillation reactor were generated. For the chemical process industry these reactors are well-known options. For biochemical reactions however these are not feasible. The reason is that the READPERT module was designed for the chemical industry and not for biochemical synthesis. For biochemical reactions the stirred tank and the draft tube reactor seem to be a logical choice since backmixing is selected while giving input to READPERT. READPERT suggested the above reactor options after analyzing the given reaction sequence by applying a number of criteria such as reaction type, recycle structure, operation mode, feed options, product removal, heat supply/ removal, pressure levels, yield, concentration of reactant feed, temperature levels, etc. This seems logical in selecting a reactor type. A detailed description of the procedure of reactor selection and questions asked by the expert system is given in the Appendix. Data supplied to READPERT was incomplete (reaction component data). Also no properties calculations were selected. Therefore READPERT gave reactive crystallization and distillation as potential options. For a biochemical reaction under consideration it seems illogical, but if all the component data are supplied READPERT may come up with accurate calculations and suggestions on selecting reactive crystallization and distillation options for carrying out the given reaction. Different ranking criteria applied for the generated list of reactors seems to be logical as READPERT suggests the potential reactor to be used based on the ranking criteria imposed. E.g. foaming criteria removes stirred tank form potential reactor list. While using development effort as ranking criteria, it has given results that tubular reactor is more expensive than reformer and Sulzer-mixer reactor, which seems to be illogical and it should be other way around. PROSYN is not capable to suggest the separation sequence for the given feed mixture.
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7.3.6
READPERT is capable of generating number of reactor options for thermally/catalytically activated reactions from its reactor model library. But, READPERT is not able to generate the reactor type for the polymerization reactions and reactions containing solids as reactants or intermediates. Also, no special provision for bio-chemical reaction has been seen in the READPERT module (e.g. shear sensitivity, biochemical reaction kinetics, etc.). It saves a lot of time and effort in finding suitable literature for selecting the reactor type. While selecting a reactor type a number of criteria such as reaction type, recycle structure, operation mode, feed options, product removal, heat supply/ removal, pressure levels, yield, concentration of reactant feed, temperature levels, etc. are applied. In a relatively short time (hours) a list of potential reactors is generated. Based on the reaction heat effects, READPERT can suggest various configurations and auxiliary heat transfer equipment to carry out the given reaction. If the user is not able to answer a question, the UNKNOWN option is of great help in finding an appropriate answer. PROSYN is not suitable for generating separation option for biological component mixture, because of lack of data on antibody, DNA, RNA and protein properties and interaction with each other. Also, because of the absence of a module on downstream separation operations such as chromatography (adsorption chromatography, ion exchange chromatography, size exclusion chromatography, affinity chromatography, hydrophobic interaction chromatography, reversed phase chromatography, ion exchange chromatography), adsorption, electrophoresis, etc. In principle as an alternative SOLPERT could be used to select a suitable solvent, but lack of information physical properties of antibody, DNA, and protein prevents using this module.
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7.3.7
Conclusions
PROSYN READPERT module generated a list of reactor types in a short time, which are plausible according to the input conditions specified. The reactor list generated by the READPERT can be sorted by applying different constraints and ranking criteria to identify the desired reactor configuration for considered reaction sequence. But, additional information related to biochemical reactors (such as shear sensitivity, kinetics) needs to be included in READPERT. READPERT allows designers to narrow down the spectrum of possibilities in the initial design process and provides information for preliminary screening and necessary for conceptual design stage. Clear explanation should be given for the meaning and the purpose of the questions and a Go Back option should be provided as suggested for other modules. Because of the complex component mixture and lack of component information, it was not possible to identify potential separation options. PROSYN is not suitable for generating separation options for biological component separation, because of lacking modules for the unit operations such as chromatographic separation and adsorption, which are most widely used for the separation of antibodies, DNA, RNA and protein mixture.
7.3.8
Recommendations
Flow of algorithm for reactor selection is very clear in first three steps (Such as break down of the complex reaction into simple single step reactions and reaction conditions, etc.), but the step-3 of technical reactor is very confusing and needs to be explained in the help option or by providing some text guidelines, specifically the use of ranking criteria. Separation operations for biochemical products such as chromatography, adsorption, etc. need to be included in the PROSYN module library. A special consideration for the biochemical reactions, e.g. shear sensitivity, needs to be addressed in the READPERT module, i.e. READPERT should incorporate the extra steps to design biochemical reactors.
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7.4
CASE 4 - Cosun Treating of wastewater containing: Nitrogen, Phosphate and Potassium from wastewater.
7.4.1
Process description
This case concerns the removal of nitrogen, phosphate and potassium from an aqueous effluent. Although the recovery is not straightforward because of lower concentration of required components, an economically viable solution is required for this case. The stream to be treated has a pH = 3.26. The content of the effluent stream is provided in the following table:
7.4.2
Design objective
To generate an economically viable options using PROSYN for removal of components containing nitrogen, phosphate and potassium from given stream.
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7.4.3
Results In order to identify alternative separation options, the BIKOM and MEMPERT module within the PROSYN software package was used. BIKOM is an abbreviation which stands for Behandlung Industrieller Abwsser mit KOMbinationsverfahren (Industrial wastewater treatment with combined processes). This expert system module combines knowledge from databases and heuristic rules concerning the waste water treatment. The database contains rules of thumb as well as typical operating conditions, economic data, and energy use for 35 waste water treatment processes (see appendix 4). In addition it can give advice in setting up a sequence of treatment processes to ensure meeting the demands required for clean water. Also the module contains the regulations for waste water treatment according to the German law around 1995. Economic data are provided in DM (Deutsch Marks) and these data are valid for the year 1995. The navigation as well as the input and output are entirely in the German language. When running a simulation with BIKOM the user has to enter the input data for the waste stream, which concerns the minimum and maximum concentration of the contaminant as well as the state, i.e. dissolved, dispersed etc. Currently BIKOM can only handle an influent stream which contains just one component. Next the user has to specify the target concentration of the contaminant in the effluent stream. This can be done either manually by entering a value or use can be made of the regulations according to the German law (see above). Finally an exploration for suitable treatments can be started. BIKOM provides a list of suitable processes and it suggests the most preferred one. The MEMPERT module was also used to check the suitability of membrane separation method to achieve the objective. The MEMPERT module can perform calculations for six membrane processes i.e. ultrafiltration, micro-filtration, nanofiltration, reverse osmosis, pervaporation, vapor permeation. MEMPERT suggests, based on the molecular size, which membrane process is suitable for the given feed mixture. MEMPERT is able to perform a shortcut simulation to calculate investment and operating cost to give insight into the economic feasibility of the particular membrane process. Details of results obtained using BIKOM and MEMPERT is given in the Appendix D.
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1.1.1
Assessment of the Design Process The navigation within the BIKOM module is straightforward. Influent parameters have to be entered as well as targets for the effluent. The module proposes a number of alternative waste water treatment steps. Sessions with BIKOM consume very little time. For a given waste stream a proposal for a treatment sequence can be generated within half an hour. Many industrial waste waters contain a mixture of contaminants that have to be removed. BIKOM is not able to generate an influent matrix containing all these contaminants. The user has to perform the assessment for each component separately. Afterwards the user has to construct a waste water treatment sequence which meets the demands for all these contaminants. It might not be straightforward to find such a solution. A drawback of the module is that navigation and input/output is entirely in the German language. Moreover data concerning the German legislation on waste water as well as economic data are valid for the year 1995. Also all prices are based on the DM currency. Selecting the potential membrane process using MEMPERT for the given problem takes very little time and requires little efforts. MEMPERT can generate an economic evaluation in DM for the different membrane processes selected, which will be beneficial in the preliminary screening of the separation options. MEMPERT cannot be used yet for a mixture having tendency of dissociation in ions and changes in molecular size. MEMPERT cannot handle a large number of feed components and can allow only one component as permeate. Also, MEMPERT cannot access the membrane module data.
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7.4.4
Conclusions
Different options for the regeneration of the components containing nitrogen, phosphorus and potassium using PROSYN have been identified, but economic viability of these options cannot be compared directly as these options assume different parameters for the economic calculations. BIKOM is an efficient tool to identify suitable options for waste water treatment for a given process stream. This PROSYN module provides information on the raw materials required for the treatment as well as information on energy use and total costs. MEMPERT is useful tool for analysis and selection of different membrane processes in the initial stage of the process design. MEMPERT can check applicability of the membrane processes, rating of the permeate and retentate components and can perform a shortcut simulations for the suggested membrane processes to give a rough idea about the economic and process parameters, which helps in the screening of the separation processes. MEMPERT cannot handle a large number of components or components undergoing dissociation or change in molecular sizes.
Recommendations
In order to make the module more accessible it is required that all texts need to be translated from German into English. Moreover economic figures should be updated to current levels based on currency. Finally the module should be able to handle waste streams containing more than one contaminant. Cost data and membrane module data in MEMPERT needs to be updated to the current technology level.
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REFERENCES
[1] Schembecker G., Simmrock K. H., and Wolf A., 1994. Synthesis of chemical process flowsheets by means of co-operating knowledge integrating systems, I. Chem. E. Symp. Ser. 133, 333-341. [2] Grievink J., Swinkels P. An Advanced Strategy for Conceptual Process Design. TUDelft. 2009. [3] J. D. Seader; E. J. Henley. Separation Process Principles. 2nd edition. New York, John Wiley & Sons, 2006. [4] T. Bieker, and K.H. Simmrock, Knowledge integrating system for the selection of solvents for extractive and azeotropic distillation, Computers chem. Engng., Vol 21, Suppl., p. S25-S29, 1994. [5] L. Berg, R.H. Ewell, and J.M. Harrison, Azeotropic distillation, Ind. Eng. Chem., 36(10), p. 871-875, 1944. [6] Mahin Rameshni, Impurities Removal Options in Sour Gas Field Developments. [7] Schembecker G., Droge T., Westhaus U., and Simmrock K. H., 1995. READPERT Development, selection and design of chemical reactors. Chemical Engineering and Processing, 34, 317-322.
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9
9.1
APPENDICES
Appendix 1: Huntsman case
MEMPERT: Membrane Processes
9.1.1
A. Pervaporation
A preliminary calculation for the membrane process by using PROSYN manager gives the following results: No | retentate | permeate | rating ----+-------------------+-------------------+----------------------1 | [MDA] | [Aniline,Water]| less promising 2 | [Aniline,MDA] | [Water] | preferable 3 | [MDA,Water] | [Aniline] | possible in principle Based on the above results, it is decided to carry out pervaporation process in 2 stages; first stage is nd to remove water from ternary mixture and 2 stage to separate Aniline and MDA. Specifications and results for 1 and 2
st nd
pervaporation module:
Figure 1. pervaporation process PROSYN suggested that second stage of pervaporation is less promising, so other operations (extraction and crystallization) were considered for the separation of MDA and Aniline. Many more hybrid operations are possible in principle to test, but due to time constraints only 2 options were tested and results for them are given in following points.
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9.1.2
First step in designing the liquid-liquid extraction process is to select the suitable solvent. In order to screen and select the best suited solvent, SOLPERT is used, which starts automatically when the algorithm reaches the stage of solvent specification. SOLPERT is an abbreviation which stands for solvent selecting expert system. This expert system combines knowledge from databases, heuristic rules and numerical methods. The design of SOLPERT was mainly focused on the use of suitable solvents in extractive or azeotropic distillations, although it can also be applied for the screening of solvents for LLE operations. From the list of screened solvents, octadecanol was selected as most suited solvent based on polarity (SOLPERT). The ternary system generated when octadecanol is added to the mixture MDA-Aniline is type II, i.e. two immiscible pairs are formed. For this type of ternary systems is desirable to use a liquid-liquid extraction with extract reflux since without a plait point, it is possible with reflux to achieve a sharp separation [3]. Therefore, a liquid-liquid extraction with extract reflux should be implemented when, as in the present case study, high purity is required in the products. Solvent: Octadecanol Using Octadecanol as a solvent, the following procedure is carried out in LILEX and the summary of results obtained is given below: Input:
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Estimated ranking of equipment used for extraction according to modified Mycin algorithm : Table 13 Liquid-Liquid Extraction equipment rating Apparatus/Equipments Mixer-settler tower Asym. rotating disc contactor Pulsed packed column Podbilniak centrifugal extractor Kuehni column Robatel centrifugal extractor Pulsed sieve plate extractor Rotating disc contactor Single mixer-settler Sieve plate extractor Rating 68.2 71.6 71.6 75.7 91.9 95.2 97.5 98.1 98.3 99.6
Where the area of suitability is defined as follows: 0 30 = well suited; 30 70 = moderately suited; 70 90 = limited suited; > 90 = not suited.
9.1.3
The CRYSPERT module was used to simulate the separation sequence as an alternative for second stage pervaporation to separate MDA and Aniline. The input supplied to CRYSPERT and the results obtained are summarized below: Input: Stream Feed Data: Temperature [K] Pressure [MPa] Phase Mole flow [kmol/h] Mass flow [kg/h] Stream composition: MDA Aniline Stream Flow rate: MDA Aniline 363.15 0.10 liquid 416.7 57900 0.62 [kg/kg] 0.38 [kg/kg] 36013.8[kg/hr] 21886.2 [kg/hr]
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Proposed phases/separation: Liquid phase MDA Aniline Simulation Results: Solid phase MDA
a. Investigated classification of crystallization type: Crystallization from solution b. Investigated eutectic/peritectic points: Eutectic mixture : MDA/Aniline Eutectic temperature: 264.85 K Eutectic composition: Component | mole frac. | mass frac. | [mol/mol] | [kg/kg]
MDA Aniline | 0.035 | 0.965 | 0.0716 | 0.9284 .
d. Investigated melting point: 306.73 K (solid phase: MDA) e. Proposal for expected operating temperature range: 273 K to 313 K f. solidification temperature [K] No. | temperature | component | MDA | Aniline | method or | origin | [K] | [-] |[mol/mol]|[mol/mol]| database | -----+----------------+--------------+-----------+-----------+-------------------------+-------1 | 334.0 | MDA | 0.44 | 0.56 | Equilibrium Calculation | No. 1
g. Yield calculation results: max. achievable yield (molar): 41.5% max. achievable yield (mass) : 59.3% operating temperature : 264.86 K h. Investigated yield: Yield at 292.15 K: 52.1 % (solid phase: MDA) i. Investigated proposals for Crystallizer equipment:
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j.
Summary of conditions selected for crystallization: Operating mode : continuous Crystallization class : Crystallization from solution Crystallization type : Cooling crystallization Heat exchange : indirect cooling
k. Significant rating criteria: Crystal purity requirement Density difference solid/liquid Production scale Operation flexibility Cascade structure Scaling tendency Average crystal size Crystal size distribution Attrition Solvent inclusions l. Crystallizer rating:
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Table 15 Crystallizer rating. Criteria crystal purity requirement Density difference solid/liquid Production scale Cascade structure Total rating Ranking Value Ranking SCC + + + + + 20 1 DT + o o + + 37.8 2 SSC O O + O + 41.1 3 SV o o o + + 41.1 4 SSV o o o + + 41.1 5 DTB + -+ + -90.1 6 CDC O O + --91.1 7 GC o -+ -96.2 8 FB O ---101.2 9
m. Add-on equipment available for crystallizers: Clear liquor advance Fines destruction loop Classified product removal Elutriation leg n. Material Balance on Crystallizer: E.g. Forced circulation Cooling (Swenson)(SSC): Heat exchanger type Type of cascade flow Crystallizer Add on equipment Heat duty Operating yield Operating temperature Operating pressure Operating mode Crystallization class Crystallization type Heat exchange Heat exchanger type Type of cascade flow external + scraped cross flow Forced Circulation Cooling (Swenson) Elutriation leg -3801.06 kW 52.1 % 292 K 0.10 MPa continuous Crystallization from solution Cooling crystallization indirect cooling external + scraped cross flow
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Stream data of Solids: (Solid -Sub Stream) temperature [K] 292 pressure [MPa] 0.1013 phase solid mole flow [kmol/h] 152.2 mass flow [kg/h] 30165.9 component | [mol/mol] | [kg/kg] -----------+-----------+--------MDA | 1.0 | 1.0 component | [kmol/h] | [kg/h] -----------+----------+--------MDA | 152.15 | 30165.9
Stream data of Mother liquor(Liquid sub stream) temperature [K] 292 pressure [MPa] 0.1013 phase liquid mole flow [kmol/h] 264.6 mass flow [kg/h] 27734.1 stream composition: component | [mol/mol] | [kg/kg] -----------+-----------+--------MDA | 0.111 | 0.21 Aniline | 0.889 | 0.79 component | [kmol/h] | [kg/h] -----------+----------+----------MDA | 29.42 | 5824.16 Aniline | 235.14 | 21909.94
9.1.4
TEAGPERT: Conventional distillation and extractive distillation The TEAGPERT module conceptually designs the separation of azeotropic and close boiling mixtures. TEAGPERT has embedded models which make the calculations for the following separation processes:
Simple distillation of nonideal mixtures Extractive distillation with mass agent Heteroazeotropic distillation (without mass agent) Heteroazeotropic distillation (with mass agent) Homoazeotropic distillation with internal recycle
In the conceptual designs of separation processes which require the addition of a mass agent, TEAGPERT calls the SOLPERT module.
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In order to separate the mixture MDA, Aniline and water the following separation processes were proposed and investigated by TEAGPERT module:
1. Simple distillation of nonideal mixtures 2. Extractive distillation with mass agent 3. Homoazeotropic distillation with internal recycle
A summary of results obtained is given below: 9.1.4.1 Simple distillation of nonideal mixtures
The boiling temperature of stream (STP1) is 374.77 K. A heat exchanger is needed for the temperature shift from 363.15 K to 374.77 K. Mass balance on column (0.101325 MPa): Table 16 Material balance for simple distillation sequence.
Component MDA[wt%] Aniline[wt%] Water[wt%] Flow rate (kg/h) Feed 60 36.5 3.5 60000 Distillate Product 0 91.25 8.75 24000 Bottom Product 100 0 0 36000
9.1.4.2
A heat exchanger is needed for the temperature shift from 363.15 K to 374.77 K. Mass balance of column (0.101325 MPa):
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SOLPERT was used to select the mass agent for extractive distillation. Following is the list of solvent tested for the extractive distillation sequence and results are presented in the table. i. ii. iii. iv. Ethanone, 1-phenyl- (9CI) Benzene, nitro- (8CI, 9CI) Acetamide, N,N-dimethyl- (8CI, 9CI) Methane, sulfinylbis- (9CI) (Tb: 475.1 K) (Tb: 483.9 K) (Tb: 439.1 K) (Tb: 466.7 K)
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Table
Solvent
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9.2
9.2.1
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In the component screening the selection criteria can be given (minimum b.p., maximum b.p. and polarity). The minimum b.p. is set at 390K, and the maximum b.p at 600 K. The selection criterion is set at polarity. In the next panel all functional groups are selected for screening. In a subsequent panel where the increments can be chosen all increments are selected. Next the question is asked if a minimum azeotrope is being formed for the listed components. This is answered with OK in order to circumvent a screening regarding azeotropy, which is not required for this project. Next it is asked whether the listed components are miscible with water. One by one the components are checked for their solubility in water. Finally the system asks which components are suitable according to polarity. This is answered by UNKNOWN. The system returns a list of components, which are provided in table 2. It shows that group III as well as group IV solvents are not suitable in view of their miscibility with water. Therefore only group V solvents are appropriate. In the case a boiling point temperature range is omitted the solvent carbon disulfide (CS2) is not identified as a suitable solvent, although it is referred to in the help file (see appendix 1). The solvent xylene (dimethyl-benzene) however is identified by the expert system. In a next step a LLE ternary diagram can be displayed for the three components involved, i.e. water, sulfur and the solvent.
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9.3
9.3.1 Step: 1 General Reactor Type: Input: Reactants: A, B. Products: P. Catalyst: E. 1. On the start of the program, the following message appears on the screen. - only thermally or thermally/catalytically activated reactions - no polymerisations - no solids as reactants or intermediates
2. Specify ALL components: A, B, EAB, EP, and P are specified. 3. Do you want to apply the physical support system for calculation during the investigations done by READPERT ? If the specified reactant and product are known i.e. present in the database then, READPERT uses the P^3 module to calculate all the properties required for the reactor selection. 4. Break down complex reactions into subreactions.
Use the format >>> reactant? type of reaction? products? <<<. Known substances: A / B / EAB / EP / P
5. Specify the type of reaction: Selected option: Reversible/ Equilibrium. Other options available: Irreversible, reaction which depends upon the presence of catalyst, an autocatalytic reaction, an inhibited reaction. 6. Enter the location of the equilibrium for the above reaction. Selected option: totally on the side of the product Other options: totally on the side of the reactant Mostly on the side of the product Mostly on the side of the reactant In the middle between reactant and product 7. Please enter the phase of total reaction system
Selected option: liquid Other options: gas Gas-liquid Liquid-liquid Gas-liquid-catalyst Liquid-catalyst Gas-catalyst
8. Main Products?
Selected option: P Other option: EAB, EP
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10.
12. Please enter the backmixing characteristic for the listed system.
Selected Option: UNKNOWN Other options: Total Backmixing, No Backmixing, First total then no backmixing
13. Please enter the qualitative concentration level for A and B in the reactor.
Selected option: UNKNOWN Other option: medium, low, High
14. Please enter the shape of the reaction rate vs. conversion plot for the reaction system.
Selected option: UNKNOWN
15. Please enter the reaction heat for the listed system.
Selected option: THERMONEUTRAL
20. Please enter the temperature profile for the listed system.
Selected option: Constant as low as possible Other options: Constant (as high as possible/ medium temperature) Falling (as high as possible/ medium temperature) Rising (as high as possible/ medium temperature) Without influential
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22. Enter the reactants for which this method should be applied.
Selected option: A and B
23. Please enter the mode of component removal for the reaction.
Selected option: No special component removal Other options: - products separation during reaction: separation of products and intermediates - component separation during reaction: separation of side products
24. Please enter possible recycle streams.(Streams which will be recycled after product separation.)
Selected option: No recycle Other options: recycle of reactants Recycle of side products Recycle of inerts
9.3.3
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The list of reactors generated by READPERT for reaction under consideration is as follows;
1. 2. 3. 4. 5. 6. 7. 8. 9.
Tubular reactor Reformer Sulzer mixer-reactor Draft tube Stirred tank Reactive destillation column Multichamber tank Falling-film reactor Reactive crystallization, separation function
A. Applying constrains that reactive crystallization is not applicable for the given reaction, then list narrow down to;
In: Tubular reactor Reformer Sulzer mixer-reactor Draft tube Stirred tank Reactive distillation column Multichamber tank Falling-film reactor Out: Reactive crystallization, separation function Reactive crystallization, separation function
B. Applying constrains that reactive distillation is not applicable for the given reaction, then list narrow down to;
In: Tubular reactor Reformer Sulzer mixer-reactor Draft tube Stirred tank Multichamber tank Falling-film reactor Out: Reactive distillation column
C. Applying constrains of tendency of deposit formation for the given reaction, and then list of reactor is;
In: Tubular reactor Reformer Sulzer mixer-reactor Draft tube Stirred tank Multichamber tank Falling-film reactor Out:
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Next, ranking criteria can be used to select the best suited reactor from the above listed reactors;
1. Foaming
In: Tubular reactor Reformer Sulzer mixer-reactor Draft tube Out: Stirred tank Multichamber tank Falling-film reactor
2. Capacity
In: Tubular reactor Reformer Sulzer mixer-reactor Draft tube Out:
3. Development efforts
In: Reformer Sulzer mixer-reactor Out: Tubular reactor Draft tube 9.3.4 Step: 4 Investigation of HEAT TRANSFER Do you want to investigate the heat transfer with regard to the technical reactors? >>> No Figure 4. Screen shot for the step of ranking the technical reactors.
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9.4
9.4.1 BIKOM Module Separate simulations have been performed to get the suitable separation process options for the regeneration of the nitrogen, phosphorus and potassium respectively as BIKOM module can handle stream with only one solute component. 9.4.1.1 Regeneration of Nitrogen:
For the removal of ammonia (see table 1) from the waste stream a target concentration of 800 mg/L is entered. BIKOM proposes the following two potential methods: Aerobic biologic treatment Gas stripping According to BIKOM aerobic biological treatment can reduce the ammonia concentration down to 800 mg/L. Surprisingly the module does not continue after this point. In table 19 the results are given.
Also gas stripping was selected as an option. This treatment can decrease to concentration down to 16 mg/L. The results are given in table 20 and in table 21 the economics are provided. Please note that BIKOM estimates the COD for the streams.
Additional waste components: 35 45 Nm laden strip gas. Separated waste components: 35 45 3 Nm waste gas. Proposal for waste disposal: incineration.
Removal of phosphate
For the removal of phosphate from the waste stream a target concentration of 1 mg/L is assumed. BIKOM proposes the following treatment sequence: 1) 2) 3) 4) 5) Precipitation with Fe Flocculation Partial filtration back washing water Precipitation with Fe Ionic exchange regenerate
In table 22 the influent and effluent conditions are given for the individual steps.
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Precipitation
Flocculation
Filtration
Ionic Exchange
Table 22 Composition of the wastewater in every single step of the removal process
Stream Component/Concentration Chloride, dissolved Phosphate, dissolved Phosphate, precipitated Total filterable compounds Conductivity, dissolved [S/cm] 1 mg/l 2 mg/l 3 mg/l 27.8 0.1-0.8 74.9-149 74.9-149 160-321 4 mg/l 5 mg/l 6 mg/l 27.8-55.5 0.1-0.8 0-1 0-1 43.4-89.4
0.037-0.296 0.00074-0.00592 0,1-0,8 0-1 0-1 0.144-3.13 0.002-0.016 0-0.02 0-0.02 0.00287-0.0627
For step 4) these conditions were not shown by BIKOM. Eventually a phosphate concentration < 0.02 mg/L is obtained, which is smaller than the demand of 1 mg/L. In table 23 the raw material use, energy use and economics are given of the various process steps. 3 Additional waste streams: 0.0 0.0 L/m eluate. No separated waste components
Table 23 Overview
Treatment step Precipitation, Fe Flocculation Partial filtration Precipitation, Fe Ionic exchange Waste material 0.0-0.0 kg solid content/m precipitation sludge 3 0.0749-0.149 kg solid content/m flocculation sludge 3 3 0.01-0.05 m /m back washing water 3 0.0 0.0 solid content/m precipitation sludge 3 0.0 0.0 L per m eluate
3
Raw material use 0.0 0.008 0.00824 - 0.0164 3 kg floc. agent/m 3 3 0.01 0.05 m /m 0.0 0.008 0.0 0.0 3 L eluent agent/m
Total cost 3 [DM/m ] 3.5 5.5 0.5 1 0.2 0.3 3.5 5.5 2-5
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9.4.1.3
Regeneration of potassium
For the removal of potassium from the waste stream a target concentration of 100 mg/L is assumed. BIKOM proposes the following treatment sequence: 1) Electrodialysis 2) Ion exchange The influent and effluent conditions for both steps are provided in the flowing two tables. In table 22 an overview is given of the raw material use, energy use and economics of both steps.
The conductivity figures as provided in this table are estimated by BIKOM. 3 3 Additional waste streams are 0.5-0.64 m concentrate per m concentrate and separated waste 3 3 streams are 0.5-0.64 m concentrate per m concentrate.
Table 26 Overview
Treatment step Electrodialysis Ion exchange Waste material 3 0.5-0.64 m concentrate 3 per m concentrate 3 0.0 0.0 L per m eluate Raw material use 0 0 L eluent 3 material /m Energy use 3 4-80 kWh/m 0.44-1 kWh/m
3
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9.4.2 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35.
Sedimentation Adsorption Activated aerobic bio treatment Activated anaerobic bio treatment Vaporization Electro dialysis Electro flotation Dissolved air flotation Precipitation, CaAl Precipitation, Ca(OH)2 Precipitation, CO2 Precipitation, Fe Precipitation, MAP Precipitation, NaOH Precipitation, S Fixed aerobic bio treatment Fixed anaerobic bio treatment Flocculation Hypochlorite Ionic exchange Ozone Ozone & UV Partial filtration Steam stripping Gas stripping High pressure Oxidation (> 5 bar) Normal pressure Oxidation (< 5 bar) Ultrafiltration Reversed Osmosis 120 bar Reversed Osmosis 200 bar Reversed Osmosis 60 bar Reversed Osmosis 80 bar Incineration Peroxide Peroxide & UV
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9.4.3
MEMPERT Module
MEMPERT was not able to handle more components, so all acid components fractions are considered into acetic acid fraction and other inorganic component such as calcium, sodium fractions are considered in the fraction of phosphate and potassium. Furthermore it is assumed that the given stream is aqueous and contains 95% water. Following input is specified in the MEMPERT, Temperature Pressure Phase condition Mole flow Mass flow [K] : 298 [MPa] : 0.1013 [-] :l [kmol/h] : 9514.5 [kg/h] : 174562.5 (Key-) Component Water Potassium nitrate Potassium phosphate Ammonia Acetic acid Potassium [kmol/kmol] 0.96993 5.0e-5 0.0003 0.01852 0.00219 0.00901 [kg/kg] 0.95265 0.00029 0.00351 0.01719 0.00716 0.0192
In MEMPERT, the procedure is divided into different stages of investigation such as operating conditions specifications, applicability, rating and shortcut simulations. If the number of components specified is higher, MEMPERT was not able to proceed beyond the applicability stage. After specifying the given feed stream in MEMPERT, in the next step applicability of the MEMPERT process can be checked. Following result was obtained in the applicability step: Applicability of selected membrane process unit operations: Possible in principle | apparently impossible -----------------------+----------------------Nanofiltration | Microfiltration Reverse osmosis | Ultrafiltration Pervaporation | Vaporpermeation Next step is rating of the separating cuts in particular membrane processes. Rating of the separating cuts for the three most suitable processes is given below; Nanofiltration: Table of rated separating cuts: Retentate: Permeate: Rating: Potassium phosphate [Acetic acid,Ammonia,Potassium,Potassium nitrate,Water]| Worth considering
Reverse Osmosis and pervaporation: Table for rating of separating cuts for Reverse osmosis and pervaporation is given on the next page. After rating of the separating cuts for the three suitable membrane processes, MEMPERT suggest Nanofiltration and Reverse osmosis as the best potential option and Pervaporation as less promising option. The shortcut simulation option has not returned any results, because MEMPERT got stuck in the session.
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Reverse Osmosis
Retentate | permeate | rating ---------------------------------------------------------------+-------------------------------------------------------------------+------------------[Potassium phosphate] | [Acetic acid,Ammonia,Potassium,Potassium nitrate,Water] | preferable [Potassium nitrate,Potassium phosphate] | [Acetic acid,Ammonia,Potassium,Water] | worth considering [Acetic acid,Potassium,Potassium nitrate,Potassium phosphate] | [Ammonia,Water] | less promising [Acetic acid,Potassium nitrate,Potassium phosphate] | [Ammonia,Potassium,Water] | less promising [Potassium nitrate] | [Acetic acid,Ammonia,Potassium,Potassium phosphate,Water] | less promising [Potassium,Potassium phosphate] | [Acetic acid,Ammonia,Potassium nitrate,Water] | less promising [Potassium,Potassium nitrate,Potassium phosphate] | [Acetic acid,Ammonia,Water] | less promising [Potassium,Potassium nitrate] | [Acetic acid,Ammonia,Potassium phosphate,Water] | less promising [Potassium] | [Acetic acid,Ammonia,Potassium nitrate,Potassium phosphate,Water] | less promising [Acetic acid,Potassium phosphate] | [Ammonia,Potassium,Potassium nitrate,Water] | less promising [Acetic acid,Potassium nitrate] | [Ammonia,Potassium,Potassium phosphate,Water] | less promising [Acetic acid,Potassium,Potassium phosphate] | [Ammonia,Potassium nitrate,Water] | less promising [Acetic acid,Potassium,Potassium nitrate] | [Ammonia,Potassium phosphate,Water] | less promising [Acetic acid,Potassium] | [Ammonia,Potassium nitrate,Potassium phosphate,Water] | less promising [Acetic acid] | [Ammonia,Potassium,Potassium nitrate,Potassium phosphate,Water] | less promising
Pervaporation:
Retentate | permeate | rating -----------------------------------------------------------+-----------------------------------------------------------------------+-----------------[Acetic acid,Potassium,Potassium nitrate,Water] | [Ammonia,Potassium phosphate] | less promising [Acetic acid,Potassium,Water] | [Ammonia,Potassium nitrate,Potassium phosphate] | less promising [Acetic acid,Water] | [Ammonia,Potassium,Potassium nitrate,Potassium phosphate] | less promising [Acetic acid,Potassium phosphate,Water] | [Ammonia,Potassium,Potassium nitrate] | less promising [Acetic acid,Potassium nitrate,Water] | [Ammonia,Potassium,Potassium phosphate] | less promising [Acetic acid,Potassium nitrate,Potassium phosphate,Water] | [Ammonia,Potassium] | less promising [Acetic acid,Potassium,Potassium phosphate,Water] | [Ammonia,Potassium nitrate] | less promising [Water] | [Acetic acid,Ammonia,Potassium,Potassium nitrate,Potassium phosphate] | less promising [Potassium,Water] | [Acetic acid,Ammonia,Potassium nitrate,Potassium phosphate] | possible in principle [Potassium phosphate] | [Acetic acid,Ammonia,Potassium,Potassium nitrate,Water] | possible in principle [Potassium phosphate,Water] | [Acetic acid,Ammonia,Potassium,Potassium nitrate] | possible in principle [Potassium nitrate,Water] | [Acetic acid,Ammonia,Potassium,Potassium phosphate] | possible in principle [Potassium nitrate,Potassium phosphate,Water] | [Acetic acid,Ammonia,Potassium] | possible in principle [Potassium,Potassium phosphate,Water] | [Acetic acid,Ammonia,Potassium nitrate] | possible in principle [Potassium,Potassium nitrate,Water] | [Acetic acid,Ammonia,Potassium phosphate] | possible in principle [Potassium,Potassium nitrate,Potassium phosphate,Water] | [Acetic acid,Ammonia] | possible in principle [Potassium nitrate,Potassium phosphate] | [Acetic acid,Ammonia,Potassium,Water] | possible in principle [Potassium nitrate] | [Acetic acid,Ammonia,Potassium,Potassium phosphate,Water] | possible in principle [Potassium,Potassium phosphate] | [Acetic acid,Ammonia,Potassium nitrate,Water] | possible in principle [Potassium,Potassium nitrate,Potassium phosphate] | [Acetic acid,Ammonia,Water] | possible in principle [Potassium,Potassium nitrate] | [Acetic acid,Ammonia,Potassium phosphate,Water] | possible in principle [Potassium] | [Acetic acid,Ammonia,Potassium nitrate,Potassium phosphate,Water] | possible in principle [Acetic acid,Potassium,Potassium nitrate,Potassium phosph.] [Ammonia,Water] | possible in principle [Acetic acid,Potassium nitrate,Potassium phosphate] | [Ammonia,Potassium,Water] | possible in principle [Acetic acid,Potassium phosphate] | [Ammonia,Potassium,Potassium nitrate,Water] | possible in principle [Acetic acid,Potassium nitrate] | [Ammonia,Potassium,Potassium phosphate,Water] | possible in principle [Acetic acid,Potassium,Potassium phosphate] | [Ammonia,Potassium nitrate,Water] | possible in principle [Acetic acid,Potassium,Potassium nitrate] | [Ammonia,Potassium phosphate,Water] | possible in principle [Acetic acid,Potassium] | [Ammonia,Potassium nitrate,Potassium phosphate,Water] | possible in principle [Acetic acid] | [Ammonia,Potassium,Potassium nitrate,Potassium phosphate,Water] | possible in principle
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